Elektrolytische Abscheidung von Aluminium‐Magnesium‐Legierungen aus aluminiumorganischen Komplexelektrolyten

Electrolytic Deposition of Aluminium‐Magnesium‐Alloys from Electrolytes Containing Organo‐Aluminium Complexes The galvanic deposition of pure aluminium from fluoride‐containing electrolytes has been developed further and for the first time aluminium and magnesium have been deposited from a toluene‐solution of a halide‐free organo‐aluminium complex electrolyte. The rate of incorporation of magnesium can be controlled over a wide range by either adjusting the composition of the aluminium‐magnesium anode or by using separate aluminium or magnesium anodic circuits. The current efficiency for both anode and cathode approaches 100%. The resulting coating is optically attractive and, depending upon the magnesium‐content or the cathodic current density, can be formed as a dull or polished surface. Investigations using an electron microscope show that the surface, in contrast to that of pure aluminium, consists of spherical particles. The aluminium‐magnesium coating provides excellent protection against the corrosion of magnesium components. Electrochemical investigations using, for example 25% by weight magnesium incorporation, indicate a pronounced passivity interval compared to the alloy AZ91hp. In contrast to galvanic zinc‐plated and silicate‐sealed examples, cyclic corrosion tests on screws simulating 10 years of exposure, show no corrosion.     

Herausforderungen an Füge‐ und Oberflächentechnik für zukünftige Leichtbaukonstruktionen im Automobilbau

For the reduction of the weight of vehicle hot‐rolled magnesium alloys as well as carbon fiber reinforced plastics (CFK) shall be integrated into the body structure. Both light weight materials electrochemically are not compatible with galvanized steels or aluminium alloys, unless great efforts of corrosion protection measures are taken. From electrochemical investigations an oxidceramic surface layer deposited by plasmachemical oxidation can be recommended as a promising solution. The low‐porous oxidation deposit with limited insulation effect can be painted by e‐coat in high quality after joining in the body shop and before the full paint system will be deposited. In opposite to magnesium CFK parts have, however, electrochemically a very noble character causing galvanic corrosion of attached metallic parts when the carbon fibers are not fully embedded in the matrix or damaged by the cutting. Only joining elements made from stainless steels or titanium alloys (e. g. Ti‐6Al‐4V) are suitable for the joining of CFK by screwdriving and riveting technology to avoid galvanic corrosion. From view of compatibility of materials, a severe anodic corrosion risk can be eliminated by isolation through adhesive bonding in the flanges and an additional sealing to prevent from electrolyte ingress.     

A study of corrosion performance of electroless Ni–P and Ni–W–P coatings on AZ91D magnesium alloy

The autocatalytic nature of the electroless nickel‐based alloy coating process will inevitably produce H₂ bubbles which may be left in electroless nickel‐based alloy coating. If the H₂ cannot be removed and left in the coating, it can lead to its poor corrosion resistance due to hydrogen cracks. So, the post treatment is an essential step for electroless deposition process. In this paper, electroless Ni–P and Ni–W–P coatings with chromium‐free pretreatment and dehydrogenation post treatment have been successfully prepared on AZ91D magnesium alloy, and the corrosion behaviors of the two kind coating samples in NaCl solution, HCl solution, and H₂SO₄ solution have been investigated. Both the polarization test and immersion tests show that the electroless Ni–W–P coating has better corrosion resistance than that of electroless Ni–P coating.     

Design of wear and corrosion resistant PVD‐coatings for magnesium alloys

Although magnesium alloys became popular in the first half of the 20^th century, the bad corrosion properties prevented their breakthrough in industrial mass production. Since the technology for the production of high purity alloys was introduced in the 1970s, magnesium alloys became more and more in the focus of industrial attention. Today magnesium alloys are state of the art in structural parts in automotive industry. Despite its outstanding properties like good castability, low density and nearly unlimited availability the negative aspects like weak corrosion and wear behaviour still limit the application of magnesium in industry [1]. So, the only economic solution is the deposition of a coating or a suitable surface treatment which provides both, wear and corrosion resistance. Today, plasma electrolytic anodisations are state of the art [2–5]. They provide acceptable corrosion resistance and protect the magnesium from mechanical damage due to their high hardness. On the other hand, their high porosity limits their use in combination with electrochemically noble materials, leading to galvanic corrosion [6]. In addition, the high surface roughness of the plasma electrolytic anodisations restricts their use in tribological applications, particularly under dry sliding conditions [7]. On the other hand, due to the high life time recommendations the application of magnesium in the automotive industries motion component field is a long term process. Nevertheless, there is a quite high industrial interest to apply magnesium in the motion component field in consumer applications like do‐it‐yourself or gardenig. Some examples are motor components of lawnmovers, motor saws or drills. Especially for these fields of application there are quite high demands on the corrosion properties due to undefined storage and the conditions during usage. In order to achieve smooth surfaces with high quality, the PVD technology moves into the centre of interest. Since the 1980s PVD coatings are well established and widely used for different industrial applications, mainly for steel and tool coatings. The authors were the first who carried out serious studies on the development of PVD coatings for magnesium alloys since 1999 [6, 7]. The extensive research activities lead to the recent development of a coating system, which provides both, good wear properties as well as good corrosion behaviour.     

