Effect of neodymium stearate on cure and mechanical properties of epoxidized natural rubber

The effect of neodymium stearate (NdSt) on cure and mechanical properties of expoxidized natural rubber with 25 mol.% epoxida-tion (ENR25) was studied in the concentration range of 0 to 2 phr, and the relationship between structure and mechanical properties of ENR25 vulcanizates was also discussed. Neodymium sterate was synthesized by saponification of stearic acid with newly formed rare earth hydroxide in water medium, and the structure of NdSt was investigated by Fourier transform infrared spectroscopy (FTIR). Crosslinking den-sity of vulcanized natural rubber was studied by equilibrium swelling method. The results indicated that the interaction force between carbox-ylic ion of NdSt prepared in the lab and Nd ion was mainly ionic bond through FTIR analysis. NdSt could accelerate the vulcanization of ENR25 and influence the network structure of ENR25 vulcanizates. The incorporation of 1 phr NdSt for ENR25 vulcanizates showed the op-timal aging resistnce.     

Thermo-oxidative ageing behavior of cerium oxide/silicone rubber

Cerium oxide/silicon rubber was prepared via mechanical blending.Mechanical and frictional properties,as well as thermal stability after thermo-oxidative ageing were investigated in this rubber composite.3D surface profilometry,scanning electron microscopy(SEM) and thermogravimetry analysis(TGA) were used to study the friction surface characteristics,friction mechanism and thermal stability,respectively.Additionally,swelling experiments were carried out to investigate the variation of crosslinking density.After thermo-oxidative ageing,the tear strength of cerium oxide/silicon rubber decreases.However,in the early ageing stage,improvements in tensile strength,elongation at break,and frictional performance are caused by crosslinking density increments.Moreover,the addition of cerium oxide remarkably improves the re-cross linking degree during ageing process,which in turn decreases the number of holes on the friction surface and endows the silicon rubber with better mechanical and frictional properties,as well as thermo-oxidative ageing resistance.     

煤的氧化和热解反应的动力学研究

用热分析手段研究了不同煤化程度煤的氧化热解反应。结果表明,在空气中,煤在整个氧化热解过程中,可分为水分蒸发、吸氧增重、受热分解、燃烧与燃尽五个阶段。吸氧增重阶段的氧化反应为1级化学反应,受热分解阶段为1.5级的化学反应。求解出不同煤样在不同氧化阶段的平均表观活化能E和lnA的值,分析了煤氧化过程的特点与E和lnA值在不同氧化阶段的规律性,并用作图方法检验了所求氧化动力学参数的正确性。     

硬脂酸镧对LLDPE热氧化分解行为的影响

通过热失重和氧化诱导期方法研究了硬脂酸镧对LLDPE(线性低密度聚乙烯)热氧化分解行为的影响,在添加一定浓度的硬脂酸镧时,LLDPE的50%失重温度可大幅提高。研究表明,硬脂酸镧不能阻止LLDPE在热氧化分解温度较低阶段时的氧化反应,但可对高温阶段的断链反应有抑制作用,这可能是由硬脂酸镧对LLDPE氧化过程中产生的交联结构有稳定作用而造成的。硬脂酸镧和抗氧剂1010的复合使用对LLDPE热稳定性的提高存在加合效应,可使LLDPE的综合性能得到提高。     

Study on Kinetics of Natural Rubber Vulcanization by S/La（DiPDP）3

Kinetics of natural rubber （NR） vulcanization by lanthanum O, O＇-diisopropyldithiophosphate [ La（DiPDP）3 ] was studied. La（DiPDP）3 had remarkable accelerating effect on the vulcanization of NR. The rate constant k6 of the reaction that turned polysulphidic cross-links into the modified main chain was higher than that of desulfuration reaction of polysulfidic cross-links （k3 ）. The activation energies （Ea2, Ea3, and Ea6） of the formation, desulfuration, and decomposition of polysulfidic cross-links were 87.57,102.34, and 95.01 kJ · mol^-1, respectively. Activation energy （Eas） of the reaction that turned the cross-link precursors into the modified main chain was 82.67 kJ · mol^-1. It could be concluded that the proportion of polysulphidic cross-links was higher than mono- and di- sulphidic cross-links during induction and curing periods, mono- and di- sulphidic cross-links increased as curing temperature rose. In the temperature range of 140 - 160 ℃, the amounts of polysulphidic cross-links were similar. However, over 160℃, mono- and di- sulphidic cross-links increased rapidly. Moreover, cross-link density of the vulcanizates was determined from the equilibrium-swelling data. A chemical probe detected the concentration of polysulphidic cross-links of vulcanizates. The change trend of the results predicated from equation corresponded to that of the experimental results.     

