Spray forming of high density sheets

Porosity is one of the most important quality criteria of spray‐formed materials in the as‐sprayed condition. Typically, spray‐formed sheets have a porous rim close to the substrate and depending on the spray conditions cold or hot porosity may also be present in the core of the deposit. This porosity has to be removed or minimized to make further processing steps such as rolling, forging or extrusion possible. In this paper, the influence of both substrate temperature and deposit surface temperature on porosity in spray‐formed sheets is studied. For this purpose spray forming experiments (sheet size 1000 mm × 250 mm) were carried out using three different materials: aluminium‐bronze, tin‐bronze and a nitriding steel. For the copper‐base alloys preheated steel‐substrates with different temperatures were moved through a scanning spray cone. In the case of steel a ceramic substrate at room temperature was used. In addition to the variation of the substrate temperature, the gas to metal mass flow ratio (GMR) was varied to achieve different deposit surface temperatures. During the run the surface temperature in the deposition zone was measured using a scanning, multi‐wavelength pyrometer. Samples of the deposits were polished and rasterized by light microscopy. The local porosity was characterized by digital image analysis. The influence of the substrate temperature and the GMR on the porosity in the vicinity of the substrate is evaluated and discussed in detail. The impact of the deposit surface temperature on the porosity was analyzed and is discussed as well. It was found that the deposit surface temperature has a strong impact on porosity for spray‐formed sheets. Finally, experimental results were used to develop a new approach to predict the porosity in spray‐formed sheets. The results clearly show the dependence on material properties. This approach can be used to identify process parameters to generate high density sheets in the future.     

Numerical simulation of gas-droplets mixing and spray evaporation in rotary spray desulfurization tower

Motion and evaporation of droplets significantly affect the semidry flue gas desulfurization efficiency and long-term operation. Both the flow field distribution and the heat and mass transfer in the spray towers are studied by numerical simulation, and the process of droplet motion and evaporation is analyzed in detail. Then, two indices, mixing variance and droplet mass-weighted life, are provided to quantify gas droplet mixing and the droplet group evaporation time. The simulation results show that the radial penetration distance of the droplets is longer with the diameter increase, and the appropriate swirl number improves the mixing between the flue gas and droplets. With the increase of droplet diameter and velocity, the droplet distribution in the tower is more widely, obtaining the optimum mixing variance. The droplet mass-weighted life is promoted linearly with the increase of average droplet diameter and the decrease of flue gas temperature. With flue gas temperature increase from 458 k to 488 K, the droplet mass-weighted life decreases linearly by 31%. In comparison, the initial droplet velocity and spray angle have a slight effect on the droplet mass-weighted life.     

Spray forming: Science and technology

Spray forming involves sequential gas atomization of a melt into a spray of fine droplets and their deposition on a substrate to build up a high-density preform. The rapid solidification inherent in spray deposition generates refined, equiaxed and low segregation microstructures. A number of promising features of this near-net shape manufacturing process are highlighted and compared, wherever possible, with the conventional casting and PM techniques. Some commercial nozzles used to create spray and mechanisms associated with spray generation are described. The consolidation of the droplets and the development of the microstructure in the deposit are primarily governed by the nature of the spray and the thermal state of droplets on the deposition surface. Several microstructural characteristics of the deposit are presented and their origin in spray deposition is discussed.     

Droplet cooling in atomization sprays

Transport between droplets/particles and a gas phase plays an important role in numerous material processing operations. These include rapid solidification operations such as gas atomization and spray forming, as well as chemical systems such as flash furnaces. Chemical reaction rates and solidification are dependent on the rate of gas-particle or gas-droplet transport mechanisms. These gas-based processes are difficult to analyze due to their complexity which include particle and droplet distribution and the flow in a gas field having variations in temperature and velocity both in the jet cross-section and in the axial distance away from the jet source. Thus to study and properly identify the important variables in transport, these gas and droplet variations must be eliminated or controlled. This is done in this work using models based on a single fluid atomization system. Using a heat transport model (referred to as thermal model) validated using single fluid atomization of molten droplets and a microsegregation model, the effect of process variables on heat losses from droplets was examined. In this work, the effect of type of gas, droplet size, gas temperature, gas-droplet relative velocity on the heat transport from AA6061 droplets was examined. It is shown that for a given gas type, the most critical process variable is the gas temperature particularly as affected by two-way thermal coupling and the droplet size. The results are generalized and applied to explain the difference in droplet cooling rate from different atomization processes.     

