风化煤腐植酸与Ca(H2PO4)2相互作用机理的研究

采用化学法及ＩＲ、ＸＲＤ、ＸＰＳ等综合解析手段,研究了风化煤腐植酸（ＨＡ）、腐植酸钾（ＨＡ－Ｋ）与磷酸一钙「Ｃａ（Ｈ２ＰＯ４）２」之间的反应特征,探讨了二者的反应机理。结果表明,磷酸一钙与ＨＡ基本未发生反应,而与ＨＡ－Ｋ反应后生成ＫＨ２ＰＯ４以及ＨＡ与ＣａＨＰＯ４的有机－无机复合物,但该复合物不太稳定,在水溶液中易水解生成腐植酸钙（ＨＡ－Ｃａ）和Ｃａ（Ｈ２ＰＯ４）２。本研究将为研制以煤炭腐植酸为基     

混合微乳液的增敏作用研究：Cd（Ⅱ）—5—Br—PADAP的分光光度测定

研究了在Ｏ／Ｗ混合微乳液ＳＤＳ－ＯＰ／ｎＣ４Ｈ９ＯＨ／ｎ－Ｃ７Ｈ１６／Ｈ２Ｏ介质中，Ｃｄ（Ⅱ）－５－Ｂｒ－ＰＡＤＡＰ的显色反应。结果表明显色反应的灵敏度较单一的ＳＤＳ微乳液，单一的ＯＰ的微乳液，混合ＳＤＳ－ＯＰ胶束的介质中，具有更好的增敏作用和稳定性，Ｃｄ浓度在０－５μｇ／１００ｍＬ范围内符合比尔定律。方法用于废水和环境水样中微量Ｃｄ的测定，结果满意。     

钙矾石吸附水的模型及等温式

钙矾石３ＣａＯ·Ａｌ２Ｏ３·３ＣａＳＯ４·３２Ｈ２Ｏ是水泥熟料水化的重要产物．它易被空气中的ＣＯ２ 分解,常温下的分解反应为３ＣａＯ·Ａｌ２Ｏ３·３ＣａＳＯ４·３２Ｈ２Ｏ ３ＣＯ２ →３ＣａＣＯ３ Ａｌ２Ｏ３·ｘＨ２Ｏ ３（ＣａＳＯ４·２Ｈ２Ｏ） （２６ -ｘ）Ｈ２Ｏ分解机理［１ ,２］是：Ｈ２Ｏ先吸附在钙矾石表面的活性中心上,吸附态水再吸收ＣＯ２ 成为Ｈ２ＣＯ３ ,然后碳酸与钙矾石反应,实现碳化（即分解）．其分解速率［３］为ｖ＝ｋｐｃｏ２ ｐＨ２ｏ（１）可见水的吸附是钙矾石碳化分解的关键步骤,因此探讨…     

LASER-ENHANCED ELECTROCHEMICAL DOPING OF POLY (N-VINYLCARBAZOLE)

ＬＡＳＥＲ－ＥＮＨＡＮＣＥＤ　ＥＬＥＣＴＲＯＣＨＥＭＩＣＡＬ　ＤＯＰＩＮＧ　ＯＦ　ＰＯＬＹ　（Ｎ－ＶＩＮＹＬＣＡＲＢＡＺＯＬＥ）ＬＡＳＥＲ－ＥＮＨＡＮＣＥＤＥＬＥＣＴＲＯＣＨＥＭＩＣＡＬＤＯＰＩＮＧＯＦＰＯＬＹ（Ｎ－ＶＩＮＹＬＣＡＲＢＡＺＯＬＥ）Ｙａ...     

SYNTHESIS AND ~（183）W NMR CHARACTERIZATION OF P_4W_（30）Al_4（H_2O）_2O_（112）~（20－） HETEROPOLYANION

ＳＹＮＴＨＥＳＩＳ　ＡＮＤ　~（１８３）Ｗ　ＮＭＲ　ＣＨＡＲＡＣＴＥＲＩＺＡＴＩＯＮ　ＯＦ　Ｐ_４Ｗ_（３０）Ａｌ_４（Ｈ_２Ｏ）_２Ｏ_（１１２）~（２０－）　ＨＥＴＥＲＯＰＯＬＹＡＮＩＯＮＳＹＮＴＨＥＳＩＳＡＮＤ~（１８３）ＷＮＭＲＣＨＡＲＡＣＴＥＲＩＺ?..     