Zn-Al-La hydrotalcite-like compounds as heating stabilizer in PVC resin

ZnAlLa-CO 3 layered double hydroxides (LDHs) with different Zn/Al/La molar ratios were prepared by the constant pH coprecipitation method. The synthetic materials were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), Brunauer-Emmett-Teller method (BET) and particle analysis. The results showed that the hydrotalcite-like materials had a layered structure. The ZnAlLa-CO 3 -LDHs as stabilizers were mixed with PVC resin. The tests of thermal aging, mass loss test and Congo red for the PVC composites were carried out at 180±1 oC, respectively. The results showed that ZnAlLa-CO 3 LDHs used as single thermal stabilizers could enhance both the long-term thermal stability and initial thermal stability of PVC, and 2.4 phr (parts per hundred PVC resin) ZnAlLa-CO 3 -LDHs with Zn/Al/La (molar ratio)=20/8/2 had a better stabilizing effect on PVC than others. Compared with single thermal stabilizers, the composite thermal stabilizers including 0.3 phr calcium stearate (CaSt 2 ), 0.4 phr β-diketone and 2.4 phr ZnAlLa-CO 3 -LDHs significantly enhanced the thermal stability of PVC sample. And rare earth ion could optimize the conformation of PVC and refrain the initiation of the thermal stability and the thermal stable time was over 220 min. The main reason could be concluded to the special structure of rare earth ion, which had longer atom radius and more coordination numbers. So the rare earth ion (RE δ+ ) could react with the labile chlorine atoms (Cl r- ) to form a stable coordinate complex.     

热剥离法制备含缺陷g-C3N4纳米片及光催化性能

以三聚氰胺为前驱体,采用热剥离法在不同温度制度下制备了g-C₃N₄纳米片,通过X射线衍射(XRD)、场发射扫描电镜(FESEM)、透射式电子显微镜(TEM)、紫外-可见漫反射(UV-Vis DRS)对其晶型结构、微观形貌、光吸收性能进行了表征。并以盐酸四环素(TC-HCl)和罗丹明B(RhB)为目标降解物,评价了材料的光催化活性。结果表明,当热剥离温度为550℃时,g-C₃N₄纳米片显示出最佳的降解性能。4 h对TC-HCl的降解效率为82.9%,2 h对RhB的降解效率为97%。这是由于,随着热剥离温度的升高,B-g-C₃N₄被逐渐剥离为g-C₃N₄纳米片,550℃剥离的纳米片厚度为9.346 nm,减少的厚度显著增大了光催化材料的比表面积。并且由于氧气的刻蚀,在g-C₃N₄纳米片表面会产生大量缺陷,为降解物提供活性位点。随着温度升高,g-C₃N₄纳米片的禁带宽度由2.47 eV拓宽至2.65 eV,抑制了光生电子-空穴的复合。其中还原电位由-1.37 eV移动至-1.46 eV,为光催化材料提供了更强的还原能力,氧化电位由1.10 eV移动至1.19 eV,为光催化材料提供了更强的氧化能力。     

Effects of Moisture on Pyrolysis of Polypropylene

The thermal degradation kinetics of polypropylene (PP) in steam was investigated with a thermal gravimetric analysis (TGA) reaction system. The experiments were carried out in the 500–800 K temperature range at various constant heating rates of 1, 2, and 5 K∕min. The partial pressure of steam in the system was adjusted to 0.24 atm, which is seen in most municipal solid waste (MSW) incinerators in Taiwan. The results indicated that the water molecule significantly enhanced the thermal degradation rate of PP. The corresponding activation energy, preexponential factor, and reaction order were determined. It was found that thermal degradation of PP in steam can be adequately described by an overall rate equation.     

Novel lanthanide coordination polymers based on mixed N,O-donor ligands and their visible-light-driven photocatalytic performance

In the present work,we prepared three isostructural lanthanide(Ln) coordination polymers(CPs).namely [Ln(Hhpc)(phen)(NO₃)](Ln=Gd(1),La(2),Y(3),H₃ hpc=5-hydroxy-1 H-pyrazole-3-carboxyIic acid,phen=1,10-phenanthroline) by hydrothermal method.Their structures were characterized by single crystal X-ray diffraction,Fourier transform infrared spectrum,elemental analysis,powder X-ray diffraction and thermal gravimetric analysis.CPs 1-3 are isostrutural and exhibit two-dimensional(...     

