高岭石/甘氨酸插层复合物的制备与表征

通过取代法成功地将甘氨酸插入到高岭石层间，制备出高岭石／甘氨酸插层复合物，XRD显示插层复合物1．0nm出现衍射峰，红外光谱表明甘氨酸分子中的N、O原子与高岭石片层间离子形成了氢键。     

高岭石/苯甲酰胺插层复合物的制备与表征

以高岭石／二甲亚砜作为前驱物,用熔融插层法成功制备了高岭石／苯甲酰胺插层复合物,产物用X射线粉晶衍射和Fourier变换红外光谱进行了表征。实验结果表明：高岭石／苯甲酰胺插层复合物中,高岭石的层间距扩张到1.428nm,插层率达到了82．5％;苯甲酰胺分子的氨基与高岭石的内表面羟基形成了氢键,苯甲酰胺分子可能以单分子层垂直排列于高岭石层间。高岭石／苯甲酰胺插层复合物在140～180℃的温度范围内,会发生苯甲酰胺的脱嵌过程。     

苯甲酰胺分子在高岭石层间的成键和取向

利用X射线粉末衍射和Fourier变换红外光谱实验分析了2种高岭石及其苯甲酰胺插层复合物的结构.结构表征与分析表明:复合物的层间距分别扩张到1.437 nm和1.444 nm,苯甲酰胺分子在高岭石层间均呈单分子竖直排列,但与层间表面的倾斜状况不同.在佛山高岭石/苯甲酰胺插层复合物中,氨基和羰基同时参于与内表面羟基的作用;而在苏州高岭石/苯甲酰胺插层复合物中,只有氨基与内表面羟基成键,且苯甲酰胺分子还部分嵌入高岭石的复三方空穴.     

置换插层制备高岭石--甲醇复合物的机理

分别以高岭石--二甲基亚砜插层复合物和高岭石--尿素插层复合物为前驱体,采用多次逐步置换插层方法制备高岭石--甲醇插层复合物。通过X射线衍射和红外光谱测定不同插层阶段产物的结构,对不同前驱体制备高岭石--甲醇插层复合物的置换插层机理进行了探讨。结果表明:前驱体不同,其置换过程行为不一样。以高岭石--二甲基亚砜插层复合物为前驱体,甲醇分子首先以分子状态进入层间,随着置换次数和时间的增长,逐渐以化学键结合于层间,表现为变化较大的层间距;以高岭石--尿素插层复合物为前驱体,甲醇分子直接以化学键结合于层间,表现为比较稳定的层间距。红外光谱研究表明甲醇分子主要与高岭石晶层中的内表面羟基发生作用,形成新的化学键接枝于高岭石层间。     

高岭石-氨基硅烷插层复合物的制备与表征

以高岭石-甲醇(K-M)复合物为前驱体,利用置换法于常温下制备了3种高岭石-氨基硅烷插层复合物。用X射线衍射、Fourier变换红外光谱仪、透射电子显微镜、热分析仪等对复合物进行了表征。结果表明:3种高岭石-氨基硅烷插层复合物的层间距均扩大至2nm以上,插层率都大于95%。3种氨基硅烷分子均和K-M前驱体的甲氧基共同存在于高岭石层间,均呈两层倾斜排列,倾斜程度不同。氨基硅烷的插入破坏了高岭石层间的氢键,加剧了高岭石自身结构中硅氧四面体片层与铝氧八面体片层之间的错位,使得复合物片层出现不同程度的卷曲变形。3种高岭石-氨基硅烷插层复合物的热分解过程均分三步进行:表面水的蒸发及层间甲氧基的脱嵌分解、插层剂氨基硅烷分子的脱嵌、高岭石脱羟基。     

高岭石--烷基胺插层复合物的制备与纳米卷的形成

以张家口高岭土、用二甲基亚砜、甲醇和不同烷基胺为原料,通过插层和置换反应,制备出了高岭石--不同烷基胺(一异丙胺、正丁胺、正己胺、十二胺)插层复合物,并对其结构和形貌进行了表征。结果表明:烷基胺以甲氧基嫁接的高岭石为前驱体进入高岭石层间,使高岭石层间距由0.71nm扩大至1.24～4.23nm。随烷基胺分子碳链的增长,相应的高岭石插层复合物层间距亦增大,结构稳定性增加。烷基胺的插层可使高岭石片层剥离卷曲形成直径为30～100nm、长度为250～2 000nm的纳米管。纳米管的形貌及产率与烷基胺分子结构有关:烷基胺分子碳链越长,纳米卷产率越大,形貌越完整、直径越均一。烷基胺插层进入高岭石层间,不仅极大地降低了高岭石晶层间氢键,而且为高岭石片层向管状卷曲提供了充分自由空间。     