Aluminization of nickel-formation of intermetallic phases and Ni2Al3 coatings

The occurrence and growth mechanisms of the various intermetallic phases of the Al-Ni system formed during pack aluminization of unalloyed nickel have been investigated with respect to the aluminium activity in the pack. Several types of coatings were obtained: (1) a Ni₂Al₃ coating formed by inward aluminium diffusion in a high activity cement of pure aluminium; (2) a Ni-rich NiAl coating formed by outward nickel diffusion in a low activity pack constituted by an Al-Ni alloy; (3) a mixed type of coating exhibiting the phases Ni₂Al₃, Al-rich NiAl, Ni-rich NiAl and Ni₃Al in four superposed layers, formed in a pack containing an Al-Cr alloy; (4) a high temperature, high activity type of coating formed above 950° C with an outer layer exhibiting a hypereutectic structure of NiAl₃ grains in a eutectic matrix due to precipitation from the liquid state. The optimum cementation conditions, for the production of maximum thickness and quality Ni₂Al₃ coatings were determined. The influence of surface reactivity and pack activity on the coating quality parameters was investigated.     

Microstructural analysis of germanium modified tin‐copper brazing filler metals for transient liquid phase bonding of aluminium

The present contribution summarises first results that have been achieved with the new brazing material Sn75Cu20Ge5 (wt‐%) for transient liquid phase (TLP) bonding of aluminium cast alloy AlSi7Mg0.3 (wt‐%). The microstructure of the braze ribbons and the obtained joints have been thoroughly investigated on different length‐scales using scanning and transmission electron microscopy as well. Whereas the braze ribbon material is only composed of beta‐tin, η‐phase (Cu₆Sn₅) and some germanium rich precipitates, the transient liquid phase joint displays a much more complex microstructure that consist mainly of beta‐tin and different aluminium‐copper and aluminium‐germanium phases. In addition small silicon oxide rods and a hitherto unreported hexagonal aluminium‐copper‐magnesium‐germanium phase with approximated lattice parameters a = 0.7123 nm, c = 2.40 nm have been found in the seam of the joint.     

Schwingfeste Auslegung von Schweiß‐ verbindungen aus der Magnesiumknetlegierung AZ31(ISO‐MgAl3Zn1) mit dem Konzept der fiktiven Ersatzradien von rf = 1,0 mm und 0,05 mm

Fatigue design of welded joints from the wrought magnesium alloy AZ31 (ISO‐MgAl3Zn1) by the local stress concept with the fictitious notch radius of r_f = 1.0 mm and 0.05 mm The investigations were carried out with three different types of MIG‐ and TIG‐welded magnesium joints of the alloy AZ31. The evaluation of the results showed that the local stress concept using the fictitious notch radius of r_f = 1.0 mm can be applied to magnesium welded joints from plates with thicknesses t ≥ 5 mm independently of the weld geometries (fully or partially penetrated butt welds, transversal stiffeners). Design curves are proposed for different stress ratios, i.e. R = ‐1 as well as 0 and 0.5, which allow the consideration of residual stresses as well as load induced mean stresses. The results permit also the suggestion of Δσ = 28 MPa as FAT‐value for the IIW‐Fatigue Design Recommendations. Further, the FAT‐value Δσ = 73 MPa for the fictitious radius of r_f = 0.05 mm to be applied to welded thin magnesium joints is derived, too. These FAT‐values are compared with already known data for steel and aluminium joints. A linear relationship between the FAT‐values and the Young’s modulus is determined.     

Analysis of morphology and microstructure of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> layers

The paper presents the characterization of obtaining Al₂O₃ oxide layers on AlMg₂ aluminum alloy as a result of hard anodizing by the electrolytic method in a three-component electrolyte. The Al₂O₃ layers obtained on the AlMg₂ alloy in the three-component SBS electrolyte were subjected to detailed microstructural investigations (by means of a scanning electron microscope). By using X-ray diffraction, the phase compositions of obtained oxide layers were examined. It was found that the Al₂O₃ oxide layers obtained via hard anodizing in a three-component electrolyte are amorphous. The chemical composition of the Al₂O₃ layers is presented and compared with the results of stechiometric calculations for the Al₂O₃ layer. Surface morphologies of the obtained oxide layers are characterized and discussed in nano- and microscopic scales. The surface morphologies of the layers obtained have a significant influence on their properties, including their susceptibility to further modification (e.g., to incorporation of graphite), their wear resistance, and the capacity for sorption of lubricants.     

