火法Bi捕集废汽车催化剂中的Pd、Pt、Rh

建立以绿色、无毒、低熔点的金属Bi为捕集剂,选取Na_2O-Si O_2-Al_2O_3-Bi_2O_3渣型的火法熔炼新工艺,从废汽车催化剂中回收铂族金属,研究熔渣碱度、金属Bi质量、熔炼温度、捕集时间和硅硼质量比等因素对Pd、Pt、Rh捕集行为的影响。熔渣碱度0.71、金属Bi 1.9 g、硅硼质量比0.94:1、1100℃熔炼10 min的优化条件下,熔渣易分离、贵铋表面光亮,Pd、Pt、Rh的回收率分别为98.90%、95.02%、97.00%,熔渣经二次熔炼后,Pd、Pt、Rh的总回收率均大于99%;熔炼过程中Pd、Pt、Rh优先被还原,以原子态或原子团簇形态与金属Bi键合,可形成α-Bi_2Pd、Bi_2Pt、Bi_4Rh等二元金属间化合物,有利于降低体系自由能,实现金属Bi对Pd、Pt、Rh的良好捕集。该工艺的成功开发为废汽车催化剂中铂族金属的综合回收开辟了一条新思路。     

固态还原铁捕集法回收铂族金属二次资源

研究固态还原铁捕集法回收铂族金属二次资源。结果表明:在铁精矿与铂族金属二次物料质量比为1.5:1,还原温度1220℃,还原时间6 h,还原剂配比9%,添加剂配比10%的条件下所得产物经湿式磁选,获得含铂族金属铁粉,其中Pt、Pd和Rh含量分别为110.4、27.3和52.1 g/t,Pt、Pd和Rh回收率分别为98.6%、91.7%和97.6%。该过程的机理主要在于固态还原过程中微量铂族金属优先转化为原子态或原子团簇,与新生金属Fe中自由电子键合在一起,同时,新生γ-Fe与Pt,Pd和Rh具有相同的晶体结构和相近的晶胞参数,从而形成合金;铁氧化物还原为Fe,Fe原子通过扩散方式凝聚在一起形成晶核粒子,Fe晶粒不断聚集长大,还原产物通过球磨磁选分离,实现铂族金属的回收。     

固态还原铁捕集法从废有机催化剂中回收铑的研究

我国铑资源十分稀少,需求量大,废催化剂资源丰富,开展从废催化剂中回收铑意义重大。提出采用固态铁捕集法从废有机催化剂富集回收铑的工艺,重点研究了还原制度、添加剂、还原剂、捕集剂对铑回收率的影响。结果表明,在还原温度为1200℃,还原时间为6 h,还原剂煤粉配比为9%,添加剂Ca O配比为8%的条件下进行固态还原,还原产物经细磨、摇床分选后获得含铑铁粉,其中铑的含量为106 g/t,回收率为96.53%。     

Pt替代Pd方案GPF涂层开发及性能对比

开发出Pt/Rh方案GPF(Gasoline Particulate Filter,汽油颗粒捕集器)样件，并与常规Pd/Rh方案样件进行了包括背压、台架性能、整车排放性能和积碳-再生性能的对比。结果表明，Pt替代Pd的应用不会对GPF背压造成负面影响，并且可有效提高台架老化态的起燃和空燃比窗口转化率性能以及整车WLTC(Worldwide Harmonized Light Vehicles Test Cycle,轻型车测试循环)排放性能。Pt/Rh方案样件在贵金属总量低于对比Pd/Rh样件的前提下，其积碳再生起燃温度要低于Pd/Rh件，同时前者的碳颗粒稳态再生速率和断油再生效率还有大幅度提高。因此，Pt替代Pd方案可应用于GPF涂层，在降低催化剂成本的同时催化性能还可得到提升。     

比较酸溶法消解催化剂中Pt、Pd、Rh的研究

实验比较研究了盐酸、硝酸、氢氟酸、高氯酸、硫酸等几种酸以一定的配比混合消解催化剂试样,采用光度法测定试样中贵金属Pt、Pd、Rh的含量。结果表明：采用聚四氟乙烯消化罐,试剂用HCl-HF-H2O2溶解催化剂试样,更利于Pt、Pd、Rh的溶出,Pt、Pd、Rh的回收率分别为99.5%、99.8%、101.6%,相对标准偏差分别为3.04%、2.71%、1.80%。结果满意,方法简便,容易操作。     