微波活化对过硫酸盐降解典型选矿药剂苯胺黑药的影响

采用微波活化过硫酸盐的高级氧化技术处理选矿废水中残留的典型选矿药剂苯胺黑药,研究了反应条件、微波功率、过硫酸盐浓度、反应溶液初始pH、金属离子Fe2+和Cu2+、水中常见阴离子（Cl-、HCO₃-、NO₃-和SiO₃2-）等变化因素对苯胺黑药降解效果的影响,并对反应产物和降解机理进行了分析。结果表明:微波活化过硫酸盐能够有效降解苯胺黑药;随着微波功率和过硫酸盐投加浓度的增加,苯胺黑药的降解率也随之升高;当溶液初始pH=3时苯胺黑药的降解效果最好;较低浓度金属离子Fe2+和Cu2+的添加可以有效辅助活化过硫酸盐,促进反应体系中苯胺黑药的降解;水中常见阴离子Cl-、HCO₃-、NO₃-和SiO₃2-对苯胺黑药的降解均为抑制效果;在反应体系中氧化降解苯胺黑药的过程中微波热效应为主要作用,而且在反应过程中SO₄-·起主导作用;反应180 min后,苯胺黑药的矿化效率为45.27%;通过液相色谱检测,推测苯胺黑药经微波活化过硫酸盐体系处理后先被氧化为邻二苯酚,再进一步被氧化降解为其他小分子物质、二氧化碳和水。      

Synthesis of lanthanum ricinoleate and its effect on thermal stability and mechanical properties in PVC

The lanthanum ricinoleate（abbreviated as Lari3） of rare earth heat stabilizer was synthesized by the reaction of ricinoleic acid, lanthanum nitrate and sodium hydroxide. The IR and fluorescence spectra methods confirmed the structure of the product. The thermal stability of PVC in the presence of Lari3 was studied by the Congo method and using TG analysis. The results showed that Lari3 could be used as a thermal stabilizer for PVC. When the ratio of Lari3/pentaerythritol was 3：1, the complex exhibited better synergistic effect. Incorporation of Lari3 to PVC resulted in a marked increase of maximum and onset degradation temperature as well as elongation and impact strength of PVC. Lari3 might replace the labile chlorine atoms to interrupt the formation of conjugated double bonds in PVC chains and act as HCl scavenger to restrain the self-catalyticdehydrochlorination.     

含油污泥铁组元的高效分离及其制备复合纳米催化剂

钢铁含油污泥是轧钢工艺过程中产生的一种危险性废物(HW08),其资源化利用难度大。采用碱洗法对含油污泥进行分离处理,并将分离所得的铁组元制备成复合纳米催化剂。碱洗脱油研究表明,当温度为80 ℃、碱溶液/含油污泥的质量比为1∶2、碱浓度为15%、反应时间为1 h时,含油污泥的脱油率达到94.14%,并得到铁质量分数为62.49%的固相。将脱油后的含铁固相通过共沉淀方法,得到粒径约为8 nm的磁性纳米Fe₃O₄,并与硅藻土通过溶剂热法制备了复合纳米催化剂,应用于罗丹明B催化降解,其降解率达到99.53%。本方法实现了对含油污泥的无害化处理和资源化利用。     

改性钢渣/橡胶复合材料导热性能及耐久性研究

利用自制钢渣助磨改性剂处理热闷渣、电炉渣与风淬渣,将改性后的钢渣微粉与炭黑、橡胶基体等复合形成改性钢渣/橡胶复合材料.采用导热系数仪,测定三种改性钢渣/橡胶复合材料热氧老化1、3、5、7、9、11 d的导热系数;根据Young’s与Flory方程计算出三种改性钢渣/橡胶复合材料热氧老化前后的接触角θ与交联密度;采用热重分析仪(TGA)、场发射扫描电镜(SEM)进行热氧老化前后分析.未热氧老化时,在三种改性钢渣/橡胶复合材料中改性电炉钢渣/橡胶复合材料的导热系数最低,为0.187 W·m^-1·K^-1,是因为改性电炉渣粒中位径(d₅₀)最小,即3.49μm,形成更致密的胶裹渣结构,不易形成导热通路,使其导热系数降低.热氧老化时,破坏胶裹渣结构,改性电炉渣/橡胶复合材料形成的孔隙大,分散性最好,降低界面热阻,更易形成导热通路,使其导热系数最高.热氧老化后,橡胶复合材料表面粗糙度变大且存在较长裂纹与较深孔洞,导致橡胶复合材料吸水性增加,接触角下降.由于改性热闷渣的粒径最大,在热作用下氧气更容易进入橡胶复合材料中与橡胶分子链(双键...     

