Simplified quantitative analysis method and its application in the insitu synthesized copper-based azide chips

Copper-based azide(Cu(N_(3))2 or CuN_(3),CA)chips synthesized by in-situ azide reaction and utilized in miniaturized explosive systems has become a hot research topic in recent years.However,the advantages of in-situ synthesis method,including small size and low dosage,bring about difficulties in quantitative analysis and differences in ignition capabilities of CA chips.The aim of present work is to develop a simplified quantitative analysis method for accurate and safe analysis of components in CA chips to evaluate and investigate the corresponding ignition ability.In this work,Cu(N_(3))2 and CuN_(3)components in CA chips were separated through dissolution and distillation by utilizing the difference in solubility and corresponding content was obtained by measuring N_(3)-concentration through spectrophotometry.The spectrophotometry method was optimized by studying influencing factors and the recovery rate of different separation methods was studied,ensuring the accuracy and reproducibility of test results.The optimized method is linear in range from 1.0-25.0 mg/L,with a correlation coefficient R^(2)=0.9998,which meets the requirements of CA chips with a milligram-level content test.Compared with the existing ICP method,component analysis results of CA chips obtained by spectrophotometry are closer to real component content in samples and have satisfactory accuracy.Moreover,as its application in miniaturized explosive systems,the ignition ability of CA chips with different component contents for direct ink writing CL-20 and the corresponding mechanism was studied.This study provided a basis and idea for the design and performance evaluation of CA chips in miniaturized explosive systems.

Metal-organic-framework-derived copper-based catalyst for multicomponent C-S coupling reaction

Copper-based metal-organic frameworks(Cu-MOFs)are a promising multiphase catalyst for catalyzing C-S coupling reactions by virtue of their diverse structures and functions.However,the unpleasant odor and instability of the organosulfur,as well as the mass-transfer resistance that exists in multiphase catalysis,have often limited the catalytic application of Cu-MOFs in C-S coupling reactions.In this paper,a Cu-MOFs catalyst modified by cetyltrimethylammonium bromide(CTAB)was designed to enhance mass transfer by increasing the adsorption of organic substrates using the long alkanes of CTAB.Concurrently,elemental sulfur was used to replace organosulfur to achieve a highly efficient and atom-economical multicomponent C-S coupling reaction.

A highly hydrothermal stable copper-based catalyst for catalytic wet air oxidation of m-cresol in coal chemical wastewater

Catalytic wet air oxidation(CWAO) can degrade some refractory pollutants at a low cost to improve the biodegradability of wastewater. However, in the presence of high temperature and high pressure and strong oxidizing free radicals, the stability of catalysts is often insufficient, which has become a bottleneck in the application of CWAO. In this paper, a copper-based catalyst with excellent hydrothermal stability was designed and prepared. TiO_(2) with excellent stability was used as the carrier to ensure the longterm anchoring of copper and reduce the leaching of the catalyst. The one pot sol–gel method was used to ensure the super dispersion and uniform distribution of copper nanoparticles on the carrier, so as to ensure that more active centers could be retained in a longer period. Experiments show that the catalyst prepared by this method has good stability and catalytic activity, and the catalytic effect is not significantly reduced after 10 cycles of use. The oxidation degradation experiment of m-cresol with the strongest biological toxicity and the most difficult to degrade in coal chemical wastewater was carried out with this catalyst. The results showed that under the conditions of 140℃, 2 MPa and 2 h, m-cresol with a concentration of up to 1000 mg·L^(-1) could be completely degraded, and the COD removal rate could reach 79.15%. The biological toxicity of wastewater was significantly reduced. The development of the catalyst system has greatly improved the feasibility of CWAO in the treatment of refractory wastewater such as coal chemical wastewater.

