一级回火和烧结温度对掺Dy2O3的Nd-Fe-B磁性能影响

研究了一级回火和烧结温度T对掺Dy2O3烧结钕铁硼磁体的磁性能和微观结构的影响.结果表明:一级回火和烧结温度对磁体磁性能影响显著,尤其对矫顽力Hcj的影响.当添加2%(质量分数,下同)的Dy2O3时,一级回火可以明显提高磁体的Hcj,但烧结温度影响甚微;当添加5%的Dy2O3时,随烧结温度的提高,磁体的Hcj显著提高,但是一级回火使Hcj提高不明显.这主要归因于:一是Dy2O3发生置换反应生成Nd2O3颗粒影响烧结和回火制度,二是烧结温度影响Dy原子扩散.     

金属合金化X（X=Sr、Zr、Sn、Ce）对RuAl抗氧化性能影响的计算研究

目的研究RuAl的金属合金化及其氧化物Al_2O_3和RuO_2两相组的氧化关系,揭示其抗氧化性能机理。方法采用密度泛函理论的第一性原理,建立RuAl掺杂金属原子X及其间隙添加O原子的RuAl-X-O晶胞模型与其氧化产物Al_2O_3和RuO_2的晶胞模型。结果计算的Al_2O_3和RuO_2氧化能结果显示,Al_2O_3的氧化能(-11.43 eV/O_2)比RuO_2的氧化能(-2.28 eV/O_2)小,RuO_2的氧化能值与0值较为接近,在高温下结构稳定性较差,比较容易发生分解,RuAl的抗氧化能力主要依靠氧化产物Al_2O_3来进行。金属X合金化后,RuAl的氧化产物Al_2O_3和RuO_2的氧化能都增加,氧化能差值(eV/O_2)从大到小依次为Zr(0.29)Ce(0.28)Sn(0.22)Sr(-0.49),其中,金属Zr合金化对提高RuAl抗氧化能力的效果最好。计算的氧间隙形成能和电荷密集数等结果显示,金属X原子对RuAl的合金化降低了RuAl中的O固溶度,从而导致RuAl中内氧化速度降低。结论金属X原子对RuAl的合金化,阻碍RuAl表面的O向其内部扩散,障碍"内氧化"的生成条件,在RuAl表层界面的横向方向上容易形成连续、致密的Al_2O_3氧化层,提高RuAl的抗氧化性能。     

Fe3O4@SiO2磁性复合微球的制备与表征

采用化学共沉淀法制备Fe_3O_4颗粒,在其制备过程中控制Fe_3O_4核的长大时间,加入油酸钠作为表面修饰剂来控制Fe_3O_4核的尺寸,然后加入正硅酸乙酯(TEOS)生成纳米级Fe_3O_4@SiO_2复合纳米粒子和亚微米级Fe_3O_4@SiO_2复合微球。通过X射线衍射、透射电镜、能谱分析和红外光谱分析证实Fe_3O_4颗粒表面包覆有SiO_2,并研究了复合粒子的形貌和成分组成,然后进行了磁性能分析。结果表明,Fe_3O_4纳米颗粒、Fe_3O_4@SiO_2复合纳米粒子和亚微米级Fe_3O_4@SiO_2复合微球的饱和磁化强度分别为79.95、34.85和61.51 A·m2/kg,对应的剩磁分别为1.73、1.05和3.07 A·m2/kg,矫顽力分别为1083、755和2002 A/m,亚微米级复合微球的剩磁和矫顽力都显著增大。     

含Co、Ni、Fe锂铝硅玻璃的析晶机制

以Li2O-Al2O3-SiO2（锂铝硅）微晶玻璃为研究对象,采用DTA、XRD、IR和SEM等测试技术研究含Fe2O3、Co2O3、Ni2O3锂铝硅玻璃的析晶动力学和晶化过程,分析着色剂成分Co2O3、Ni2O3对锂铝硅玻璃晶化过程及结构的影响机制。结果表明：着色剂成分不仅决定锂铝硅微晶玻璃的着色度,而且还影响锂铝硅玻璃的析晶过程和显微结构;着色剂的加入可提高锂铝硅玻璃的析晶温度,但降低析晶动力学参数,且高Co2O3含量的降幅大于高Ni2O3含量的。着色剂对锂铝硅玻璃析晶能力的影响主要与着色离子的离子半径、电场强度及对断裂硅氧四面体联结能力有关。     