高岭石-甲醇插层复合物的结构及热分解行为

采用多次置换插层法制得高岭石-甲醇插层复合物,用X射线衍射、傅里叶变换红外光谱、热重和差示扫描量热技术对产物的结构和热分解行为进行了表征.结果表明:甲醇插入到高岭石层间,高岭石层间距由0.71 nm扩大到0.93 nm,插层率为100％.插层复合物中,甲醇分别以与高岭石内表面范德华力结合、氢键键合及嵌入复三方孔穴三种形态存在.在加热过程中,插层复合物分三步分解.第一步分解发生于30～120℃,为层间范德华力结合的甲醇分子的脱嵌过程;第二步发生于120～350℃,是氢键键合的甲醇的脱嵌过程;第三步发生在400～ 600℃,对应于高岭石脱羟基和嵌入高岭石晶格内部的甲醇的脱嵌过程.计算得到复合物体系中高岭石与甲醇的分子摩尔比为1∶0.7,其中以范德华力结合、氢键键合和嵌入复三方孔穴的甲醇的摩尔比为5.2∶11.8∶1.     

季铵盐与烷基胺插层高岭石结构及其热动力学对比

采用X射线衍射、Fourier变换红外光谱及热分析等表征方法对高岭石/十二烷基三甲基氯化铵(Kaol-DTAC)及高岭石/十二胺(Kaol-DA)插层复合物的结构进行对比研究,并进一步研究了插层复合物的热动力学。结果表明:插层作用使高岭石在加热过程中脱羟基温度降低了10℃左右。由于插层分子DTAC与DA的结构差异,致使其在高岭石层间的排列方式存在差异。前者主要以呈90°夹角垂直于高岭石晶层面的方式单层排列,后者则以分子链与高岭石晶面呈39.9°夹角双层倾斜排列为主,且二者在高岭石层间排列方式的不同导致其结构稳定性存在差异。采用KAS法和Ozawa法对Kaol-DTAC和Kaol-DA插层复合物进行热力学分析并且分别计算其活化能。Kaol-DTAC的活化能为102.44 k J/mol,Kaol-DA的活化能为130.80 k J/mol,进一步说明DA比DTAC在高岭石层间更为稳定。     

高岭石/聚苯乙烯插层复合物碳热还原反应制备碳化硅晶须/氧化铝复相陶瓷粉体

以二甲基亚砜(dimethylsuIfox.de,DMSO)为插层剂制得高岭石/DMSO插层复合物,将苯乙烯单体与高岭石,DMSO插层复合物进行置换反应, 成功地将苯乙烯单体引入高岭石层间,层间苯乙烯在加热条件下聚合,制得高岭石/聚苯已烯捅层复合物.以高岭石/聚苯乙烯插层复合物为原料,在氩气保护气氛下,于1500℃碳热还原反应制备碳化硅晶须/氧化铝(SiCw/Al2O3)复相陶瓷粉体.结果表明:在高岭石/聚苯乙烯插层复合物中,高岭石 的层间距由0.717nm扩张到1.130nm,插层率接近100%.插层作用影响了层间羟基基团的振动,使其键合方式发生改变.X射线衍射和扫描电镜分 析表明:合成出SiCw/Al2O3复相陶瓷粉体中SiC和Al2O3为主品相,SiC呈晶须状,其直径≤200nm,长度≥3μm.     

阳离子对醋酸盐插层高岭石影响的研究

采用研磨法制备了高岭石/醋酸钠和高岭石/醋酸钾钠插层复合物,并用XRD、FI-IR、TG-DSC对插层复合物进行表征,探讨了阳离子不同对插层结果的影响.结果表明: K~+、Na~+的不同对插层结果有很大影响,与醋酸钾插层复合物只有一个1.365 nm衍射峰不同,醋酸钠插层复合物,出现了0.979 nm和0.765 nm两个衍射峰,醋酸盐分子在高岭石层间直立取向,阳离子和甲基可能进入到了复三方孔中.     