Microstructural features induced by spray forming of a ternary Pb-Sn-Sb alloy

An alloy containing Pb-12% Sn-12% Sb with small addition of copper and arsenic was spray deposited employing two different atomization gas pressure and nozzle to substrate distances. The temperature of the spray-deposit was measured during deposition at a distance of 2 and 10 mm above the substrate-deposit interface. Thermal profile data indicated small variation in temperature with time during deposition stage whereas during post deposition stage an exponential decrease in temperature was recorded. Second phase particle size along the thickness of the deposit varied from 4 to 8 μm compared to 70 to 80 μm size of these particles in the as cast alloy. Maximum porosity occurred in the section of the deposit near the contact surface of the substrate and also in its peripheral regions. X-ray diffraction analysis exhibited the formation of additional Cu₂Sb phase in the spray-deposit and CuSn and Cu_3.3Sb phases in atomized powders compared to that of the as cast alloy. The microstructural evolution during spray deposition of this alloy is discussed.     

A simple transient numerical model for heat transfer and shape evolution during the production of rings by centrifugal spray deposition

Centrifugal spray deposition, the atomisation of a liquid metal by centrifugal force and the subsequent collection of the atomised droplets on a reciprocating collector, is currently being developed for the production of high performance Fe, Ni and Ti based ring-shaped components for use in aerospace and gas turbine containment applications. The process combines the technical, economic and metallurgical benefits of more conventional gas-assisted spray forming techniques with the advantage that it can easily operate under vacuum, reducing potential problems from gas entrapment and thermally induced porosity. In order to aid process development, understanding and optimisation, a transient numerical heat and mass transfer model has been developed that is capable of predicting the evolution of the deposit temperature distribution during spraying. The model has been validated experimentally using thermocouple measurements obtained during the production of 35 kg (340 mm diameter) IN718 rings and qualitative correlations have been observed between the predicted data and the type/distribution of porosity and second phase precipitates in the deposit. The model is currently being further developed and integrated with droplet size distribution and cooling models to provide a better insight into the physics and operational parameters which control deposit shape and microstructure.     

Droplet breakup in electrostatic spray based on multiple physical fields

A droplet breakup model was proposed for simulating electrostatic spray in multiple physical fields. The static electricity, laminar flow and droplet atomization in COMSOL Multiphysics were coupled completely, and a two-dimensional simulation model was established. The process of droplet breakup and movement of electrostatic spray was revealed under the action of electric field, gravity field and air field. The electric field distribution under the needle ring electrode configuration was studied. The effects of different electrostatic voltage, needle ring distance and ring electrode diameter on droplet breakup characteristics, distribution uniformity and charge characteristics were analyzed. When the electrostatic voltage is -6 ～ -7 kV, the needle ring distance is 4 mm, and the ring electrode diameter is 30 mm, the electrostatic spray effect is better, and the density standard deviation is as low as 0.04528 /mm², 0.0559 /mm² and 0.06016 /mm², respectively. Electrostatic spray has the characteristics of refining droplets, improving the uniformity of droplets distribution and controlling spray morphology, which provides a strong basis for the application of electrostatic spray in surface film preparation, dust removal, fuel injection and other practical engineering fields.     

On the role of particle state and deposition procedure on mechanical,tribological and dielectric response of high velocity oxy-fuel sprayed alumina coatings

It is well known that the high velocity oxy-fuel based thermal spray process impart high density and reduced porosity in coatings compared to those produced by other ambient thermal spray processes. The benefits of HVOF have largely remained in the domain of metals and cermets and limited investigations have been carried out in ceramic coatings. The ability to produce high density ceramic coatings (e.g. alumina) offers potential in high performance applications in the field of wear, corrosion resistance and dielectric coatings. However, due to extreme operational limits of the HVOF process, the fundamentals of process–structure–property relationships are not fully understood.In this paper, we report an integrated approach to establish processing–microstructure–property correlations in order to optimize coatings for such applications. This approach involves diagnostic studies, microstructure development and its resultant influence on properties of high velocity oxy-fuel (HVOF) sprayed alumina coatings. The diagnostic studies were aimed to investigate the effects of fuel gas/oxygen ratio and amount of total gas flow on the particle temperature and velocity. Furthermore, splats and coatings were deposited to investigate the relationship between diagnostic data, melting behavior and droplet substrate interactions. Such a comprehensive study, coupled with property measurements of the coatings, demonstrates critical operational variables among deposition procedure, coating microstructure and the deposit properties.     

