Electrolytic Tin Research Articles

Nanomechanical and Electrochemical Corrosion Testing of Nanocomposite Coating Obtained on AZ31 via Plasma Electrolytic Oxidation Containing TiN and SiC Nanoparticles

Lightweight magnesium alloys offer excellent benefits over Al alloys due to their high specific strength and damping properties, but they are more prone to galvanic corrosion. Plasma electrolytic oxidation (PEO) coatings reinforced by nanoparticles have been shown to improve corrosion resistance and possess better mechanical properties. A lot of research has been published that focuses on the effect of nanoparticle concentration in the PEO electrolyte solution, and the type of nanoparticle, on the properties obtained. The aim of paper is to study the effect of processing time on the nanoparticle-reinforced PEO coating on AZ31 magnesium alloy. TiN and SiC nanoparticles were produced using plasma chemical synthesis and added to KOH-based electrolyte to develop PEO coatings. The concentration of nanoparticles was kept constant at 0.5 g/L and the treatment time was varied as follows: 1, 2, 3, 5, and 10 min. The coatings were tested for their microstructure, phase, chemical makeup, nano-mechanical properties, and corrosion resistance. Nanoparticles were found to be clustered in the coating and spread unevenly but led to a decrease in the size and number of pores on the PEO coating surface. The corrosion resistance and nano-mechanical properties of the coating improved with treatment time. The hardness and contact modulus of coatings with TiN particles were 26.7 and 25.2% greater than those with SiC particles. Addition of TiN nanoparticles resulted in improved corrosion resistance of the PEO coatings when the processing time was 5 or 10 min. The lowest corrosion rate of 6.3 × 10−5 mm/yr was obtained for TiN-added PEO coating processed for 10 min.

Studies on the Reversibility of Electrolytic Tin Powder Obtained from an Ionic Liquid

Studies on the Reversibility of Electrolytic Tin Powder Obtained from an Ionic Liquid

Characteristics of Electroless Sn Plating Electrolyte using a Choline Chloride-Based Ionic Liquid

In the present study, a choline chloride(ChCl)-based ionic liquid(IL) was used as an electrolyte to confirm the characteristics of electroless tin plating. The effect of the type of additive and reducing agent, as well as the addition of complexing agent and water, on the properties of the ChCl-based IL, including the freezing point, viscosity, conductivity, open circuit potential, and plating thickness, was investigated. The results showed that the crystallization temperature was 25 ℃ when the ChCl-thiourea molar ratio was 1:1, and it decreased to 10 ℃ upon adding the additive, while the conductivity increased and viscosity decreased. Dimethylthiourea was added to promote the electroless plating reaction. Electrolytic tin plating was performed at 70 ℃ using ChCl -thiourea-based IL as the electrolyte. The thickness of the tin-plated layer was 1.5 μm when malonic acid and dimethylthiourea were used. The addition of a small amount of water increased the plating speed and thickness, and the maximum thickness of 2 μm for the tin-plated layer was obtained after 30 min. These characteristics demonstrate the potential applications of these environmentally friendly electrolytes for fast, thick, and dense electroless tin plating using ILs at low temperatures. (Received May 4, 2018; Accepted July 2, 2018)

Improving the punch and die wear behavior in tin coated steel stamping process

Prestigious brands of cookies usually use metallic tins as packaging to distribute and sell their products, trying to impress the customer through the appearance of the packaging and simultaneously avoiding smashing or damaging of the cookies during logistics operations. These packages are commonly made in a tin coated (2.8g/m2) thin steel sheet (ARCELOR electrolytic Tin plate), which causes severe wear problems on both die and punch tool components during the stamping process at room temperature. The border of the package presents an inconsiderable deformation, despite its almost perpendicular orientation to the top surface, but this top is usually patterned, which also implies the flow of the sheet between the top and bottom die surfaces. Due to the softness of the Tin coating, it easily adheres to the die, generating premature wear and several other concerns in maintaining the required final shape of the tin lid. Lubrication would be an easy way to solve the problems referred above however, lubricated operations should be avoided as these kinds of packages are for food purposes.This study started by identifying the main wear mechanism developed in the main surfaces of the stamping tool, promoted by the Tin coated steel sheet used in the packages. Two advanced PVD coatings (B4C and Mo) were tested, leading to the improvement of the punch and die wear behavior under these working conditions. The transfer of Tin material from the metallic sheet to the punch and die was studied, as well as the friction coefficient of this sheet against some selected coatings, while also trying to minimize the Tin adherence to the surface of the tool. Tribological tests under medium loads were carried out in order to ascertain what kind of coating presents better wear behavior in the referred work conditions. Regarding the obtained results, some improvements will be applied to the coating structure to adjust the deposition parameters in order to go forward to industrial tests. Worn surfaces were studied by Scanning Electron Microscopy (SEM) and material transfer was analyzed by Energy Dispersive Spectroscopy (EDS).Results obtained with some of the tested coatings confirm that it is possible to minimize the Tin transfer from the covered steel sheet to the die and punch, ensuring a longer life of these parts, decreasing the tool maintenance operations and improving the Overall Equipment Efficiency (OEE) of that stamping process.