Standard energies of combustion and standard enthalpies of formation for the complexes RE （Et2dtc）3（phen） （RE = Ho, Er, Tm, Yb, Lu）

The treatment of RECl3.xH2O （RE = Ho, Er, Tm, Yb, Lu; x = 3-4） with sodium diethyldithiocarbamate （NaEtEdtc-3H2O） and 1,10-phenanthroline hydrate （o-phen.H2O） in absolute ethanol yielded five ternary solid complexes RE（EtEdtC）a（phen）. IR spectra of the complexes showed that RE^3＋ coordinated to two sulfur atoms in NaEt2dtc and two nitrogen atoms in o-phen. The constant-volume energies of combustion of the complexes have been determined by a precise rotating-bomb calorimeter at 298.15 K. The standard enthalpies of combustion and standard enthalpies of formation were calculated.     

Pd-Ni-Al涂层的高温短期氧化行为

在M38镍基高温合金上电镀Pd-20 mass%Ni合金，采用低压固体粉末包埋渗铝方法制备钯改性铝化物涂层，XRD分析表明，涂层主要由β-(Ni,Pd)Al相组成.利用TGA、SEM等方法，研究了涂层在800℃、900℃和1100℃的高温氧化行为表明，β-(Ni,Pd)Al涂层恒温氧化动力学遵循抛物线规律；1000℃氧化动力学则不遵循抛物线规律.在800℃和900℃下，β-(Ni,Pd)Al 涂层表面氧化产物包括α-Al2O3、θ-Al2O3和少量的γ-Al2O3；在1000℃下，涂层表面存在α-Al2O3和θ-Al2O3两种氧化物；在1100℃下，涂层表面氧化产物主要是α-Al2O3.此外，在各温度下涂层表面的氧化产物中都含有少量的TiO2，随着温度升高，其含量增加.     

Al2O3/ZrO2(Y2O3)复合材料的可靠性、磨损形态及其切削耐用度

研究了Al2O3和Al2O3/ZrO2(Y2O3)复合刀具材料的Weibull分布、磨损形态及其切削耐用度。用一元线性回归方法确定Al2O3/ZrO2(Y2O3)刀具的耐用度参数,分析切削条件对Al2O3/ZrO2(Y2O3)复合刀具材料寿命的影响。结果表明:Al2O3和含2%(摩尔分数)及3%Y2O3的ZrO2/Al2O3(Al2O3/ZrO2(2Y)及Al2O3/ZrO2(3Y))复合刀具材料Weibull模数的m值分别是5.6、10.2和11.7,说明Al2O3/ZrO2(3Y)陶瓷的可靠性最优;Al2O3/ZrO2(3Y)复合刀具切削40CrMoNiA合金钢的磨损形态主要来自磨粒磨损和粘结磨损,耐用度参数vc、f、ap的指数值分别为1.3、1.69和0.66,陶瓷刀具更适合高速切削,最大影响因素是进给量(f),在最佳切削条件下(vc=140 m/min,ap=0.5 mm和f=0.3 mm/r)切削耐用度为3 h。     

A2W3O12（A=Y, Er, Ho, Yb）型稀土钨酸盐的高温XRD研究及结构精修

用高温固相反应法制备出A_2W_3O_(12) 型稀土钨酸盐材料(A=Y,Er,Ho,Yb),用室温及高温XRD测定其在不同温度下的结构、晶胞参数及晶胞体积,并用TOPSA软件对其结构进行精修.发现除HO_2W_3O_(12)外,都具有较大的负热膨胀系数.据A. W. Sleight预测,HO_2W_3O_(12)具有较大的负热膨胀特性,但本实验却发现它并没有负热膨胀性,反而具有非常大的正热膨胀系数.     