高岭石/苯甲酰胺插层复合物的制备和表征

在60℃下,高岭石与二甲基亚砜反应制备高岭石/二甲基亚砜插层复合物,使用X衍射分析、热分析、红外光谱分析对其进行表征。在140℃下,苯甲酰胺与高岭石/二甲基亚砜插层复合物反应4 d,得到高岭石/苯甲酰胺插层复合物,对其进行表征,然后与高岭石/二甲基亚砜插层复合物进行对比。结果表明：在没有二甲基亚砜作为前驱体的情况下,苯甲酰胺不能与高岭石直接进行反应;高岭石/苯甲酰胺插层复合物结构的稳定性好,是由于苯甲酰胺插层内羰基中的氧原子与高岭石层间表面上的铝硅酸盐形成氢键。     

Stability of kaolinite dispersions in the presence of sodium and aluminum ions

The stability of colloidal kaolinite dispersions in the presence of NaCl and AlCl₃ was studied by measuring turbidity, electrophoretic mobility and adsorption. The kaolinite particles coagulated at pH 2.5–3.5 and were dispersed at pH >4.5. These results well obeyed the classic DLVO theory if the mean zeta potential of the kaolinite particles in aqueous solutions was taken into account in the computation of potential energy of electrical double layer repulsion, which suggests that the kaolinite particles might coagulate in the same way as normal colloidal particles. The kaolinite particles in aqueous aluminum salt solution only coagulated at a medium AlCl₃ concentration, and formed a stable dispersion at a high salt concentration. This is caused by Stern-layer adsorption of hydrolyzed aluminum species, probably adsorbed on the kaolinite surfaces through hydrogen bonds between the hydroxyl groups of the aluminum species and the oxygen atoms on the kaolinite surfaces.     

松香树脂酸和甲醛的Prins加成反应研究

以对甲苯磺酸为催化剂,对含有多种树脂酸的松香和甲醛的Prins加成反应进行了系统研究,产物纯化后进行了FTIR1、HNMR、GC-MS检测。结果表明:在Prins反应过程中含共轭双键的树脂酸反应活性高,反应原料的转化率达78.97%;FTIR谱图表明产物中出现羟甲基吸收峰,1HNMR表明产物中松香环上烯碳上氢消失,出现了两个羟基氢。初步确认反应主要产物是由单羟甲基树脂酸、二羟甲基树脂酸、三羟甲基树脂酸组成,其质量分数分别是:17.316%、37.971%、19.353%;对反应机理进行了初步探讨。     

Original preasphaltenes and asphaltenes in coals

The preasphaltene (PA) and asphaltene (A) fractions from untreated coal show a direct relationship of PA/A (w/w) to the carbon content of coal. Their thermal stability was investigated by in-situ pyrolysis FTIR, and the results show that PA has higher thermal stability than A. By means of a vacuum FTIR method, five types of hydrogen bonds formed by hydroxyl groups were clearly observed in PA and A, i.e., OH-π, self-associated OH, OH–ether oxygen, cyclic OH groups, and OH–N. The self-associated OH and OH–ether oxygen are the two main hydrogen bonds. The insolubility of PA in benzene and A in hexane is determined by the hydrogen bond strengths of the acid/base fraction but is not strongly related to their structural parameters and molecular weight. The acid/base associated strength of preasphaltenes and asphaltenes is estimated to be within the following ranges, asphaltenes, <5.15 kJ/mol; preasphaltenes, 5.15–30.9 kJ/mol.     

不需预保护羟基的侧链亲水非离子水性聚氨酯的制备与性能

以酒石酸与聚乙二醇单甲醚(MPEG)为原料,在不需预保护酒石酸中羟基的情况下,经过酯化反应合成了酒石酸聚乙二醇单甲醚酯(TMPEG),以其为亲水单体通过预聚体法制备了一系列非离子型水性聚氨酯(TWPU)。通过1HNMR、FTIR、TGA、拉伸测试对TMPEG和TWPU进行了结构表征与性能测试。考察了亲水单体TMPEG质量分数对TWPU贮存稳定性、力学性能、吸水率的影响。结果表明：当TMPEG质量分数为24%（以TMPEG、聚己二酸-1,4-丁二醇酯二醇、异佛尔酮二异氰酸酯、三羟甲基丙烷、乙二胺反应合成的预聚体的总质量为基准,下同）时,TWPU乳液平均粒径为85nm,TWPU胶膜接触角为84°,拉伸强度为7.9MPa,断裂伸长率为768%。     

Development of ZrO2‐MgO nanocomposite powders by the modified sol‐gel method

The ZrO₂‐MgO nanocomposites were synthesized using a new sol‐gel method with sucrose and tartaric acid as a gel agent. The samples were characterized by thermal analysis (TG/DTA), X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FESEM), energy‐dispersive X‐ray mapping (EDX mapping), and Ultraviolet‐visible spectroscopy (UV‐vis). The results showed that the cubic phase of ZrO₂‐MgO was formed in the presence of both gel agents. The average particle size of the samples synthesized with sucrose was lower (30 nm) than that of tartaric acid (50 nm). Finally, the formation mechanism and the optical properties of zirconia‐magnesia have been discussed.     