Increasing the stamping tools lifespan by using Mo and B4C PVD coatings

Prestigious brands of cookies usually use metallic tins as packaging to distribute and sell their products, trying to impress the customer through the appearance of the packaging and avoiding smashing or damages to the cookies during logistics operations. These packages are commonly made in a tin coated (2.8g/m2) thin steel sheet (ARCELOR electrolytic Tin plate), which causes severe wear problems on both die and punch tool components during the stamping process at room temperature. The border of the package presents an inconsiderable deformation, despite its almost perpendicular orientation to the top surface, but this top is usually patterned, which also implies the flow of the sheet between the top and bottom die surfaces. Due to the softness of the Tin coating, it easily adheres to the die, generating premature wear and several other concerns in maintaining the required final shape of the tin lid. Lubrication would be an easy way to solve the problems referred above, but lubrication operations should be avoided because these kind of packages are for food purposes.This study started by identifying the main wear mechanism developed in the stamping tool main surfaces, characterized by the Tin coated steel sheet used in the packages and testing two advanced PVD coatings (B4C and Mo) leading to the improvement of punch and die wear behavior under these work conditions. The transfer of Tin material from the metallic sheet to the punch and die was also studied, as well as the friction coefficient of this sheet against some selected coatings, while also trying to minimize the Tin adherence to the tool surfaces. Tribological tests under medium loads were carried out in order to ascertain what kind of coating presents better wear behavior in those work conditions. Regarding the results obtained, some improvements will be applied to the coating structure to adjust the deposition parameters in order to go forward to industrial tests. Worn surfaces were studied by Scanning Electron Microscopy (SEM) and material transfer was analyzed by Energy Dispersive Spectroscopy (EDS).Results obtained with some of the tested coatings confirm that it is possible to minimize the Tin transfer from the covered steel sheet to the die and punch, ensuring a longer life of these parts, decreasing the tool maintenance operations and improving the Overall Equipment Efficiency (OEE) of that stamping process.

Complex evaluation and development of electrolytic tin refining in acidic chloride media for processing tin-based scrap from lead-free soldering

Different ways of investigation were applied to address the main difficulties of electrolytically refining the tin-based lead-free soldering waste materials in chloride solutions. The characteristics of electrorefining and the phenomena of electrocrystallisation have been targeted by examining the electrode processes with different copper and silver concentrations in the anodes. Galvanostatic experiments were carried out using a specially developed system detecting the changes in the electrode masses continually, complemented by the recording of the electrode potentials. In order to clarify the main cathode and anode processes, further investigations were carried out by the potentiodynamic technique. Galvanostatic results pointed out the causes of current losses and rough deposit structure. Potentiodynamic examinations have demonstrated the strong influence of material transport on the electrode processes. Nevertheless, with a quasi-optimised procedure, cathode tin of higher purity than technical standards could be achieved from the soldering waste material in a conventional cell.

Effect of the nature of a ligand on electrochemical characteristic of tin films in cycling in lithium-ion batteries

Potentiodynamic and galvanostatic cycling in 1 M ethylene carbonate-dimethyl carbonate solution of LiClO4 were used to study electrolytic tin films deposited from complex (tartrate, citrate, and citrate-trilonate) electrolytes. It was shown that the nature of a ligand strongly affects the electrochemical characteristics, specific capacity of tin films, and efficiency of their cycling in lithium power sources. The most stable charge-discharge characteristics are inherent in tin films deposited from the citrate electrolyte.

The Elimination of Whiskers from Electroplated Tin

Purpose – The purpose of this paper is to present new developments in electrolytic tin plating designed to eliminate the formation of whiskers over time, when tin is plated on copper.Design/methodology/approach – Two main approaches were undertaken to achieve the desired results. The first was modification of the copper substrate prior to plating and the second was to modify the crystal structure of the tin deposit.Findings – With the use of specific additives to the tin plating bath it was possible to achieve a crystal structure similar to that of the non‐whiskering tin/lead.Research limitations/implications – The technology is presently available commercially to plate electronic parts such as connectors and lead frames, etc.Originality/value – The paper details a modified electroplating tin bath that produces a deposit that will not form whiskers over time.