汽车尾气净化催化剂中Pt、Pd、Rh含量的测定

试样在聚四氟乙烯压力罐内加HCl-H2 O2 于 1 50℃浸出 ,用吸光度法测定汽车催化剂中贵金属元素 (Pt、Pd、Rh )的含量。Pt、Pd用二苄基二硫代乙二酰胺 -碘化钾 -抗坏血酸体系双波长分光光度法同时测定 ;Rh用 2 -巯基苯并噻唑 -溴化亚锡萃取光度法测定。对 2种汽车催化剂 (陶瓷蜂窝状 )ATCTL - 1 (新 )和ATCTL -GM (废 )测得Pt、Pd、Rh含量分别为 :Pt 979± 5 5μg/g和 964± 6 8μg/g ;Pd 1 68± 2 5μg/g和 1 65± 6 0 μg/g ;Rh 1 0 6± 1 8μg/g和 1 0 4± 2 6μg/g     

等离子体质谱法测定地质样品超痕量贵金属和铼

用等离子体质谱法同时测定地质样品中超痕量Au、Pt、Pd、Os、Ir、Ru、Rh和Re.试验了HCl/H2O2封闭溶样法,研究了ZPA4螯合树脂富集8元素的条件,并通过树脂灰化、HCl/H2O2封闭分解制备成试液,供ICP-MS测定.本法的检出限(ng/g)分别为0.21Au、0.12Pt、0.20Pd、0.024Os、0.016Ir、0.028Ru、0.022Rh、0.22Re,方法的相对标准偏差(RSD)为3.1%～14.8%.本法的特点是有效地降低了空白值,提高了仪器的检测能力.     

4-羟基萘-1-亚甲基若丹宁柱前衍生高效液相色谱法测定Pt、Pd、Rh

研究了用4-羟基萘-1-亚甲基若丹宁(HNR)为柱前衍生试剂,安捷伦ZORBAXStableBound(4.6×50mm,1.8μm)快速分离柱为固定相,62%的甲醇(内含0.5%的醋酸)为流动相,高效液相色谱分离,二极管矩阵检测器检测Pt、Pd和Rh的方法。3种贵金属离子的络合物在2.0min内可达到基线分离。根据信噪比(S/N=3)测得各金属离子的检测限分别为:Pt1.0μg/L、Pd0.6μg/L和Rh0.8μg/L,方法用于废汽车尾气催化剂中痕量Pt、Pd和Rh的测定,相对标准偏差为1.8%～2.1%,标准回收率为97%～103%,结果令人满意。     

低温碱性一步熔炼处理分银渣

采用低温碱性一步熔炼处理分银渣生产贵铅合金,产出的碱浮渣再经水浸获得含锡、锑、砷溶液。考察了碱渣比、盐渣比、碳粉加入量、熔炼温度、熔炼时间对锡、锑、砷浸出率以及铅、铋回收率的影响。结果表明:熔炼过程的优化条件为:碱渣比0.6,盐渣比0.4,熔炼温度600℃,熔炼时间6 h,碳粉加入量为20%。在此优化条件下,锡、锑、砷浸出率分别为85.95%、93.06%和98.62%,铅、铋被还原为单质捕集贵金属形成贵铅合金,回收率分别为93.17%和99.99%。本工艺流程短、试剂耗量少,实现了分银渣中有价金属的高效初步分离富集。     

低品位红土镍矿还原-磁选镍铁的实验研究

利用碳还原-磁选工艺回收低品位红土镍矿中的铁和镍。在对矿物成分、物相分析的基础之上,考察还原反应温度、配碳比(C/O)、助熔剂的添加量(Ca O%)和还原时间等因素对Fe、Ni回收的影响,结果表明,还原反应温度1 375℃、配碳比(C/O)0.8、助熔剂的添加量(Ca O%)12%、还原时间300 min的条件下,低品位红土镍矿中镍和铁的回收率分别为99.47%和97.54%,同时尾矿中Ni、Cr含量低于0.04%。     

解决晶闸管装置互相干扰问题一例

如果晶闸管整流器负载是感性的，那么触发器的电流值是从零开始上升，而且电感量越大，电流上升越慢，可能造成触发脉冲过后因通导电流太小而截止或造成对电源的适应性降低。在设计中必须考虑晶闸管维持电流值和通导电流上升率的关系问题。     

Refinement and strengthening mechanism of Mg−Zn−Cu−Zr−Ca alloy solidified under extremely high pressure