Kinetics of dehydration–polymerization of aspartic acid and synthesis of polyaspartate catalyzed by potassium bisulfate

The dehydration–polymerization kinetics of DL ‐ and L ‐aspartic acid, either in the absence or presence of KHSO₄, from 323 to 573 K, was studied by thermogravimetric analysis (TGA), and the synthesis of polyaspartate through the polymerization of L ‐aspartic acid was investigated by a thin‐layer polymerization method. The TGA results revealed that the dehydration–polymerization of both type of aspartic acids proceeds in two steps: first, the loss of one water molecule through the reaction of an amino group of one aspartic acid molecule and a hydroxyl group of another aspartic acid molecule, forming amide bonds, and secondly, the loss of another water molecule through the amide hydrogen and another hydroxyl group, leading to the formation of a succinimide ring. The kinetic parameters of the extrapolated onset temperatures of dehydration—the first and the second maxima—were obtained by a method similar to that of Ozawa–Flynn–Wall. The kinetic results indicate that the dehydration of L ‐aspartic acid is slightly more difficult than for DL ‐aspartic acid, and that the presence of potassium bisulfate effectively catalyzes the dehydration–polymerization of aspartic acid. In the synthesis of polyaspartate, the product with a weight‐average molecular mass (M_w) of 5000 g mol^?1 was obtained in the absence of catalyst. However, in the presence of potassium bisulfate, the products obtained had M_ws of up to 7000 g mol^?1 Copyright © 2003 Society of Chemical Industry     

Study of interactions at water-soluble polymer/Ca(OH)2 or gibbsite interfaces by XPS

In an attempt to better understand interactions occuring at hydrated cement/organic polymer interfaces, the reaction mechanism and products formed at the interfaces between poly(acrylic acid), p(AA) or poly(acrylamide), p(AM), and Ca(OH)₂ or gibbsite, Al₂O₃·3H₂O, were explored using x-ray photoelectron spectroscopy (XPS). It was estimated that at p(AA)/Ca(OH)₂ interfaces, a Ca-complexed carboxylate interfacial reaction product was formed by an ionic reaction between the COOH in p(AA) and Ca²⁺ ions from Ca(OH)₂. A similar reaction product was formed at p(AM)/Ca(OH)₂ interfaces as a result of an inter-facial transformation of amide in p(AM) into carboxylic acid, caused by the alkali-catalyzed hydrolysis of the amide. The proton-accepting hydroxyl groups existing at the outermost surface sites of Al₂O₂·3H₂O react favorably with proton-donating COOH groups in p(AA). This acidbase interaction at the p(AA)/Al₂O₃·3H₂O joint formed hydrogen bonds. Whereas, when the p(AM) was applied on Al₂O₃·3H₂O surfaces, interfacial electrostatic bonds were formed through charge-transferring reaction mechanisms in which the charge density was transferred from the Al in Al₂O₃·3H₂O to the C=0 oxygen in p(AM).     

Preparation and Characterization of 4-Methoxy Cinnamoyl Glycerol

Glycerol was reacted with 4-methoxy cinnamic acid to prepare the corresponding 4-methoxy cinnamoyl glycerol. The reaction proceeded in toluene under reflux conditions with p-toluenesulfonic acid catalyst. Reaction of equimolar amounts of reactants produced the monoester in 20% yield after 2 h. The product was isolated and characterized by FTIR, mass spectrometry, and NMR techniques. Results of mass spectrometry and NMR experiments showed that the ester linkage formed between the carboxylic acid and the primary hydroxyl of glycerol. The ester displayed strong absorbance between 250 and 350 nm and shows potential as a UV filter in formulations where hydrophilic compounds are advantageous. Disclaimer The use of trade, firm, or corporation names in this publication is for the information and convenience of the reader. Such use does not constitute an official endorsement or approval by the United States Department of Agriculture or the Agricultural Research Service of any product or service to the exclusion of others that may be suitable.     

Preparation of LiNiVO4 nano-powder using tartaric acid as a complexing agent

LiNiVO₄ was prepared from Li₂CO₃, Ni(CH₃COO)₂·4H₂O and NH₄VO₃ using tartaric acid as a complexing agent with 1:1–1:4 mole ratios of metals:tartaric acid and subsequent calcination at 350–700 °C for 6–12 h. Inverse spinel LiNiVO₄ was detected using XRD. FTIR and Raman analyses revealed the presence of stretching band of VO₄ tetrahedrons. Only Ni, V and O were detected by EDX. The 1:4 mole ratio for the product with 450 °C calcination for 6 h analyzed by SEM, TEM and electron diffraction (ED) composes of LiNiVO₄ nano-powder with 10–30 nm in diameter.