一种新型化学溶液沉积法制备涂层导体用RE2O3（RE=Y, Sm, Eu, Dy, Yb）缓冲层

用一种新的化学溶液沉积方法在双轴织构NiW (200)合金基底上制备了涂层导体用稀土氧化物RE2O3(RE=Y, Sm, Eu, Dy, Yb)缓冲层.分别利用X射线衍射,扫描电子显微镜,原子力显微镜对制得的RE2O3缓冲层的相结构、织构、表面形貌和平整度进行了检测.结果表明,RE2O3缓冲层具有较好的双轴织构,表面平整无裂纹.     

有机大阳离子与HnXW12O40·nH2O（X=B，Si，P）多金属氧酸盐的合成及热行为

合成了3种新的多金属氧酸盐(CTMA)5BW12O40·8H2O,(CTMA)4SiW12O40·3H2O,(CTMA)3PW12O40·2H2O,利用元素分析、IR光谱和TG-DTA技术对其进行了表征.IR光谱表明这些化合物不仅含有Keggin型结构,而且存在有机大阳离子的特征吸收峰;TG-DTA曲线显示它们的热行为是一个多步分解过程,首先这些化合物在大约269℃以下脱去水分子,然后它们的无水多金属氧酸盐经历了两步或3步的分解过程,分别脱去CTMA分子及其碎片,并伴随Keggin型结构的塌陷.通过XRD和IR光谱确证其最终分解产物是一个含有WO3与B2O3,SiO2或P2O5的混合物.同时还提出了这些化合物可能的热分解过程.     

基于基团贡献法估算锂离子动力电池正极材料LiNixCoyMnzO2的ΔHf,298θ和ΔGf,298θ

基于基团贡献法对裡离子动力电池正极材料LiNi0.6Co0.2Mn0.2O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.8Co0.1Mn0.1O2和LiNi1/3Co1/3Mn1/3O2的△Hf,298θ和△Gf,298θ进行估算。首先采用基团贡献法对56种固体无机化合物的△Hf,298θ和△Gf,298θ进行估算,估算值与文献值相比,相对误差绝对值都在4%之内。基于基团贡献法首次构建了估算锂离子动力电池正极材料LiNixCOyMnzO2的△Hf,298θ和△Gf,298θ的数学模型,结合XPS实验数据分析结果,对LiNi0.6Co0.2Mn0.2O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.8Co0.1Mn0.1O2和LiNi1/3Co1/3Mn1/3O2正极材料的Hθf,298和ΔGθf,298进行估算,对应正极材料的△Hf,298θ和△Gf,298θ估算值分别为-705.39,-703.90,-695.67,-705.17 kJ·mol^-1和-647.98,-640.04,-631.10,-642.41 kJ·mol^-1。     

Synthesis and electrochemical properties of Li[NixCoyMn1-x-y]02 (x, y=2/8, 3/8) cathode materials for lithium ion batteries

The uniform layered Li(Ni2/8Co3/8Mn3/8)O2, Li(Ni3/8Co2/8Mn3/8)O2, and Li(Ni3/8Co3/8Mn2/8)O2 cathode materials for lithium ion batteries were prepared using the hydroxide co-precipitation method. The effects of calcination temperature and transition metal contents on the structure and electrochemical properties of the Li-Ni-Co-Mn-O were systemically studied. The results of XRD and electrochemical performance measurement show that the ideal preparation conditions were to prepare the Li(Ni3/8Co3/8Mn2/8)O2 cathode material calcined at 900℃ for 10 h. The well-ordered Li(Ni3/8Co3/8Mn2/8)O2 synthesized under the optimal conditions has the I003/I104 ratio of 1.25 and the R value of 0.48 and pedance of 558 Ω after the first cycle. The decrease of Ni content results in the decrease of discharge capacity and the bad cycling perform-ance of the Li-Ni-Co-Mn-O cathode materials, but the decreases of Mn content and Co content to a certain extent can improve the electro-chemical properties of the Li-Ni-Co-Mn-O cathode materials.     