Mg?Zn?Cu?Zr?Ca samples were solidified under high pressures of 2–6 GPa. Scanning electron microscopy and electron backscatter diffraction were used to study the distribution of Ca in the microstructure and its effect on the solidification structure. The mechanical properties of the samples were investigated through compression tests. The results show that Ca is mostly dissolved in the matrix and the Mg₂Ca phase is formed under high pressure, but it is mainly segregated among dendrites under atmospheric pressure. The Mg₂Ca particles are effective heterogeneous nuclei of α-Mg crystals, which significantly increases the number of crystal nuclei and refines the solidification structure of the alloy, with the grain size reduced to 22 μm at 6 GPa. As no Ca segregating among the dendrites exists, more Zn is dissolved in the matrix. Consequently, the intergranular second phase changes from MgZn with a higher Zn/Mg ratio to Mg₇Zn₃ with a lower Zn/Mg ratio. The volume fraction of the intergranular second phase also increases to 22%. Owing to the combined strengthening of grain refinement, solid solution, and dispersion, the compression strength of the Mg–Zn–Cu–Zr–Ca alloy solidified under 6 GPa is up to 520 MPa.     

Fabrication of fine-grained,high strength and toughness Mg alloy by extrusion−shearing process

A novel extrusion?shearing (ES) composite process was designed to fabricate fine-grained, high strength and tough magnesium alloy. The structural parameters of an ES die were optimized by conducting an orthogonal simulation experiment using finite element software Deform-3D, and Mg?3Zn?0.6Ca?0.6Zr (ZXK310) alloy was processed using the ES die. The results show that the optimized structural parameters of ES die are extrusion angle (α) of 90°, extrusion section height (h) of 15 mm and inner fillet radius (r) of 10 mm. After ES at an extrusion temperature and a die temperature of 350 °C, ZXK310 alloy exhibited good ES forming ability, and obvious dynamic recrystallization occurred in the forming area. The grain size decreased from 1.42 μm of extrusion area to 0.85 μm of the forming area. Owing to the pinning of second phase and formation of ultrafine grains, the tensile strength, yield strength and elongation of alloy reached 362 MPa, 289 MPa and 21.7%, respectively.     

PMMA表面高功率脉冲磁控溅射制备ITO涂层的研究

采用高功率脉冲磁控溅射技术在PMMA基体上制备了ITO涂层。利用XRD、SEM对涂层进行了相结构的分析,并进行了划痕实验、光电性能测试,结果表明：偏压、氢氩流量比等工艺参数对涂层的相结构、膜基结合力、光电性能均有影响。增大偏压,膜基结合力将增强,偏压达到240 V时,膜基结合力最好（56.5N）。偏压由0 V增加到160 V的过程中,涂层晶粒增大,透射率变高（ 由82.24% 增至 89.82%）,电阻率变低（由0.006571 减至 0.000543 Ω.cm）。氢氩流量比由0增至0.05,透射率变低（由89.82%减至56.12% )。氢氩流量比由0增至0.03,电阻率变低(由0.000543减至0.000212 Ω.cm ) ;氢氩流量比由0.03增至0.05,电阻率变高由0.000212 增至0.000373 Ω.cm)。     

Hot deformation behaviors and dynamic recrystallization mechanism of Ti-35421 alloy in β single field

Hot deformation behaviors and microstructure evolution of Ti?3Al?5Mo?4Cr?2Zr?1Fe (Ti-35421) alloy in the β single field are investigated by isothermal compression tests on a Gleeble?3500 simulator at temperatures of 820?900 °C and strain rates of 0.001?1 s^?1. The research results show that discontinuous yield phenomenon and rheological softening are affected by the strain rates and deformation temperatures. The critical conditions for dynamic recrystallization and kinetic model of Ti-35421 alloy are determined, and the Arrhenius constitutive model is constructed. The rheological behaviors of Ti-35421 alloys above β phase transformation temperature are predicted by the constitutive model accurately. The EBSD analysis proves that the deformation softening is controlled by dynamic recovery and dynamic recrystallization. In addition, continuous dynamic recrystallization is determined during hot deformation, and the calculation model for recrystallization grain sizes is established. Good linear dependency between the experimental and simulated values of recrystallized grain sizes indicates that the present model can be used for the prediction of recrystallized grain size with high accuracy.     