Interfacial reaction behavior and mechanical properties of 5A06 Al alloy soldered with Sn-1Ti-xGa solders at a low temperature

Active soldering of 5A06 Al alloy was performed at 300 ℃ by using Sn-1Ti and Sn-1Ti-0.3Ga active solders, respectively. Theeffects of soldering time on the microstructure and mechanical properties of the joints were investigated. The results showed that the Sn-1Tisolder broke the oxide film on the surface of the Al substrate and induced intergranular diffusion in the Al substrate. When Ga was added tothe solder, severe dissolution pits appeared in the Al substrate due to the action of Sn-1Ti-0.3Ga solder, and many Al particles were flakedfrom the matrix into the solder seam. Under thermal stress and the Ti adsorption effect, the oxide film cracked. With increasing solderingtime, the shear strength of 5A06 Al alloy joints soldered with Sn-1Ti and Sn-1Ti-0.3Ga active solders increased. When soldered for 90 min,the joint soldered with Sn-1Ti-0.3Ga solder had a higher shear strength of 22.12 MPa when compared to Sn-1Ti solder.

Preventing formation of intermetallic compounds in ultrasonic-assisted Sn soldering of Mg/Al alloys through pre-plating a Ni coating layer on the Mg substrate

Magnesium and aluminum alloys are widely used in various industries because of their excellent properties,and their reliable connection may increase application of materials.Intermetallic compounds(IMCs)affect the joint performance of Mg/Al.In this study,AZ31 Mg alloy with/without a nickel(Ni)coating layer and 6061 Al alloy were joined by ultrasonic-assisted soldering with Sn-3.0Ag-0.5Cu(SAC)filler.The effects of the Ni coating layer on the microstructure and mechanical properties of Mg/Al joints were systematically investigated.The Ni coating layer had a significant effect on formation of the Mg_(2)Sn IMC and the mechanical properties of Mg/Al joints.The blocky Mg_(2)Sn IMC formed in the Mg/SAC/Al joints without a Ni coating layer.The content of the Mg_(2)Sn IMC increased with increasing soldering temperature,but the joint strength decreased.The joint without a Ni coating layer fractured at the blocky Mg_(2)Sn IMC in the solder,and the maximum shear strength was 32.2 MPa.By pre-plating Ni on the Mg substrate,formation of the blocky Mg_(2)Sn IMC was inhibited in the soldering temperature range 240–280℃and the joint strength increased.However,when the soldering temperature increased to 310℃,the blocky Mg_(2)Sn IMC precipitated again in the solder.Transmission electron microscopy showed that some nano-sized Mg_(2)Sn IMC and the(Cu,Ni)_(6)Sn_(5)phase formed in the Mg(Ni)/SAC/Al joint soldered at 280℃,indicating that the Ni coating layer could no longer prevent diffusion of Mg into the solder when the soldering temperature was higher than 280℃.The maximum shear strength of the Mg(Ni)/SAC/Al joint was 58.2 MPa for a soldering temperature of 280℃,which was 80.7%higher than that of the Mg/SAC/Al joint,and the joint was broken at the Mg(Ni)/SAC interface.Pre-plating Ni is a feasible way to inhibit formation of IMCs when joining dissimilar metals.

Effect of Sb content on properties of Sn-Bi solders

The effect of Sb content on the properties of Sn-Bi solders was studied. The nonequilibrium melting behaviors of a series of Sn-Bi-Sb solders were examined by differential scanning calorimetry （DSC）. The spreading test was carried out to characterize the wettability of Sn-Bi-Sb solders on Cu substrate. The mechanical properties of the solders/Cu joints were evaluated. The results show that the ternary alloy solders contain eutectic structure resulting from quasi-peritetic reaction. With the increase of Sb content, the amount of the eutectic structure increases. At a heating rate of 5 ℃/min, Sn-Bi-Sb alloys exhibit a higher melting point and a wider melting range. A small amount of Sb has an impact on the wettability of Sn-Bi solders. The reaction layers form during spreading process. Sb is detected in the reaction layer while Bi is not detected. The total thickness of reaction layer between solder and Cu increases with the increase of the Sb content. The shear strength of the Sn-Bi-Sb solders increases as the Sb content increases.

Design of Pb-free solders in electronic packaging by computational thermodynamics and kinetics

Computational thermodynamics and kinetics were used to design the Pb-free micro-solders for replacing the conventional Sn-Pb solders because of the health and environmental safety problem. On the basis of CALPHAD (Calculation of Phase Diagrams) method we can easily calculate properties such as the liquidus projection, isothermal and vertical sectional diagrams and phase fraction in multi-component system including Ag, Bi, Cu, In, Sb, Sn, Zn and Pb elements. In addition, other related information such as the surface tension, viscosity of the liquid phase and solidification simulation can also be obtained. DICTRA (Diffusion Controlled Transformation) software was used to simulate the interfacial reactions between substrate and Pb-free solders, which can easily give the information on the growth of intermetallic compounds and moving speed of interface between substrate and solders etc.