DIRECT ELECTROCHEMICAL SYNTHESIS AND CHARACTERIZATION OF SAMARIUM （Ⅲ） COMPLEX WITH 2－HYDROXY－2， 4， 6－CYCLOHEPTATRIENONE （TROPOLONE）

ＤＩＲＥＣＴ ＥＬＥＣＴＲＯＣＨＥＭＩＣＡＬ ＳＹＮＴＨＥＳＩＳ ＡＮＤ ＣＨＡＲＡＣＴＥＲＩＺＡＴＩＯＮ ＯＦ ＳＡＭＡＲＩＵＭ （Ⅲ） ＣＯＭＰＬＥＸ ＷＩＴＨ ２－ＨＹＤＲＯＸＹ－２，４，６－ＣＹＣＬＯＨＥＰＴＡＴＲＩＥＮＯＮＥ （ＴＲＯＰＯＬ...     

APPLICATIONS OF ULTRASONICALLY DISPERSED POTASSIUM（UDP）PART 4：REDUCTIVE COUPLING OF CHALCONES IN THE PRESENCE OF UDP，COMMENTS ON THE MECHANISM OF ALKALIMETAL REDUCTION OF α，β－UNSATURATED ENONES

ＡＰＰＬＩＣＡＴＩＯＮＳＯＦＵＬＴＲＡＳＯＮＩＣＡＬＬＹＤＩＳＰＥＲＳＥＤＰＯＴＡＳＳＩＵＭ（ＵＤＰ）ＰＡＲＴ４：ＲＥＤＵＣＴＩＶＥＣＯＵＰＬＩＮＧＯＦＣＨＡＬＣＯＮＥＳＩＮＴＨＥＰＲＥＳＥＮＣＥＯＦＵＤＰ，ＣＯＭＭＥＮＴＳＯＮＴＨＥＭＥＣＨＡＮＩＳ...     

含膦,氮配体的混合膦酸锆—钯催化剂的研制

用氯化二苯基膦为膦化试剂,首次对多乙烯多胺乙基膦酸－磷酸氢锆Ｚｒ（ＨＰＯ４）１．３５（Ｏ２ＰＣＨ２ＣＨ２（ＮＨＣＨ２ＣＨ２）ｍＮＨ２）０．６５·Ｈ２Ｏ（ＺＰ－ＰＥＰＡＥＰＡ,ｎ＝０,１,２,３,４）载体表面进行二苯基膦化,合成了一类含膦氮配体的新型混合膦酸锆载体及负载钯催化剂。研究了有机膦酸侧链不同链长和Ｐｈ２ＰＣｌ用量对配体载体制备的影响,并用ＩＲ,ＴＧ,ＤＴＧ,ＤＴＡ对这类载体及催化剂进行表征     

SYNTHESIS AND CHARACTERIZATION OF NEIV PICKET FENCE CROWN－PORPHYRIN AND ITS Zn（Ⅱ），Fe（Ⅲ） COMIPLEXES

ＳＹＮＴＨＥＳＩＳＡＮＤＣＨＡＲＡＣＴＥＲＩＺＡＴＩＯＮＯＦＮＥＩＶＰＩＣＫＥＴＦＥＮＣＥＣＲＯＷＮ－ＰＯＲＰＨＹＲＩＮＡＮＤＩＴＳＺｎ（Ⅱ），Ｆｅ（Ⅲ）ＣＯＭＩＰＬＥＸＥＳ￥ＹａｎｇｄｅＷＵ，ＦａＣｈｅｎｇＱＩＡＮ，ＬｉａｎＦａｎｇＳＨＥＮａ（Ｄｅ...     

SYNTHESES， CHARACTERIZATION AND CATALYSIS OF （dppe）Rh（μ－CO）_2M（CO）_3（M＝CR，Mo，W） CARBONYL COMPOUNDS

ＳＹＮＴＨＥＳＥＳ，ＣＨＡＲＡＣＴＥＲＩＺＡＴＩＯＮ ＡＮＤ ＣＡＴＡＬＹＳＩＳ ＯＦ （ｄｐｐｅ）Ｒｈ（μ－ＣＯ）_２Ｍ（ＣＯ）_３（Ｍ＝ＣＲ，Ｍｏ，ｗ）ＣＡＲＢＯＮＹＬ ＣＯＭＰＯＵＮＤＳ￥ＣｈａｎｇＰｉｎｇＳＨＡＯ；ＪａｉｅＹｕＷＡＮＧ；ＸｉｕＺ...     