Effect of yttrium and calcium additions on electrochemical behaviors and discharge performance of AZ80 anodes for Mg−air battery

The effects of yttrium (Y) and yttrium + calcium (Y+Ca) additions on the electrochemical properties and discharge performance of the as-extruded Mg?8Al?0.5Zn?0.2Mn (AZ80) anodes for Mg?air batteries were investigated. The results show that the addition of 0.2 wt.% Y increased the corrosion resistance and discharge activity of AZ80 anode. This was attributed to the fine and spherical β-Mg₁₇Al₁₂ phases dispersing evenly in AZ80+0.2Y alloy, which suppressed the localized corrosion and severe “chunk effect”, and facilitated the rapid activation of α-Mg. Combinative addition of 0.2 wt.% Y and 0.15 wt.% Ca generated grain refinement and a reduction of the β-Mg₁₇Al₁₂ phase, resulting in a further enhancement in discharge voltage. However, the incorporation of Ca in Mg₁₇Al₁₂ and Al₂Y compounds compromised the corrosion resistance and anodic efficiency of AZ80+0.2Y+0.15Ca anode. Consequently, AZ80+0.2Y anode exhibited excellent overall discharge performance, with the peak discharge capacity and anodic efficiency of 1525 mA·h·g^?1 and 67% at 80 mA/cm², 13% and 14% higher than those of AZ80 anode, respectively.     

NaCl溶液中AZ91D的腐蚀性能--RE与Sb及Si对AZ91D合金在NaCl溶液中腐蚀速率的影响

通过静态失重法研究了RE、Si和Sb元素加入后对AZ91D合金在NaCl溶液中腐蚀速率的影响.结果表明, RE加入可以提高AZ91D合金的腐蚀速率,而Si和Sb的加入使合金的腐蚀速率加大.     

Effects of annealing at 800 and 1000 °C on phase precipitates and hardness of Al7Cr20FexNi73−x alloys

The effects of Fe content on the microstructure, phase constituents and microhardness of the as-cast, 800 °C- or 1000 °C-annealed Al₇Cr₂₀Fe_xNi_73?x (x=13?66) alloys were investigated. Not all these alloys are composed of the single FCC phase. The BCC and B2 phases are found. It is confirmed that the BCC phase in the Al₇Cr₂₀Fe₆₆Ni₇ alloy is transformed from the FCC phase at about 900 °C during cooling. While in the 800 °C-annealed Al₇Cr₂₀Fe₆₀Ni₁₃ alloy, the FCC phase is stable and the hardness decreases. After annealing at 1000 °C, for the precipitation of the B2 particles, the Al content in the FCC phase decreases, which results in decreasing of the alloy hardness. Moreover, after annealing at 800 °C, a small amount of Al-rich B2 particles precipitate at the phase boundary and some nanocrystal BCC phase precipitates in the FCC matrix, which increases the hardness of the Al₇Cr₂₀Fe_xNi_73?x (x=41?49) alloys. These results will help to the composition design and processing design of the Al?Cr?Fe?Ni based high-entropy alloys.     

固溶时效对TC21钛合金准β锻后组织性能的影响

对TC21钛合金进行准β锻造,再进行固溶时效热处理实验,研究了不同固溶时效热处理制度对合金的微观组织和力学性能的影响。结果表明,TC21钛合金通过准β锻造后,再经固溶时效热处理工艺处理后,合金的微观组织呈现典型的网篮组织。随着固溶温度的上升,片状α相含量和长度显著降低,同时合金强度增加,而塑性变化呈相反趋势。随着时效温度的上升,对片状α相的影响略小,但次生α相的厚度此时显著增加,此时合金强度降低,塑性提高。断口形貌则随着固溶温度的升高,断口表面和裂纹扩展路径愈发平坦。断裂韧性值呈现下降趋势,但会随着时效温度的升高而提高。合金最大断裂韧性值可达66MPa·m1/2。考虑合金的强度、塑性和断裂韧性之间的良好匹配,经综合分析可得,TC21钛合金准β锻后最佳热处理制度为:870 ℃/2 h,AC+590 ℃/4 h,AC。     

Phase equilibria in Co−Al−Re ternary system at 1100 and 1300 °C

Isothermal sections of the Co?Al?Re ternary system at 1100 and 1300 °C were determined experimentally by electron probe microanalysis and X-ray diffraction. The results show that there are seven three-phase regions in the 1100 °C isothermal section and five three-phase regions in the 1300 °C isothermal section. The solid solubilities of αCo, εRe and CoAl increase a little with temperature increasing from 1100 to 1300 °C. The solubility of Co in compounds AlRe₂, Al₁₁Re₄ and Al₄Re is negligible, <1.5 at.%. And no ternary compounds are found.