铈元素对H13模具钢等向性能影响的研究

对H13热作模具钢进行了Ce元素处理,配合等温球化热处理工艺,开展了对H13钢等向性能的研究。采用JBN-300摆锤式冲击试验机对冲击韧性进行了检测,采用MICROHARDNESS TESTER HV-1000显微硬度仪对显微硬度进行了检测。结果表明:随Ce含量的增加,H13钢的横、纵向力学性能呈先增加后减小的趋势,当Ce含量为0.05%时钢的等向性能有大幅提高且达到最大值91.10%;Ce元素对显微硬度影响不大;添加Ce元素钢的等向性能都有不同程度的增加。     

铈对特种防护钢板组织和力学性能的影响

采用向防护钢中添加微量Ce元素的方法,研究不同Ce含量对防护钢组织和性能的影响。借助于金相显微镜、扫描电镜、能谱仪和万能拉伸试验机等检测手段,对添加Ce的防护钢的显微组织、夹杂物和力学性能进行了表征和分析。结果表明:防护钢中加入微量Ce可明显改善钢的显微组织,晶粒得到细化;钢液得到净化,钢中的氧硫含量均下降,同时钢中夹杂物得到变性,由原来多边形的Mn S夹杂转变为球状的稀土复合夹杂。钢中Ce含量达到0.084%时,其抗拉强度、屈服强度及延伸率分别比未加Ce的防护钢提高了5.24%,3.41%和43.70%。     

铈对00Cr17铁素体不锈钢高温抗氧化性的影响

利用电子分析天平、场发射扫描电镜、XRD衍射仪研究了不同Ce含量对00Cr17铁素体不锈钢高温抗氧化性的影响。结果表明:00Cr17钢中加入Ce后,钢的抗氧化性能得到提高,在1000℃以上时效果更加显著。氧化温度在700~1000℃范围内,随着Ce添加量的增加,氧化速率常数kp减小,氧化激活能提高,氧化膜由Cr2O3单相组成,而氧化温度在1100℃时,实验钢的氧化膜由Cr2O3和Fe2O3两相组成,Ce减缓了Fe2O3相的形成速率。Ce改善00Cr17铁素体不锈钢抗氧性的主要原因是降低了氧化物的生长速率,提高了氧化膜的致密性,增强了氧化膜与基体的粘附性。     

铈对202不锈钢夹杂物形态和力学性能的影响

通过金相、扫描电镜观察、能谱分析和力学性能检测,研究了加入Ce后202不锈钢的强度、塑性、冲击韧性变化。在相同的热处理工艺条件下,分别加入不同含量的Ce,与不添加Ce的202不锈钢的力学性能进行比较。结果表明:钢中加入Ce可改变夹杂物形态,并且在适当的范围内可显著提高202不锈钢的强度、塑性、横向冲击韧性。当Ce的质量分数为0.016%时,202不锈钢可获得最佳的综合力学性能。     

铈对5CrMnMo热作模具钢组织及耐磨性的影响

研究了添加4种不同含量Ce的5CrMnMo热作模具钢的组织及耐磨性，通过分析组织和磨痕形貌，以及平均磨损率和摩擦系数变化情况，与不添加Ce的5CrMnMo钢进行对比。结果表明：Ce添加量在适当的范围内组织得到显著细化，平均磨损率和摩擦系数有了明显下降，磨痕形貌也比较细而浅，从而使耐磨性得到有效提高。并且当Ce添加量为0．20％（质量分数）时，5CrMnMo钢的表面平均磨损量最少，耐磨性最好，其平均磨损率是不添加Ce的5CrMnMo钢的63．81％。     

稀土变质热锻模具铸钢高温磨损性能的研究

研究了稀土（RE）变质热锻模具铸钢的高温磨损性能，并与热锻模具钢H13钢和3Cr2W8V钢进行对比，探讨了稀土元素的作用和热锻模具铸钢的高温磨损机理。结果表明：随着RE加入量的增加，热锻模具铸钢的磨损率先减后增，RE加入量在质量分数为0．05％时热锻模具铸钢具有最佳的高温磨损性能。RE变质热锻模其铸钢的高温耐磨性明最高于H13钢和3Cr2W8V钢。高温磨损机理为氧化磨损和氧化物的疲劳剥落，磨屑为块状的Fe2O3和Fe3O4。     