三相相转移催化法制备二氧化双环戊二烯

以氯甲基化大孔聚苯乙烯-二乙烯基苯交联树脂（PS）接枝N-苄基-N,N-二甲基十二烷基季铵磷钨杂多酸盐为三相相转移催化剂,质量分数为50%的工业双氧水为氧化剂,制备了二氧化双环戊二烯（DCPDDO）。 采用FTIR和¹H NMR对产物进行表征。 考察了溶剂和催化剂用量、物料摩尔比、反应温度和时间对环氧化反应的影响。 采用正交试验法获得的最佳反应条件为（以0.05 mol双环戊二烯（DCPD）计）：1,2-二氯乙烷18 mL,催化剂2.25 g,n(DCPD)∶n(H₂O₂)=1∶2.75,反应温度60 ℃,反应时间12 h。 在此条件下,DCPDDO的收率可达89%以上,催化剂回收方便且重复使用7次未见活性明显降低。     

Energy-efficient manufacturing of polymers with tunable mechanical properties by frontal ring-opening metathesis polymerization

Frontal polymerization (FP) is a process in which the heat generated by the self-reaction transforms monomers to cured polymers. Here, in order to improve the flexibility of polydicyclopentadiene, comonomers (norbornene-terminated polyether, ND-230,400,2000) are designed and synthesized, which can copolymerize with dicyclopentadiene (DCPD) by FP. The polymers (ND) prepared by ND-2000 and DCPD have tunable mechanical properties, from thermosets to elastomers. Specifically, the breaking elongation of the polymers can be varied 69-fold, from 6.1% to 423.4% by controlling the proportion of ND-2000. Among them, ND polymer with 50 wt% ND-2000 has good elastic behavior without yield. And, the reaction mixture solutions of DCPD and ND-2000 have the characteristics of controllable gel time and shear thinning, which make it have the potential of application in additive manufacturing.     

Study on the oligomerization of cyclopentadiene and dicyclopentadiene to tricyclopentadiene through diels-alder reaction

Summary The oligomerization of cyclopentadiene (CPD) and its dimer, dicyclopentadiene (DCPD), to tricyclopentadiene (TCPD) through Diels-Alder reaction at temperatures between 120 and 150°C was investigated. The results show that reaction temperature, pressure and solvent influence the product yield; at 150°C up to 50% yield of TCPD was obtained in the absence of solvents. The ratios of isomers A to B in the product can be adjusted by using different solvents. The kinetics indicate that the rate is more sensitive to the concentration of CPD than to that of DCPD.     

Evaluating cement hydration by non-conventional DTA; An Application to Waste Solidification

This paper presents a method to study cement hydration at ambient temperatures by using a micro processed non-conventional differential thermal analysis (DTA) system, which was used to evaluate the solidification/stabilization process of tannery wastes produced in the leather industry. The DTA curves of pastes composed by slag cement, Wyoming bentonite and waste are obtained in real time and used to analyze the heat effects of the reactions during the first 24 h of hydration. By applying a deconvolution method to separate the overlapped DTA peaks, the energy released in the several hydration stages may be estimated and consequently, the effects of each component on the solidification process. The highest separated DTA peak occurs during the several early stages of cement hydration and is due mainly to tricalcium silicate hydration. Very good correlation shows that the greater is the waste content in the paste composition, the higher is its effect on the rates of reactions occurring during the induction (dormant) period of cement hydration. The presence of bentonite used as a solidification additive in the stabilization process has a similar but less dramatic effect on the dormant period. This revised version was published online in July 2006 with corrections to the Cover Date.     

添加磷酸氢钙对硅酸三钙骨水泥性能的影响

本文将磷酸氢钙(CaHPO₄·2H₂O,DCPD)添加到硅酸三钙(Ca₃SiO₅,C₃S)骨水泥中,采用X射线衍射(XRD),扫描电镜(SEM),万能力学测试机等手段对不同添加量的骨水泥进行表征,考察添加DCPD对硅酸三钙骨水泥性能的影响。实验表明,C₃S材料中添加10% DCPD有着优于单纯C₃S骨水泥的水化性能,骨水泥的初凝时间从92 min缩短到80 min;添加20%~30% DCPD能提高材料的短期力学强度,可以实现其短期抗压强度的优化;添加30%~40% DCPD的材料有着优良的生物活性与适中的可降解性能。结果表明,通过添加DCPD优化C₃S水泥的性能,对各种不同性能具有DCPD添加量的依赖性。通过进一步优化DCPD添加量,将可能获得优良的生物活性骨缺陷填充材料。     