微波辅助热解制备铁氮/生物炭及其芬顿催化活性

以油菜秸秆为生物质原料,混入比例不同的硼酸(m(硼酸)∶m(秸秆)=1∶1和m(硼酸)∶m(秸秆)=2∶1),通过微波热解结合水热法制备铁氮/生物炭。采用XRD、SEM等技术对材料形貌及结构进行表征分析,研究不同硼酸比例制备的生物炭之间的性质差异。通过控制变量法对比分析不同H₂O₂浓度、环境温度下生物炭芬顿体系降解50 mg/L亚甲基蓝的降解效率,结果表明∶通过使用m(硼酸)∶m (秸秆)=2∶1混合进行热解的生物炭在各反应条件下的芬顿体系降解亚甲基蓝性能均优于使用m(硼酸)∶m(秸秆)=1∶1混合热解的生物炭。在25℃、pH=3的条件下,降解亚甲基蓝溶液的较优H₂O₂浓度为5 mmol/L;随着反应温度的升高,亚甲基蓝的降解效率逐步提高。     

偏钒酸钾-硝酸铊纳米复合粉体的制备及其光催化降解苏丹红Ⅱ号的研究

采用硝酸铊、偏钒酸钾、亚硫酸钠、二氧化锰为反应原料,经过水热法合成出了偏钒酸钾-硝酸铊纳米复合粉体,活化该复合粉体后考察其对苏丹红Ⅱ号的降解能力,并对粉体进行SEM、XRD、XPS表征。实验结果表明,偏钒酸钾掺杂量为2.5%(质量分数)的复合粉体具有最强的催化活性,25 mg的偏钒酸钾-硝酸铊纳米复合粉体可对200 m L浓度为1×10~(-3)mol/L的苏丹红溶液有效降解。     

Preparation and performance research of Ce-TiO2/KL ball photocatalysts

The Ce-TiO2/KL （diatomite） ball photocatalyst was prepared and characterized based on the pretreated diatomite. The resuits showed that comparing with the crude diatomite, proper pretreatment could significantly improve its SiO2 purity and specific surface area. The surface of diatomite was clear with uniform pore structure and big pore size. With diatomite ball as carder, the supported Ce-TiO2/KL ball photocatalyst was prepared by sol-gel method. The photocatalytic performances of the supported Ce-TiO2/ KL ball and Ce-TiO2/KL powder photocatalysts under various preparation conditions were studied in view of photocatalytic degrada- tion rate of Rhodamine B （Rh B） solution. The degradation rate of the ball photocatalysts for Rh B reached 94.6% and could be reused for many times, which showed much better photocatalytic performance and stability than powder photocatalysts.     

Photocatalytic degradation of pesticide residues with RE³⁺-doped nano-TiO₂

The photocatalytic degradation effects of carbofuran solution under concentration of 0.2,0.4,0.8 g/L Re3+-doped nano-TiO2 were studied.The highest degradation rate of 54.89% was obtained after 4 h degradation when the concentration of nano-TiO2 was 0.4 g/L.Then field trials of photocatalytic degradation with suspension nano-TiO2 were conducted.The photocatalytic degradation effect of organic phosphorus and carbamate pesticides in tomato leaves and soil with different concentratio catalyst(0,0.2,0.4,0.6,0.8 g/L) were studied.The results showed that nano-TiO2 could significantly increase photocatalytic degradation rate of pesticide residues in tomato leaves and soil.Pesticide residues degradation rate could be increased by 20%-30% on the tomato leaves and 15%-20% in soil,and the best concentration of photocatalytic degradation was 0.2-0.4 g/L.     