The corrosion of unprotected steel in an inert-gas atmosphere containing water vapour, oxygen, nitrogen and different amounts of sulphur dioxide and carbon dioxide

The atmospheric corrosion of a commercial steel has been studied in a nominal inert gas. This gas exists inside the cargo tanks of some crude-oil tankers. The gas contained 3.0–21%O₂, 0–12%CO₂, 0–300 ppm SO₂; the balance was N₂. Relative humidity was 90% at 295 K (22.0°C). In contrast to the behaviour at moderate concentrations of SO₂ at high concentrations protective films were formed on the surface of the steel. A mechanism for the process is given. Corrosion products were studied using X-ray, i.r. and ESCA techniques. The following phases were identified: FeS, α-FeSO₃·3H₂O, γ-FeSO₂·3H₂O, FeSO₃·2H₂O and FeSO₄·7H₂O. Crystallographic data of the previously unknown phases γ-FeSO₃·3H₂O and FeSO₃·2H₂O are given.     

304不锈钢氧离子溅射的同步辐射光电子能谱原位研究Ⅰ.钢中金属元素的氧化行为

利用同步辐射光电子能谱（ＳＲ－ＸＰＳ）原位研究了经 ３ ｋｅＶ Ｏ２＋溅射的 ＳＵＳ ３０４不锈钢中 Ｆｅ、Ｎｉ、Ｃｒ合金元素与氧离子的化学反应活性差异及三种金属元素间的相互作用规律．经低能氧离子溅射后,不锈钢表面形成了一薄层氧化物膜,元素Ｃｒ和Ｎｉ分别以Ｃｒ２Ｏ３和ＮｉＯ形式存在;铁元素的氧化产物随氧离子溅射量的增加分别以ＦｅＯ、ＦｅＯ和Ｆｅ２Ｏ３。共存、全部生成Ｆｅ２Ｏ３的形式存在．在ＳＵＳ ３０４不锈钢中,铬元素与氧离子的化合能力最强,铁元素次之,镍元素的化合能力较弱．同纯金属与氧离子的化合行为比较发现：三种金属元素合金化后,铁、铬元素与氧离子的化合能力提高,而镍元素的氧化速度降低．氧化过程中铁元素与银元素间存在相互作用,只有当铁元素与氧离子反应生成Ｆｅ２Ｏ３后,镍元素才开始氧化．     

LaMgAl11O19: Mn2+和LaMgAl11O19:RE, Mn2+(RE=Eu2+, Gd3+)的发光特性

以H3BO3作助熔剂,用高温固相法在1150℃、保温4 h的条件下成功制备了LaMgAl11O19:Mn的单相粉末样品并研究了其真空紫外光激发下的一系列发光特性.在紫外光(254 nm)激发下,LaMgAl11O19:Mn不发光;真空紫外光(147 nm)激发下,观察到Mn2+很强的3d5→3d44s的跃迁发光,峰值位于516 nm,结果表明,Mn2+的掺杂浓度在0.05 mol/mol时发光最强.为了继续增强LaMgAl11O19中Mn2+的发光强度,在固定Mn2+的浓度为0.05 mol/mol的条件下又合成了LaMgAl11019:(Eu2+,Mn2+)与LaMgAl11O19:(Gd3+,Mn2+),利用(Eu2+,Mn2+)和(Gd3+,Mn2+)间存在有效的能量传递的特性,很好的达到了增强Mn2+的发光的目的.     

TiB_2和SiC_w对Al_2O_3陶瓷材料力学性能及微观结构的影响

以TiB2颗粒和SiC晶须对Al2O3陶瓷进行增韧补强,采用热压法同时了制备了Al2O3,Al2O3／TiB2和Al2O3／TiB2／SiCw三种陶瓷材料,研究了TiB2颗粒和SiC晶须对Al2O3陶瓷材料的力学性能和微观结构的影响。结果表明;因TiB2的加入可明显改善Al2O3。陶瓷材料的强度、硬度和韧性;而TiB2颗粒和SiC晶项协同对Al2O3进行增韧补强可使其断裂韧性显著提高。Al2O3／TiB2陶瓷材料的主要增韧机理有;TiB2粒子的针扎作用和使裂纹产生偏转;而Al2O3／TiB2／SiCw陶瓷材料的主要增韧机理有：晶须拔出、裂纹桥接和裂纹偏转。     

Effects of NaCl,SO2, NH3, O3, and ultraviolet light on atmospheric corrosion of Zn