Hydration and Hardening of Apatitic Cement

Abstract

Hydroxyapatite (HAp) with the general formula Ca₁₀ z(HPO₄)z (PO₄) 6-z (OH) a-z · nH₂O has become of particular interest as a bio-restorative material having good compatibility with living hard tissues. In this work, hydration and hardening properties of water-setting apatitic cements were presented. Ca₃(PO₄)2 with the formd α (α-TCP) itself was an apatitic cement which could hydrate and harden alone, and formed HAp or Ca₈H₂ (PO₄) 6 · 5H₂O (OCP). Other apatitic cements were prepared by mixing at least two compounds selected from Ca HPO₄ · 2H₂O (DCPD), α-TCP, Ca₄(PO₄)aO (TeCP) and CaCO₃. The hydraulic reaction of α-TCP was accelerated by using water-soluble additives such as NaCl, NH₄Cl, NH₄ -citrate, etc. Another way for the acceleration was the addition of DCPD. The combination α-TCP/DCPD was developed with the expectation of the reaction α-TCP + DCPD + H₂O → 1/2 OCP. Hydraulic reactions of combinations TeCP/DCPD (Brown and Chow, 1983) and DCPD/CaCO₃ were also investigated. Various setting times above 4 min were obtained at 37–40°C by using different additives and combinations. The setting and hardening was considered to be due to the entanglement of HAp or OCP microcrystals formed on original powder particles. The resulting porously hardened bodies had porosities of 46 –80%, compressive strenghts of 2–30MPa, diametral tensile strengths of 0.1–3.5MPa. These apatitic cement pastes showed different DSC characteristics;d-TCP: exothexmic peak at 70–105°C, α-TCP/DCPD:two exo. and two endothermic peaks in the range of 40 to 120°C, TeCP/DCPD:two exothermic peaks in the range of 30 to 80°C, and DCPD/CaCO₃:endothermic peak at 70–100 °C.     

低压化成铝箔磷酸处理的研究与应用

对铝电解电容器低压化成箔作表面磷酸处理,研究了磷酸浓度、温度和作用时间对铝箔比容和耐水合升压时间的影响,优化最佳工艺条件,明显提高了铝电解电容器低压化成箔的性能,并应用于生产线.     

双环戊二烯苯酚树脂的合成新工艺

以双环戊二烯（DCPD）和苯酚为原料,甲磺酸为催化剂,合成了双环戊二烯苯酚树脂。适宜工艺条件:苯酚与DCPD摩尔比为5、反应温度120 ℃、反应时间5 h、催化剂质量分数为1.5%,收率89%。所得的双环戊二烯苯酚树脂（DPR）经催化加氢法在H2气压力1.5 MPa、催化剂Pd/Al2O3用量为原料质量分数的0.5%、反应温度80 ℃条件下对树脂进行脱色处理。 得到浅黄色双环戊二烯苯酚树脂,收率89%,经IR和1H NMR表征分析其为目的产物,产物指标达到国际同类产品的质量标准。     

Swelling effects in cross-linked polymers by thermogravimetry

A Brazilian coal power plant generates a waste composed by the fly and bottom ashes produced from coal combustion and by a spent sulfated lime generated after SO₂ capture from combustion gases. This work presents a study of the early stages of the hydration of composites formed by this waste and a type II Portland cement, which will be used for CO₂ capture. The cement substitution degrees in the evaluated composites were 10, 20, 30 and 40%, and the effect of the coal power unit waste on the hydration reaction was analyzed on real time by NCDTA, during the first 40 h of hydration. The results show that the higher is the substitution degree, the higher is the retarding effect on the cement hydration process. Actually, by respective thermogravimetric (TG) and derivative thermogravimetric (DTG) analysis on initial cement mass basis, this effect is caused by double exchange reactions among Ca and Mg components of the waste, during the first 4 h of hydration, which promote a much higher exothermic effect in the NCDTA curve, simultaneously to respective induction periods. The pozzolanic reactions, due to the presence of the waste silica and alumina containing amorphous phases, consume part of the original Ca(OH)₂ content existent in the waste in the case of 30 and 40% substituted pastes, and also from part of the Ca(OH)₂ produced in cement hydration reactions, in the case of the 10 and 20% substituted pastes.     

Pozzolanic properties of a residual FCC catalyst during the early stages of cement hydration

The catalyst used in fluidized catalytic cracking (FCC) units of refineries after several recovery cycles in regeneration units, reduces its activity and it is partially substituted by new catalyst in the process. As it has a high silicon and aluminum oxides content, the pozzolanic properties of a Brazilian FCC spent residual catalyst, used in different substitution degrees to cement, were evaluated by three thermal analysis techniques during the early stages of hydration of a type II Portland cement. NCDTA curves show in real time that the residual catalyst, accelerates the stages of cement hydration. TG and DSC curves of respective pastes after 24 h of hydration evidence the pozzolanic activity of the waste, respectively, by the lower water mass loss during the dehydroxylation of the residual calcium hydroxide and by the lower dehydroxylation endothermal effect. Within the analyzed period, the higher is the cement substitution degree, the higher is the pozzolanic activity of the residual catalyst.