Spray Atomized and Codeposited Al-Li Based Metal-matrix Composites Processing and Properties

In spray atomization and codeposition, a molten stream of metal is disintegrated into a fine dispersion of droplets by high velocity gas jets. The resulting semi-solidified droplets are directed towards a substrate where they impact and collect as rapidly solidified splats. Relatively high rates of solidification are achieved as a result of the thinness of the splats and the rapid heat extraction during flight and upon impacting with the substrate. The processing method uses codeposition of the metallic semi-solidified droplets (metallic matrix) with the injected reinforcement ceramic particles. In the present paper, the microstructures, mechanical properties, interfacial properties, thermal stability and aging behaviour of spray atomized and codeposited Al-Li-X MMC's (injected X=SiC, Al2O3) are reported and correlated to the processing conditions.     

Inside Front Cover: Anti‐Lotus Effect for Nanostructuring at the Leidenfrost Temperature (Adv. Mater. 9/2007)

The scanning electron microscopy image (tilted, colored) shown on the inside cover depicts a ring of zinc oxide particles. This ring was obtained from a droplet of a highly diluted solution of zinc acetate by overheating on a 250°C hot silicon substrate, a method reported by Rainer Adelung and co‐workers on p. 1262. The overheating creates an explosion, which results in a spray of microscale droplets that form many rings similar to the one shown over a macroscopic substrate surface.     

Investigation of atomization concepts for large‐scale flame spray pyrolysis (FSP)

Flame spray pyrolysis (FSP) is a versatile process for the production of inorganic nanoparticles featuring the advantage that the reagents are directly dissolved in the liquid fuel that is atomized to form the burning flame. A majority of previous studies on flame spray pyrolysis is focused on the formation and growth processes of the nanoparticles but neglect the preceding step of precursor atomization and spray formation. In this work an atomization concept for large‐scale nanoparticle production by flame spray pyrolysis is presented. A pressure swirl nozzle is applied for creating a liquid hollow cone, and in a second step, different dispersion gas nozzles are utilized to enhance the atomization of the liquid phase and to influence the spray cone formation and geometry. The relevant parameters influencing the atomization process (dispersion gas feed rate, liquid feed rate) are investigated (for air, water) in non‐burning (cold) spray conditions in order to access the utilization of the different atomizer concepts for the flame spray pyrolysis‐process. Measurements are conducted by applying high speed camera imaging (HSC), particle image velocimetry (PIV) and laser diffraction spectroscopy (LDS). Computational fluid dynamics (CFD) revealed further insight into the gas entrainment and the trajectory of droplets within the spray. Results show that the liquid volume flow rate (and thus the productivity of the process) may be increased significantly while still maintaining an appropriate droplet size compared to the conventional atomization process conditions in flame spray pyrolysis reactors.     

A novel ceramic printing technique based on electrostatic atomization of a suspension

A novel computer-controlled method of depositing ceramic droplets, according to a pre-determined architecture is described. A 21 vol% alumina suspension flowing through a nozzle was subjected to electrostatic atomization in the cone-jet mode at different applied voltages. By using a point-like ground electrode the resulting spray was focused and printed on a substrate placed between the nozzle and the ground electrode. The substrate was moved with the aid of a 2-axis computer controlled stepper motor driven system which enabled the forming of different ceramic architectures. As an example, the word CERAMIC was printed. At an applied voltage of 10 kV, droplet relics in the print were in the size range 30–60 μm. Electronic Publication     

Influence of the HVOF spraying process on the microstructure and corrosion behaviour of Ni-20%Cr coatings

The microstructure and the aqueous corrosion resistance of coatings produced by High Velocity Oxy-Fuel (HVOF) spraying techniques has been investigated. Two types of spraying processes have been employed i.e., Topgun HVOF using propylene gas and Met-Jet II HVOF with kerosene liquid fuel together with two forms of Ni-20%Cr powders i.e., water and inert gas atomised. The oxide, porosity and the amount of melted material in the coatings were characterised using scanning electron microscopy (SEM) and X-ray diffraction (XRD), whilst the corrosion resistance of the coatings and the ability to protect the underlying mild steel substrate was evaluated by use of a salt spray chamber and potentiodynamic tests.MetJet II produced coatings from gas-atomised powder with a lower oxide content, a reduction in porosity and less melted material, as the residence time of particles in the combusted gas stream was shortened. Water atomised powder formed a higher volume fractions of unmelted material and porosity when compared with gas-atomised powder coatings. This was encouraged by the presence of a thin oxide layer, which formed during the production of the water-atomised powder. The orientation of oxides and pores in the coatings had a major effect on their aqueous corrosion behaviour. Better protection for the underlying steel substrate (>3000 h exposure in a salt spray test) was obtained with the coating produced from the gas-atomised powder with the MetJet II system, which had the lowest porosity/oxide content running perpendicular to the substrate surface. The major factor in preventing attack on the mild steel substrate is the amount of interconnecting porosity which allows the corrodant to percolate through the coating.     