The atmospheric corrosion behavior of Zn was studied in laboratory environments containing constituents that have not previously received much attention, in particular, humidity, SO₂, NH ₃, and O ₃, along with ultraviolet (UV) light irradiation and a preloading of NaCl. After exposure, corrosion rates were measured using mass loss, and corrosion products were identified by X-ray diffraction, Fourier transform-infrared spectroscopy, and energy dispersive spectroscopy. In this study, UV light and O ₃ did not significantly affect the Zn corrosion rate in the absence of Cl ⁻. However, when NaCl was present, UV light inhibited the Zn corrosion rate below 90% relative humidity (RH) and accelerated the Zn corrosion rate at 99% RH. The presence of UV light also increased the formation of zinc hydroxyl sulfate and gordaite when exposed to 120 parts per billion (ppb) SO ₂ and NaCl. The combination of SO ₂ and O ₃ with the preloading of NaCl increased the corrosion rate of Zn compared with NaCl alone. NH ₃ at a concentration of 550 ppb did not have a significant effect on the Zn corrosion rate.     

掺杂的SrAl2O4:Eux2+,Dyy3+长余辉粉的合成、表征及发光性质

采用自蔓延高温合成法制备了组成为SrAl2O4:Eu2+x,Dy3+y的2组(x:y=1:1,x:y=1:2)12种铝酸锶长余辉发光粉,测试结果表明,组成为SrAl2O4:Eu2+0.0125,Dy3+0.0125的发光亮度最好。以上述配比为依据,又分别引入了可以用于制备荧光材料的阳离子Li+、Be2+,以及既可以用于制备荧光材料也可以用于制备自激活荧光材料的阳离子Zn2+、Cd2+、Pb2+,共制得5个系列22种铝酸锶(SrAl2O4)长余辉发光粉。Zn2+0.0125的掺杂使得SrAl2O4:Eu2+0.0125,Dy3+0.0125的余辉亮度得到大幅度提高,而且SrAl2O4:Eu2+0.0125,Dy3+0.0125,Zn2+0.0125的衰减速度也明显慢于SrAl2O4:Eu2+0.0125,Dy3+0.0125。X射线衍射结果表明,掺杂少量稀土离子(Eu2+和Dy3+)不会改变SrAl2O4基质的晶体结构。另外,透射电镜分析和粒度分布结果表明,产物为疏松多孔的蘑菇云状固体,粒度在10μm左右。     

双电解质溶液HCl-H2O-MCln(M=Ni， Cu， Na， Fe)中水活度系数的计算

将水溶液中电解质处理成它们的分子形式而不是它们的离子形式，并基于两电解质之间的相互作用能相对于它们与水的相互作用能可以忽略这一假设前提，提出了简化的正规溶液模型，以计算双电解质溶液体系ＨＣｌＨ２ＯＭＣｌｎ（Ｍ＝Ｎｉ，Ｃｕ，Ｎａ，Ｆｅ）中水的活度系数。模型中所包含的两个参数为组元对的相互作用能，由实验数据估算了所讨论体系中涉及的５个组元对的相互作用能。不同双电解质体系得到的ＨＣｌＨ２Ｏ组元对的相互作用能极为吻合，表明所提出的模型是合理的。     

Abrasive wear characteristics and mechanisms of Al2O3／PA1010 composite coatings

The abrasive wear characteristics of Al2O3/PA1010 composite coatings on the surface of quenched and low-temperature temper steel 45 were tested on the tumplate abrasive wear testing machine and the same uncoated steel 45 was used as a reference material. Experimental results showed that the abrasive wear resistance of Al2O3/PA 1010 composite coatings has a good linear relationship with the volume fraction of Al2O3 particles in Al2O3/PA1010 composite coatings, and the linear correlative coefficient is 0.979. Under the experimental conditions, the size of Al2O3 particles (40.5-161.0μm) has little influence on the abrasive wear resistance of Al2O3/PA1010 composite coatings. By treating the surface of Al2O3 parti-cles with a suitable bonding agent, the distribution of Al2O3 particles in matrix PA1010 is more homogeneous and the bonding state between Al2O3 particles and matrix PA1010 is better. Therefore, the Al2O3 particles in Al2O3/PA1010 compos-ite coatings make the Al2O3/PA1010 composite coatings have better abrasive wear resistance than PA1010 coatings. The wear resistance of Al2O3/PA1010 composite coatings is about 45% compared with that of steel 45.