Environmentally friendly solders 3-4 beyond Pb-based systems

Based on environmental considerations, global economic pressures, enacted by legislations in several countries, have warranted the elimination of lead from solders used in electronic applications. Sn3.5Ag, SnAgCu, and Sn0.7Cu have emerged among various lead-free candidates as the most promising solder alloys to be utilized in microelectronic industries. However, with the vast development and miniaturization of modern electronic packaging, new requirements such as superior service capabilities have been posed on lead-free solders. In order to improve the comprehensive property of the solder alloys, two possible approaches were adopted in the current research and new materials developed were patented. One approach was involved with the addition of alloying elements to make new ternary or quaternary solder alloys. Proper addition of rare earth element such as La and Ce have rendered solder alloys with improved mechanical properties, especially creep rupture lives of their joints. Another approach, the composite approach, was developed mainly to improve the service temperature capability of the solder alloys. Composite solders fabricated by mechanically incorporating various reinforcement particles to the solder paste have again exhibited enhanced properties without altering the existing processing characteristics. The recent progress and research efforts carried out on lead-free solder materials in Beijing University of Technology were reported. The effects of rare earth addition on the microstructure, processing properties, and mechanical properties were presented. The behaviors of various Sn-3.5Ag based composite solders were also explicated in terms of the roles of reinforcement particles on intermetallic growth, steady-state creep rate, the onset of tertiary creep, as well as the overall creep deformation in the solder joints. Thermomechanical fatigue (TMF) behavior of the solder alloys and composite solders were investigated with different parameters such as ramp rate, dwell time, etc. The damage accumulation features and residual mechanical properties of the thermomechanically-fatigued composite solder joints were compared with non-composite solder joints. To match the lead-free alloys, various types of water soluble no-clean soldering flux have also been developed and their properties were presented.

Formation of Bulk Intermetallic Compound AgaSn in Slowly-Cooled Lead-Free Sn-4.0 wt pct Ag Solders

Sn-Ag alloy system has been regarded as one of the most promising lead-free solder to substitute conventional Sn- Pb eutectic solder. But the formation of bulk Ag3Sn intermetallic compounds （IMCs） during reflow and post heat treatment significantly influences the performance of the solder joints. With an effort to clarify its microstructural evolution as a function of slow cooling rates, the fraction of bulk IMCs within the slowly solidified Sn-4.0 wt pct Ag solder was investigated by standard metallographic and compared with that detected by thermal analysis. It was found that the bulk IMCs fraction determined by thermal analysis corresponds quite well with the microstructure observation results. In accordance with the conventional solidification theory, the lower the applied cooling rate, the fewer the amount of bulk Ag3Sn IMCs formed in Sn-4.0 wt pct Ag alloy. In addition, Vickers hardness measurement results indicated that the relative coarse eutectic Ag3Sn IMCs distributing in the lamellar eutectic structure favored the improvement of the mechanical performance.

Creep behavior of SnAgCu solders with rare earth Ce doping

Extensive testing was carried out to study the effects of rare earth Ce doping on the properties of SnAgCu solder alloys.The addition of 0.03%(mass fraction) rare earth Ce into SnAgCu solder may improve its mechanical properties,but slightly lower its melting temperature.The tensile creep behavior of bulk SnAgCuCe solders was reported and compared with SnAgCu solders.It is found that SnAgCuCe solders show higher creep resistance than SnAgCu alloys.Moreover,Dorn model and Garofalo model are successfully used to describe the creep behavior of SnAgCu and SnAgCuCe alloys.The parameters of the two creep constitutive equations for SnAgCu and SnAgCuCe solders are determined from separated constitutive relations and experimental results.Nonlinear least-squares fitting is selected to determine the model constants.The experimental data of the stress-creep strain rate curves are in good agreement with the theoretical ones.