Influence of substrate and selenization temperatures on the growth of Cu2SnSe3 films

The effects of substrate temperature and selenization temperature on the structure, composition, electrical and optical properties of Cu₂SnSe₃ films were studied systematically. Cu₂SnSe₃ films deposited at various substrate temperatures (303–573 K) by the flash evaporation method are found to be non-stoichiometric. To compensate the selenium deficiency and obtain a single-phase, an annealing Cu₂SnSe₃ films deposited at 573 K was performed in selenium atmosphere. Cu₂SnSe₃ films deposited at a substrate temperature of 573 K and then selenized at 673 K were single phase and polycrystalline exhibiting monoclinic structure. The films showed p-type conductivity with a direct band gap of 0.84 eV.     

Initial stages of deposition and film formation during spray pyrolysis — Nickel oxide, cerium gadolinium oxide and mixtures thereof

The formation of nickel oxide (NiO), cerium gadolinium oxide (CGO) and NiO-CGO thin films by air blast spray pyrolysis was studied at two scales. First, single droplets of precursor were deposited on sapphire substrates and the morphology of the formed residue was studied as a function of the substrate surface temperature, type of metal salt, salt saturation, and organic solvent in the precursor. Second, the synthesis of continuous films from repetitively deposited droplets and crack formation in the films were studied as a function of substrate temperature and salt decomposition kinetics. Nitrates, acetates, perchlorates and chlorides of nickel, cerium and gadolinium were the metal salts used, and mixtures of ethanol or water with di-, tri- and tetraethylene glycol were used as solvents.Regular ring- or disc-shaped deposits were formed from single droplets that evaporated without boiling and were mainly observed with metal acetate- and chloride-based spray solutions or at low substrate temperatures. Disc-shaped residues were obtained for saturated salt solutions and changed to rings with diminishing rim thickness with decreasing salt saturation. The formation of bubbles in the droplet from boiling or salt decomposition during evaporation resulted in the distortion of the circular shape and was predominantly observed for metal nitrate-based precursors and at high substrate surface temperatures.Continuous, dense and crack-free films of CGO and NiO-CGO with thicknesses up to 500 and 800 nm, respectively, were prepared from metal nitrate/chloride mixtures in a tetraethylene glycol-based solvent. The maximum crack-free thickness decreased with decreasing deposition temperature and was correlated to the metal salt decomposition kinetics.     

脱硫废水烟气喷射蒸发流动特性实验研究

确保喷雾液滴在接触烟道壁面前完全蒸发,是保障电站脱硫废水在锅炉尾部烟道内蒸发处理安全运行的关键。喷雾液滴的破碎、聚并等动力学行为,以及液滴群的粒径分布和速度等因素的影响机制,是喷雾蒸发的主要特性。设计搭建了热态风洞实验台,利用激光粒度分析仪和粒子图像测速仪（particle image velocimeter,PIV）,在不同的引射空气压力、喷嘴水流量,以及风速、加热空气温度等条件下,对喷雾液滴群的粒径变化和速度变化进行了测量和分析。实验结果表明：以大液滴形态离开喷嘴的射流在引射气流的携带作用下,因破碎而形成小液滴,而后液滴间聚并效果会显现出来。液滴初始粒径仅与引射气体压力和水流量有关;风速的提高一定程度上会促进液滴间的聚并。提高高压气体压力、温度、风速以及减小水流量均有助于提高液滴群速度,其中提高风速对液滴群的增速效果最为明显。研究结果为喷雾的数值模拟及工程应用改进方向提供了参考。     

Simulation of a spray scrubber performance with Eulerian/Lagrangian approach in the aerosol removing process