Electrolytic Deposition of Fine Pitch Sn/Cu Solder Bumps for Flip Chip Packaging

Current methods for the formation of pre-solder bumps for flip chip attachment use stencil printing techniques with an appropriate alloy solder paste. The continuing trend towards increased miniaturization and the associated decrease in size of solder resist opening, SRO is causing production difficulties with the stencil printing process. Practical experience of production yields has shown that stencil printing will not be able to meet future requirements for solder bump pitch production below 150μm for these applications. This paper describes latest developments in the electrolytic deposition of solder to replace the stencil printing process; results from production of 90μm bump pitch solder arrays with tin/copper alloy are given. The solder bump is produced with a specially developed electrolytic tin process which fills a photo resist defined structure on the SRO. The photoresist dimensions determine the volume of solder produced and the subsequent bump height after reflow. Investigations on the bump reliability after reflow are shown including copper alloy concentration at 0.7% and x-ray investigation to confirm uniform metal deposition. The self centering mechanism found in the bump production process during reflow is presented and the capability to correct photoresist registration issues. The solder bumps are shown as deposited onto an electroless nickel/gold or electroless nickel/palladium/gold final finish which serves also as a barrier layer to copper diffusion into the solder bump. Discussion of further development work in the production of alloys of tin/copper together with silver are given with first test results.

The elimination of whiskers from electroplated tin

PurposeThe purpose of this paper is to present new developments in electrolytic tin plating designed to eliminate the formation of whiskers over time, when tin is plated on copper.Design/methodology/approachTwo main approaches were undertaken to achieve the desired results. The first was modification of the copper substrate prior to plating and the second was to modify the crystal structure of the tin deposit.FindingsWith the use of specific additives to the tin plating bath it was possible to achieve a crystal structure similar to that of the non‐whiskering tin/lead.Research limitations/implicationsThe technology is presently available commercially to plate electronic parts such as connectors and lead frames, etc.Originality/valueThe paper details a modified electroplating tin bath that produces a deposit that will not form whiskers over time.

Initial stages of indoor atmospheric corrosion of electronics contact metals in humid tropical climate: tin and nickel

Samples of electrolytic tin and nickel have been exposed for 1 to 12 m in indoor environment, inside a box (rain sheltered cabinet), placed in tropical humid marine-urban climate, as a part of Gulf of Mexico. The corrosion aggressiveness of box has been classified as a very high corrosive, based on the monitored chlorides and SO 2 deposition rates, and the Temperature/Relative Humidity air daily complex. The annual mass increasing of nickel is approximately twice higher than its values of mass loss (C). The relation between nickel mass loss or increasing and time of wetness (t) of metal surface is linear and does not obey the power equation C = A t n , which has be found for tin. The SEM images reveal a localized corrosion on nickel and tin surfaces. XRD detects the formation of SnCl 2 .H 2 O as a corrosion product. Within the time on the tin surface appear black spots, considered as organic material.

Characterization of electrolytic tin dioxide deposition on Pt for lithium ion battery applications

By using cathodic electrodeposition, three structures of Sn, Sn 6O 4(OH) 4 and SnO 2 could be obtained in the 1 mM SnCl 2 aqueous solution for various aeration periods in air. In order to obtain the pure SnO 2 coatings as the anode of thin-film lithium ion battery, the aeration should proceed for 10 days to oxidize tin valence from stannous to stannic in SnCl 2 aqueous solution. The coating films were further annealed and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FTIR), thermogravimetric–differential analysis (TGA), Raman spectroscopy, and cyclic voltammetry (CV). The as-coating SnO 2 film containing 2.4 H 2O in the pristine state could be dehydrated at 300 °C for 2 h, or at 250 °C for 12 h. The crystallinity and surface coarsening of the coating films were promoted with increasing annealing temperature. The dehydrated SnO 2 film used as the anode of a lithium battery showed a reversible capacity as high as 500 mA h/g after 10 cycles at a discharging rate of 0.2 C, which could result from the nano-sized microstructure of coating film.

The effect of manganese and chromium on surface oxidation products formed during batch annealing of low carbon steel strip

Surface oxides formed at ferrite grain boundaries of low carbon steels annealed at 700 °C in 5% hydrogen 95% nitrogen atmosphere were characterized using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Two different oxides (Fe,Mn)O and MnCr 2O 4 are observed at the grain boundaries and the former is five-fold coarser than the latter. It was found at the annealing temperature of 700 °C that the mean particle size of the (Fe,Mn)O depends on the manganese content, and the mean particle size and distribution of the MnCr 2O 4 dependent on chromium, but independent of manganese. It is unlikely the coarse (Fe,Mn)O precipitates pose any potential risks to the electrolytic tin coating quality as they will be removed by the pickling operation prior to tinning. The potential risks posed by the MnCr 2O 4 to the quality of the electrolytic tin coating of tinplate products can be minimized by restricting the chromium content of the steel.