Catalytic combustion of methane over nano ZrO_2-supported copper-based catalysts

The nano ZrO2-supported copper-based catalysts for methane combustion were investigated by means of N2 adsorption, TEM, XRD, H2-TPR techniques and the test of methane oxidation. Two kinds of ZrO2 were used as support, one （ZrO2-1） was obtained from the commercial ZrO2 and the other （ZrO2-2） was issued from the thermal decomposition of zirconium nitrate. It was found that the CuO/ZrO2-2 catalyst was more active than CuO/ZrO2-1. N2 adsorption, H2-TPR and XRD measurements showed that larger surface area, better reduction property, presence of tetragonal ZrO2 and higher dispersion of active component for CuO/ZrO2-2 than that of CuO/ZrO2-1. These factors could be the dominating reasons for its higher activity for methane combustion.

Wetting kinetics of SiC nanoparticle reinforced Sn-Pb eutectic solders

SiC nanoparticles reinforced eutectic Sn-Pb solder were prepared by mechanical mixing method. Reactive wetting of the resultant composite solders on Cu substrates was investigated using real time, in-situ visualization of the triple-line movement. It was found that spreading rates of all solder pastes in this work do not obey Tanner＇ s law of non-reactive spreading. SiC nano-particles slow down both the pre-melting and post-melting spreading rates of composite solder pustes. As the content of SiC nano-particles increase, the melting point of composite solders decrease, and the spreading time of molten composite solder pastes increases.

Effect of preparation methods of aluminum emulsions on catalytic performance of copper-based catalysts for methanol synthesis from syngas

Various Cu/ZnO/Al2O3 catalysts have been synthesized by different aluminum emulsions as aluminum sources and their pertormances tor methanol synthesis from syngas have been investigated. The influences of preparation methods of aluminum emulsions on physicochemical and catalytic properties of catalysts were studied by XRD, SEM, XPS,N2 adsorption-desorption techniques and methanol synthesis from syngas. The preparation methods of aluminum emulsions were found to influence the catalytic activity, CuO crystallite size, surface area and Cu0 surface area and reduction process. The results show that the catalyst CN using the aluminum source prepared by addition the ammonia into the aluminum nitrate （NP） exhibited the best catalytic performance for methanol synthesis from syngas.

Comprehensive first-principles studies on phase stability of copper-based halide perovskite derivatives A_lCu_mX_n(A = Rb and Cs;X = Cl, Br, and I)

Recently,inorganic copper-based halide perovskites and their derivatives(CHPs)with chemical formulas AlCumXn(A=Rb and Cs;X=Cl,Br and I;l,m,and n are integers.),have received increasing attention in the photoluminescence field,due to their lead-free,cost-effective,earth-abundant and low electronic dimensionality.Ascribed to flexible valence charge of Cu(Cu1+and Cu2+)and complex competing phases,the crystal structures and phase stabilities of CHPs are complicated and ambiguous,which limits their experimental applications.Via comprehensive first-principles calculations,we have investigated thermodynamic stabilities of possible crystal phases for AlCumXn by considering all the possible secondary phases existing in inorganic crystal structure database(ICSD).Our results are in agreement with existing experiments and further predicted the existence of 10 stable CHPs,i.e.Rb3 Cu2 Br5,Rb3 Cu2 I5,Rb Cu2 Cl3,Rb2 Cu I3,Rb2 Cu Br4,Rb Cu Br3,Rb3 Cu2 Br7,Cs3 Cu2 Br7,Cs3 Cu2 Cl7 and Cs4 Cu5 Cl9,which have not yet been reported in experiments.This work provides a phase and compositional map that may guide experiments to synthesize more novel inorganic CHPs with diverse properties for potential functional applications.