Structure and morphology of TiB2 duplex coatings deposited over X40 CrMoV 5-1-1 steel by DC magnetron sputtering

The deposition of titanium diboride (TiB₂) films over tool steel substrates (AISI H13 premium/EN X40 CrMoV 5-1-1) is being investigated due to its excellent corrosion resistance and chemical stability against liquid aluminium. The use of nitrided steels as substrates for TiB₂ deposition may contribute to increase its adhesion and the overall steel resistance in applications such as forging, extrusion and die casting of aluminium. Duplex coatings were obtained by the PVD deposition of TiB₂ films over heat treated and nitrided steel using non-reactive DC magnetron sputtering from a TiB₂ target, varying the substrate bias voltage. Well structured and crystalline TiB₂ films were obtained for the selected deposition conditions, the best crystalline coatings being obtained for the positively biased substrates. Selected films produced over die-casting pins at a bias voltage of +50 V were tested for resistance to liquid aluminium soldering by immersion tests, and compared with the nitrided steel. The duplex TiB₂ coating has a much larger chemical resistance to attack by molten aluminium alloy than the just nitrided steel. Where there is soldering, steel is rapidly attacked and a complex Al-Fe-Si intermetallic forms.     

Characterization of the protective effect of aluminium surface treatments by d.c. and a.c. measurements

Steady-state and electrochemical impedance spectroscopy measurements have been made on anodic layers on 1050 and 2024T3 aluminium alloys prepared from solutions of phosphoric acid, boric acid and sodium tetraborate, before and after impregnation treatment with zinc. Corrosion characteristics of the anodic layers were dependent on the aluminium substrate and the electrolyte. Aluminium alloy composition was found to be the most important factor for corrosion resistance; alloying elements of 2024T3 alloy (like copper) had a harmful influence on this layer property. Steady-state measurements allowed the oxide layer behaviour to be studied in the anodic range by the determination of an anodic passivity domain. This domain was characterized by a weak aluminium oxidation through the oxide layer. The zinc impregnation treatment had a marked protective effect on each studied anodic layer. This treatment can be used as an alternative to hot sealing in water or chromic acid solution.     

Corrosion behaviour of some vapour deposited magnesium alloys

Abstract

Binary magnesium alloys containing chromium, manganese, or titanium were made using a physical vapour deposition technique. The corrosion resistance of the alloys was assessed in aqueous chloride solutions using total immersion tests in quiescent 600 mmol L^?1 NaCI solutions. Alloying with manganese or titanium was found to lower the corrosion rate of magnesium over most of the compositional ranges of interest, whereas addition of chromium had a detrimental effect on the corrosion resistance of magnesium. The lowest corrosion rate was recorded for a Mg–Ti alloy where the value obtained was about 80 times lower than that found for vapour deposited pure magnesium. Open circuit corrosion potential measurements conducted in 600 mmol L^?1 NaCl solution showed that additions of chromium, titanium, and manganese also produced deposits which were significantly more noble than pure magnesium, suggesting that these alloys would be less susceptible to galvanic corrosion.

MST/3064     

Surface alloying of magnesium and AZ91 by thermochemical treatment in a medium containing zinc chloride and potassium chloride

Surface layers enriched with zinc were formed on pure magnesium and AZ91 alloy by heating the specimens in contact with paste containing zinc chloride and potassium chloride at 440 °C for 2 h, using no protective atmosphere. The study involved determining the microstructure, phase composition and microhardness of the resulting layers. During the layer formation process, a transient liquid phase occurred at the substrate/paste interface. The layers fabricated on both substrates were about 200 μm in thickness and they were metallurgically bonded to the substrate material. The same process conditions were used for both types of substrates. From the experimental data it is clear that the layer fabricated on magnesium differed in microstructure from that formed on AZ91. The alloyed layer on magnesium was characterised by dendrites of a solid solution of zinc in magnesium surrounded by a lamellar eutectoid structure composed of an MgZn intermetallic phase and a solid solution of zinc in magnesium. In the layer formed on AZ91, aluminium was detected in all the structural constituents. The layer was composed of a solid solution of zinc and aluminium in magnesium and Mg₁₇(Al, Zn)₁₂ and Mg₅Al₂Zn₂ intermetallic phases. The alloyed layers had much higher hardness than the substrate materials.     