硫酸浴におけるスラッジの抑制と電気すずめっき

硫酸浴におけるスラッジの抑制と電気すずめっき

The effect of a surface oxide layer of electrolytic tin plate on the frictional properties during the ironing operation of a two-piece can-making process

Nonpassivated electrolytic tin plates without conventional chemical treatment self-oxidize in ambient atmosphere and form a yellow stain on the outermost surface during long-term storage. The degree of yellowness of the stain increased linearly with the oxide thickness due to the interference color of SnO 2. Even though the thickness of the oxide layers was very thin, less than 100 Å, it exerted an undesirable influence on the can-making processes, particularly the stripping behavior after ironing. Investigations were carried out on the morphologies of the coating layers, the changes in oxide thickness during successive can-making processes and the average friction coefficients with the different oxide thickness. These oxide layers were broken up and distributed within the bulk tin coating during the ironing process. This redistribution of the oxide layer prevented smooth pressing-aside of the tin coating layers, resulting in an increase in the ironing friction coefficient. As the friction coefficient was increased, the residual stress along the can wall thickness (i.e. the hoop stress) was also increased. Due to both the oxide layer accumulation, which increased the friction coefficient and the hoop stress, can stripping efficiency without roll-back was reduced.

The removal torque increment on metal cans containing an asphaltic pruning seal compound

AbstractA study of cap removal torque of a 16 fl.oz. electrolytic tin plate (ETP) container and closure with continuous threads as well as a 0.04 inch polyethylene (PE) liner was conducted. These packages contain a solvent asphaltic pruning seal product. At room temperature the removal torque behaviour was investigated using ETP cans with and without the product at intervals of logarithmic decades of time in days. A SWAN‐MATIC capping machine was utilized to provide predetermined application torques of 20, 30 and 40 in. lbs at 90d̀, 80d̀ and 70d̀ angles of application. The removal torque of each experimental test was measured by hand using the SECURE PAK tester machine, which provided a maximum torque reading accuracy of up to a tenth of a unit. The study revealed that ETP containers with PE‐lined ETP caps, uncontaminated with the product, exhibited logarithmic removal torque decay. However, the ETP container with the asphaltic pruning seal product spilled on the top and threads of the closure showed an increasing trend of removal torque. This occurrence was probably caused by the adhesive effect of the product at the closure.

生野製作所における錫製錬（三菱マテリアル（株））

Tin smelting at Ikuno Plant started its operation in 1913 with reverberatory furnace smelting process. In 1950, the company replaced the reverberatory furnace with an electric furnace to improve operation efficiency and recovery. In 1987, Akenobe mine was shut down. Because the production of tin concentrates was stopped, raw materials of tin decreased to half. In 1991, the tin refining plant with new technology started operation at Ikuno Plant, while the tin refining plant at Naoshima was shut down.At present, various tin bearing scraps are roasted, smelted and refined to produce about 97% crude tin. It is cast to anode and electrorefined with stainless cathode to 99.995+% electrolytic tin. Part of this electrolytic tin is reelectrorefined to 99.999+% high purity tin.Annual production of crude tin metal is 720 metric tons, electrolytic tin is 660 metric tons and high purity tin is 360kg.

Progress in materials for can stock and future trends.

Developments in electrolytic tin plate, tin-free steel and more recent low tin materials are described with emphasis on their corrosion performance and their applicability to the newer can manufacturing processes. The significance of tinplate special property tests and their relative importance are discussed as related to corrosion performance in cans for moderate to high corrosivity food products. Information regarding pitting corrosion of aluminum killed continuous cast tinplate in cans for light colored fruits is also reviewed. Tin-free and low tin materials are being used in drawn and welded cans, but better enamel coverage is required than for tinplate cans. Long term trends show that aluminum has taken over most of the beer and soft drink market but its use in food cans remains very limited. New processable multilayer plastic barrier materials have been introduced as cans, bowls and trays for single serving microwaveable foods, which could have a significant impact on metal cans. The solid waste issue and recyclability of the various materials is discussed. A new process for improving the quality of shelf stable processed foods is also described.

X-ray photoelectron spectroscopy and electrochemical analysis of passivated electrolytic tin plate surfaces

The passive layer of cathodic dichromate (CDC) and dichromate dipped (DCD) passivated tin plate was investigated by means of X-ray photoelectron spectroscopy (XPS) and electrochemical analysis.Electrochemical results were compared with atomic absorption spectroscopy and glow discharge spectroscopy data and are discussed in relation to the solid state properties of the passive layer compounds.XPS depth profiles were obtained by using a “first-principles model” for quantitative purposes and the results are evaluated on the basis of the analytical approach employed.

直島製錬所の電気錫製錬

The tin refining plant at Naoshima Smelter began operation in 1960 treating crude tin produced at Ikuno Smelter, while the tin refining plant at Osaka Refinery was shut down.At the present time, the plant, the only primary tin refinery in Japan, produces electrolytic tin of more than 99.995% at a capacity of 130 t/m.