HP295钢中含铈夹杂物形成的实验及热力学研究

采用LaCrO3高温管式炉重熔HP295钢,向钢液中加入不同量的Ce进行脱氧,用SEM及EDS对钢中含Ce夹杂物进行分析,并对Ce-Al-O-S系进行热力学计算。实验结果显示,含Ce夹杂物主要为不规则的Ce2O3和近球形的Ce2O2S,大部分夹杂物尺寸小于5μm。热力学计算表明,含Ce夹杂物的形成主要受钢液中[O],[S]及[Al]S含量的影响,本实验条件下主要形成Ce2O3和Ce2O2S夹杂物;当钢液中Ce与Al的活度比≥0.08时,Al2O3可转变为CeAlO3夹杂物。     

含铈重轨钢珠光体组织对抗大气腐蚀的影响

通过向重轨钢中添加Ce来改变重轨钢组织,研究其组织对抗大气腐蚀的影响。用中频感应炉冶炼实验用U71Mn,轧制后空冷。SEM测量了实验钢的珠光体片层距,在浓度为(1.0±0.05)×10~(-2)mol·L~(-1)的NaHSO3溶液中模拟了工业大气环境下实验钢的腐蚀,利用热力学计算、失重率、SEM、XRD和电化学方法研究了珠光体组织对抗大气腐蚀的影响。经过热力学计算,含Ce的U71Mn在1600～800℃析出的主要物相Ce_2O_2S,从而减少了MnS的析出,减少了钢中的有害夹杂析出。随着Ce加入量的增加,U71Mn钢珠光体片层间距先减小后增加,在40×10~(-6)时珠光体片层间距达到最小值0.2480μm。随着腐蚀周期的增加,失重量增加,在腐蚀的后期失重速率基本恒定,失重与时间呈线性关系,斜率分别为1.3755,1.0008,1.3396 g·(m~2·h)~(-1)。加入40×10~(-6)Ce和加入80×10~(-6)Ce相比与不含Ce的U71Mn钢耐腐蚀性能分别提升了12.50%和10.4%。电化学实验分别加入铈0,40×10~(-6),80×10~(-6)的三个样品在第五周期的电流分别为1.93×10~(-4),3.71×10~(-9),2.01×10~(-7)A。XRD物相半定量分析三组样品的稳定产物和不稳定产物的比值分别为0.670,1.625,1.110。对腐蚀样品的表面形貌进行分析,在腐蚀样品的表面均为花状γ-FeOOH,加入40×10~(-6)Ce的晶粒最大,不含Ce的U71Mn钢最小,加入80×10~(-6)Ce居中。     

Mg2+和Na+对高熔点煤灰熔融性的影响

以山西阳泉固庄高熔点煤灰为研究对象,通过向煤灰中添加不同量的MgO与Na₂CO₃,研究了Mg²⁺与Na⁺在高温下对煤灰熔融性的影响。研究结果表明,煤灰熔融温度随氧化镁的添加(5%~25%)单调下降;而随氧化钠添加(5%~25%)出现先降后升现象,在氧化钠添加量为15% 时,灰熔点达到最低。XRD分析表明,阳泉固庄煤灰熔融温度高(大于1 750℃)的原因是高温条件下耐熔矿物莫来石、方英石的存在。添加外加剂后,高温时外加剂与硅酸盐矿物反应,生成了更多的低共熔矿物霞石、堇青石等。同时,Mg²⁺和Na⁺的加入会使得非桥氧数量增多,高温煤灰低聚物增多,降低了煤灰的熔融温度。通过三元相图以及SEM分析,高温条件下煤灰中部分元素的富集以及团聚现象是导致Mg²⁺和Na⁺对煤灰熔融温度影响不同的原因。     

铈对16Mn钢中夹杂物和组织的影响

在高温钼丝炉内向16Mn钢中加入不同含量的铈进行脱氧,分析了钢中夹杂物和组织的变化,并探讨了含铈夹杂物诱发晶内铁素体形核的机制.结果表明:随钢中铈含量的增加,夹杂物依次转变为CeAlO3,Ce2O2S和Ce2S3.经铈处理后,钢液在1873 K时保温300 s,夹杂物最为细小弥散.钢中晶内铁素体随铈含量的增加而增加,但最佳的铈含量约为0.032%(质量分数).钢中Ce2O2S和Ce2S3夹杂与α-Fe相之间的错配度分别只有1.2%和0.5%,均可作为IGF非常有效的形核核心,促进其形成.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.