In this study, a mathematical model has been developed to simulate the performance of a spray scrubber in an industrial ammonium nitrate plant. The model is based on the Lagrangian approach for the droplets movement and particle source in cell (PSI-CELL) model for calculating the droplet concentration distribution. Consequently, unlike former research, the emphasis is on the droplet dynamic behavior. In the current study, for approaching a realistic model, a droplet size distribution rather than average diameter, and also liquid film formation rather than uniform and constant droplet flow rate has been applied. Also, the Eulerian method has been used for the calculation of the particles removal efficiency and energy balance has been applied on the gas to estimate the droplet size distribution. In the experimental section, the concentration of particles and their size distribution in both inlet and outlet gas of the studied scrubber has been measured for the validation of the predicted particles collection efficiency. In addition, the temperature of the gas at inlet, outlet and in the middle of the tower has been measured for the confirmation of the predicted droplet size distribution in the tower. A good consistency between the model and data has been observed. After the model is validated, it is used to investigate the various variable profiles such as liquid film, total projected surface area of the droplets, velocity profile of the droplets and some of the other parameters in the spray scrubbers.     

Influence of process variable and physicochemical properties on the granulation mechanism of mannitol in a fluid bed top spray granulator

This study investigated the influence of specific process variables, including the hydroxypropyl cellulose (HPC) binder solution atomization, on the fluidized bed top spray granulation of mannitol. Special attention was given to the relationship between wetting and the granule growth profile. The atomization of the HPC binder solution using a binary nozzle arrangement produced droplets of decreasing size as the atomization pressure was increased, while changes in the spray rate had little effect on the mean droplet size. Increasing the HPC binder concentration from 2 to 8% w/w increased the binder droplet size and was most likely attributed to higher solution viscosity. The top spray granulation of mannitol showed induction type growth behavior. Process conditions like high spray rate, low fluidizing air velocity and binder solution concentration that promote the availability of HPC binder solution at the surface of the particles appeared to be key in enhancing nucleation and growth of the granules. Increasing the bed moisture level, up to a certain value, reduced the contribution of attrition to the overall growth profile of the granule and, more significantly, produced less granule breakage on drying. It was observed that the mean granule size could be reduced as much as 40% between the end of granulation and the end of drying for lower initial bed moisture level despite a shorter drying phase. High atomization pressure, especially when maintained during the drying phase, contributed substantially to granule breakage.     

Influence of Process Variable and Physicochemical Properties on the Granulation Mechanism of Mannitol in a Fluid Bed Top Spray Granulator

This study investigated the influence of specific process variables, including the hydroxypropyl cellulose (HPC) binder solution atomization, on the fluidized bed top spray granulation of mannitol. Special attention was given to the relationship between wetting and the granule growth profile. The atomization of the HPC binder solution using a binary nozzle arrangement produced droplets of decreasing size as the atomization pressure was increased, while changes in the spray rate had little effect on the mean droplet size. Increasing the HPC binder concentration from 2 to 8% w/w increased the binder droplet size and was most likely attributed to higher solution viscosity. The top spray granulation of mannitol showed induction type growth behavior. Process conditions like high spray rate, low fluidizing air velocity and binder solution concentration that promote the availability of HPC binder solution at the surface of the particles appeared to be key in enhancing nucleation and growth of the granules. Increasing the bed moisture level, up to a certain value, reduced the contribution of attrition to the overall growth profile of the granule and, more significantly, produced less granule breakage on drying. It was observed that the mean granule size could be reduced as much as 40% between the end of granulation and the end of drying for lower initial bed moisture level despite a shorter drying phase. High atomization pressure, especially when maintained during the drying phase, contributed substantially to granule breakage.     

Solidification contact angles of molten droplets deposited on solid surfaces

Droplet impact and equilibrium contact angle have been extensively studied. However, solidification contact angle, which is the final contact angle formed by molten droplets impacting on cold surfaces, has never been a study focus. The formation of this type of contact angle was investigated by experimentally studying the deposition of micro-size droplets (∼39 μm in diameter) of molten wax ink on cold solid surfaces. Scanning Electron Microscope (SEM) was used to visualize dots formed by droplets impacted under various impact conditions, and parameters varied included droplet initial temperature, substrate temperature, flight distance of droplet, and type of substrate surface. It was found that the solidification contact angle was not single-valued for given droplet and substrate materials and substrate temperature, but was strongly dependent on the impact history of droplet. The angle decreased with increasing substrate and droplet temperatures. Smaller angles were formed on the surface with high wettability, and this wetting effect increased with increasing substrate temperature. Applying oil lubricant to solid surfaces could change solidification contact angle by affecting the local fluid dynamics near the contact line of spreading droplets. Assuming final shape as hemispheres did not give correct data of contact angles, since the final shape of deposited droplets significantly differs from a hemispherical shape.