Effects of Ag contents in Sn-xAg lead-free solders on microstructure,corrosion behavior and interfacial reaction with Cu substrate

The effects of Ag on the microstructure and corrosion behavior of pre-soldering Sn-xAg lead-free solders,and on the formation of intermetallic layer of the solders with Cu substrate were investigated.The Ag contents(x)were 0,3.0,3.5,4.0,and5.0 wt.%.The Ag content played a role in the morphology of Ag3 Sn phase in the solders.The microstructure analysis showed that theβ-Sn phase was surrounded by eutectic networks in the 3.0 Ag and 3.5 Ag solders and large plate-like Ag3 Sn formed in the 4.0 Ag and5.0 Ag solders.Nonetheless,the Ag content slightly impacted the corrosion behavior of the as-cast solders as characterized using potentiodynamic polarization test.After soldering,only a single layer of a Cu6 Sn5 intermetallic compound formed at the Sn-xAg/Cu interface.By comparison,the Cu6 Sn5 intermetallic layer of the Ag-doped solders was thinner than that of the 0Ag solder.The fine Ag3 Sn particles in the eutectic networks precipitating in the 3.0 Ag and 3.5 Ag solders effectively hindered the growth of Cu6 Sn5 grains compared to large plate-like Ag3 Sn in the 4.0 and 5.0Ag solders.

Migration of sulfur in in-situ gasification chemical looping combustion of Beisu coal with iron-and copper-based oxygen carriers

Chemical looping combustion(CLC)is an energy conversion technology with high efficiency and inherent separation of CO_(2).The existence of sulfur in coal may affect the CO_(2) purity and the performance of oxygen carrier due to the interactions between sulfur contaminants and oxygen carrier.The migration of sulfur in Beisu coal during the in-situ gasification chemical looping combustion(i G-CLC)process using two oxygen carriers(iron ore and Cu O/Si O_(2))was investigated respectively.The thermodynamic analysis results showed the formation of metal sulfides was thermodynamically favored at low temperatures and low oxygen excess coefficients,while they were obviously inhibited and the production of SO_(2) was significantly promoted with an increase in temperature and oxygen excess coefficient.Moreover,part of sulfur was captured and fixed in the forms of alkali/alkaline earth metal sulfate due to the high amount of alkali/alkaline earth metal oxides in the coal ash or/and oxygen carrier.The experimental results showed that the sulfur in coal mainly released in the form of SO_(2),and the sulfur conversion efficiency(XS)in the reduction stage were 51.04%and 48.24%when using iron ore and Cu O/Si O_(2) respectively.The existence of metal sulfides was observed in the reduced oxygen carriers.The values of XSin the reoxidation process reached 3.80%and 7.64%when using iron ore and Cu O/Si O_(2) respectively.The residue and accumulation of sulfur were also found on the surfaces of two oxygen carriers.

Influence of Cu content on microstructure,grain orientation and mechanical properties of Sn-xCu lead-free solders

The effect of Cu content on the microstructure,grain orientation and mechanical properties of Sn-xCu(x=0-4.0 wt.%)lead-free solder was studied.Results showed that added Cu induced the formation of intermetallic phases.Only theη-Cu;Sn;andε-Cu;Sn phases were present in theβ-Sn matrix.For all contents,the strongly preferred orientation of theβ-Sn phase was formed on the{001}plane.In Sn doped with 1.0 wt.%Cu,theη-Cu;Sn;phase exhibited the preferred orientation of{0001}plane,whereas doping with 3.0 or 4.0 wt.%Cu transformed the preferred orientation to the{010}plane.In addition,only the{0001}and{■}planes were present in theε-Cu;Sn phase.The high Cu contents contributed to an increased number of low-angle boundaries,high residual strain,tensile strength and microhardness.

Effects of cooling rates on microstructure and microhardness of lead-free Sn-3.5%Ag solders

The microstructure and microhardness of Sn-3.5%Ag solders were explored in the cooling rate ranging from 0.08 to 104 K/s. Under rapid cooling condition, the strong kinetic undercooling effect leads to the actual solidification process starting at the temperature lower than the equilibrium eutectic point, and the actual metastable eutectic point shifts to the higher Ag concentration. Hence, the higher the applied cooling rate is, the more the volume fraction of primary β-Sn crystal forms. At the same time, the separation of primary β-Sn crystal favors restraining the formation of bulk Ag3Sn intermetallic compounds (IMCs) in solder due to the mismatch crystalline orientation relationship, those Ag3Sn phase separating through the eutectic reaction could hardly cling to the primary β-Sn crystal and grow up. Additionally, the Vickers hardness test shows that fine β-Sn and spherical Ag3Sn phase in the rapidly solidified alloy strongly improves the microhardness of the Sn-3.5%Ag solder.