Cerium dioxide as a new reactive sorbent for fast degradation of parathion methyl and some other organophosphates

Cerium dioxide was used for the first time as reactive sorbent for the degradation of the organophosphate pesticides parathion methyl,chlorpyrifos,dichlofenthion,fenchlorphos,and prothiofos,as well as of some chemical warfare agents—nerve gases soman and O-ethyl S-[2-(diisopropylamino) ethyl] methylphosphonothioate(VX).CeO2 specimens were prepared by calcination of basic cerous carbonate obtained by precipitation from an aqueous solution.The CeO2 samples containing certain amounts(1 wt.%–5 wt.%) of the neighboring lanthanides(La,Pr,Nd) were prepared in a similar way from pure lanthanide salts.It was shown that ceria accelerated markedly the decomposition of parathion methyl causing the cleavage of the P-O-aryl bond in the pesticide molecule.A similar reaction mechanism was proposed for the degradation of other organophosphate pesticides and nerve agents.The degradation times(reaction half-times) were in an order of minutes in the presence of CeO2,compared to hours or days under common environmental conditions.The reaction in suitable organic solvents allowed conversions of about 90% for parathion methyl loading of 20 mg pesticide/g CeO2 within 2 h with a reactant half-life in the order of 0.1 min.The key parameter governing the degradation efficiency of CeO2 was the temperature during calcination.At optimum calcination temperature(about 773.15 K),the produced ceria retained a sufficiently high surface area,and attained an optimum degree of crystallinity(related to a number of crystal defects,and thus potential reactive sites).The presence of other lanthanides somewhat decreased the reaction rate,but this effect was not detrimental and permitted the possible use of chemically impure ceria as a reactive sorbent.A fast organophosphate degradation was demonstrated not only in non-polar solvents(such as heptane),but also in polar aprotic solvents(acetonitrile,acetone) that are miscible with water.This opens new possibilities for designing more versatile decontamination strategies.The cleavage of phosphate ester bonds is of a great importance not only for the degradation of dangerous chemicals(chemical weapons,pesticides),but also for interactions of ceria(especially the nano-sized one) in biologically relevant systems.     

钾、钠对焦炭劣化作用

为了研究碱金属钾、钠对焦炭劣化作用的区别,首先将焦炭置于不同含量的钾、钠气氛下进行吸附实验,然后对吸附碱金属后的焦炭进行扫描电镜观察、能谱及X射线衍射分析和热态性能测试.由于钠更加容易以表面吸附的形式覆盖在焦炭表面,所以在碱蒸气质量比相同的气氛下,钠的吸附量要高于钾.表面吸附的碱金属对焦炭溶损反应有阻碍作用.在相同吸附量情况下,吸附钾后的焦炭中与碳化学结合的钾居多,反应性更高.另外,钾金属本身对焦炭破坏作用就很大,钾原子会插入碳层引起微晶多维膨胀,使焦炭微观组织产生破裂,并且这些新生的裂纹导致吸附钾焦炭与吸附钠焦炭在溶损方式上的不同.     

Synthesis and characterization of calcium and manganese-doped rare earth oxide La_(1-x)Ca_xFe_(0.9)Mn_(0.1)O_(3-δ) for cathode material in IT-SOFC

In order to develop novel cathode materials with high performance for intermediate temperature SOFC(IT-SOFC),Ca and Mn doped rare earth oxides La1-xCaxFe0.9Mn0.1O3-δ(x=0.1,0.3 and 0.5,denoted as LCFM9191,LCFM7391 and LCFM5591) were synthesized by solid state reaction(SSR) method.The formation process,phase structure and microstructure of the synthesized samples were characterized using thermogravimetry/differential scanning calorimetry(TG/DSC),X-ray diffraction(XRD) and scanning electron microscopy(SEM).The thermal expansion coefficients(TEC) of the samples were analyzed at 100-900 oC by thermal dilatometry.The electrical conductivities of the samples were measured with direct current(DC) four-terminal method from 300 to 850 oC.The results indicated that the samples(x=0.1 and 0.3) exhibited a single phase with orthorhombic and cubic perovskite structure,respectively after being sintered at 1200 oC for 3 h.The electrical conductivity of the samples increased with temperature up to a maximum value,and then decreased.The small polaron hopping was regarded as the conducting mechanism for synthesized samples at T≤600 oC.The negative temperature dependence occurring at higher temperature was due to the creation of oxygen vacancies for charge balance.LCFM7391 had higher mixed conductivity(>100 S/cm) at intermediate temperature and could meet the demand of cathode material for IT-SOFC.In addition,the average TECs of LCFM9191 and LCFM7391 were 11.9×10-6 and 13.1×10-6 K-1,respectively,which had good thermal match to the common electrolytes.