Mechanical properties of QFP micro-joints soldered with lead-free solders using diode laser soldering technology

Soldering experiments of quad flat package(QFP) devices were carried out by means of diode laser soldering system with Sn-Ag-Cu and Sn-Cu-Ni lead-free solders, and competitive experiments were also carried out not only with Sn-Pb eutectic solders but also with infrared reflow soldering method. The results indicate that under the conditions of laser continuous scanning mode as well as the fixed laser soldering time, an optimal power exists, while the optimal mechanical properties of QFP micro-joints are gained. Mechanical properties of QFP micro-joints soldered with laser soldering system are better than those of QFP micro-joints soldered with IR reflow soldering method. Fracture morphologies of QFP micro-joints soldered with laser soldering system exhibit the characteristic of tough fracture, and homogeneous and fine dimples appear under the optimal laser output power.

Effects of Copper-based Nutritional Foliar Fertilizers on Photosynthetic Characteristics,Yield and Disease Control Efficiency of Cotton

[Objectives] The effects of copper-based nutrient foliar fertilizer on photosynthetic characteristics,yield,accumulation and distribution of trace elements in various organs,disease prevention effect and soil enzyme activity were studied,so as to provide a theoretical basis for the application of foliar fertilizers in cotton production. [Methods]Through two years of field experiments,six treatments were set in total,namely spraying water( CK),traditional Bordeaux mixture( BDM),Kocide 2000( KCD),copper-based nutrient foliar fertilizer( CF),iron-copper-based nutrient foliar fertilizer( CFFe),and zinc-boron-copper-based nutrient foliar fertilizer( CFZnB). Randomized block arrangement was adopted. Chlorophyll content in leaves was measured at each growth stage of the cotton. Photosynthetic characteristics of leaves were measured at the peak bolling stage. Plants were sampled at initial boll opening stage. The whole plant was divided into root,stem,leaf and cotton boll parts,in which the total copper,total zinc,total iron contents and accumulations were determined. Soil samples were collected from each plot,followed by the determination of soil enzyme activity. Disease index was investigated at bud,flowering and boll-forming and boll opening stage. [Results]( 1) Spraying CFFe,CFZnB,CF and KCD could significantly improve chlorophyll content of cotton leaves,and the CFFe treatment had the highest increase up to13. 30%,followed by the CFZnB treatment,which was 11. 40% higher than the CK; and photosynthetic rate,stomata conductance and transpiration rate could be improved significantly,and the CFFe treatment showed the highest photosynthetic rate,which increased by 26. 35% compared with the CK,followed by the CFZnB treatment,which increased by 17. 96% compared with CK; and intercellular CO2 concentration was significantly reduced.( 2) Spraying BDM,KCD,CF,CFFe and CFZnB can significantly increase total copper content and accumulation in various cotton organs( except the total copper content in the stem part of the CFZnB treatment; the CFZnB and CFFe treatments can significantly increase total zinc content and accumulation in various cotton organs; and spraying CFFe,CFZnB and CF can significantly increase total iron content and accumulation in various cotton organs( except the total iron content in the stem part of the CF treatment).( 3)Spraying CFFe,CFZnB,CF,KCD and BDM greatly reduced the disease index at flowering and boll-forming and boll opening stages.( 4) The CFZnB and CFFe treatments had the highest soil urease activity,which was 7. 14% higher than that of the CK,but the difference from the CK was not significant; the catalase activity of each treatment was significantly higher than that of the BDM treatment; and the sucrase activity of each treatment was significantly higher than that of the CK.( 5) Spraying CFFe,CFZnB,CF and KCD significantly improved lint yield of cotton,and the CFZnB treatment showed the highest yield increase up to 12. 34%,followed by the CFFe treatment,with an increase in the range of 8. 77%-10. 20%. [Conclusions]Copper-based nutrient foliar fertilizers have dual functions of disease control and prevention and plant nutrition and health care,and not only can significantly increase cotton yield,but also has certain disease prevention effect.It is recommended to use copper-based nutrient foliar fertilizers.