Influence of coating on short steel fiber reinforcements on corrosion behavior of aluminium base short steel fiber reinforced composites

Steel fiber reinforced aluminium composites are attractive materials of high specific strength but exhibit poor resistance against electrochemical corrosion. The study discusses the electrochemical corrosion behavior of uncoated, copper and nickel coated short steel fiber reinforced aluminium and Al–2Mg matrix composites in 1 (N) NaCl solution. Galvanic corrosion between the steel fiber and aluminium governs the corrosion behavior of these composites. It has been observed that open circuit potential (OCP) is shifted to more negative side with copper coating on the fibers and to the more positive side on coating the fibers with nickel. Compared to the uncoated fiber higher corrosion current density indicates corrosion rate was observed for the copper coated fiber reinforced composites where as a lower current density was noted for the nickel coated fiber reinforced composites was observed. Addition of 2 wt% magnesium to aluminium alloy matrix increased the corrosion current density. The corrosion mechanism in these composites is dominated by galvanic cell formation that is evident from the dissolution of Al matrix near the peripheral region of steel fibers.     

Kerbgrundkonzepte für die schwingfeste Auslegung von Aluminiumschweißverbindungen am Beispiel der naturharten Legierung AlMg4,5Mn (AW‐5083) und der warmausgehärteten Legierung AlMgSi1 T6 (AW‐6082 T6)

Fatigue design of aluminium welded joints by the local stress concept exemplarily shown on the naturally aged wrought aluminium alloy AW‐5083 and the artificially aged wrought aluminium alloy AW‐ 6082 T6 Local fatigue design concepts based on material‐ and microstructural‐related parameters, e.g. the microsupport‐concept, cannot be regarded as easily applicable. The investigations, which compared the micro‐support‐concept with the local stress concept with a fictitious notch radius r_f, were carried out with different types of MIG‐welded joints of the aluminium alloys AW‐5083 and AW‐6082 T6 under fully reversed and pulsating axial loading. The evaluation of the results showed that the local stress concept using the fictitious notch radius of r_f = 1.0 mm can be applied to aluminium welded joints from plates with thicknesses t ≥ 5 to 25 mm independently from the alloy and weld geometries (fully or partially penetrated butt welds, transversal stiffener). Master design curves are proposed for different stress ratios, i.e. R = ‐1, 0 and 0.5, which allow the consideration of residual stresses as well as load induced mean stresses. The results permit also the suggestion of Δσ = 70 MPa as FAT‐value for the IIW‐Fatigue Design Recommendations     

Application of the hybrid process ultrasound enhanced friction stir welding on dissimilar aluminum/dual‐phase steel and aluminum/magnesium joints

Friction stir welding as a solid‐state joining method with its comparatively low process temperatures is suitable for joining dissimilar materials like aluminum/magnesium or aluminum/steel. Such hybrid joints are of great interest regarding lightweight efforts in different industrial fields like the transportation area. The present work investigates the influence of additionally transmitted power ultrasound during the friction stir welding on the joint properties of EN AC‐48000/AZ91 and EN AW‐6061/DP600. Therefore, conventional friction stir welding was continuously compared to ultrasound enhanced friction stir welding. Light microscopic analysis and nondestructive testing of the joints using x‐ray and high frequency ultrasound show different morphologies of the nugget for the aluminum/magnesium joints as well as differences in the amount and size of steel particles in the nugget of aluminum/steel joints. Scanning electron microcopy proves differences in the thickness of continuous intermetallic layers for the aluminum/steel joints realized with and without power ultrasound. Regarding the tensile strength of the joints the power ultrasound leads to increased joint strengths for EN AC‐48000/AZ91 joints compared to a decrease for EN AW‐6061/DP600 joints. Corrosion investigations show an influence of the ultrasound power on the corrosion properties of EN AC‐48000/AZ91 joints which is attributed to a changed aluminum content in the nugget region. Because of the great potential difference between the magnesium and the nugget phase the transitional area exhibits strong galvanic corrosion. For EN AW‐6061/DP600 joints an increased corrosion caused by galvanic effects is not expected as the potentials of the EN AW‐6061 aluminum alloy and DP600 steel are very similar.     

Abscheidung superharter Kohlenstoffschichten mittels Laser‐Arco® auf dem Weg vom Labor in die industrielle Serienfertigung

Superhard carbon film deposition by means of Laser‐Arco® on the way from the Laboratory into the industrial series coating Diamond‐like carbon films (DLC) are more and more applied as wear protection coatings for components and tools due to their unique combination of high hardness, low friction and sticking tendency to metallic counter bodies. Up to now applied DLC films are hydrogen containing (a‐C:H) or metal carbon films (Me‐C:H) deposited by a plasma assisted CVD process from carbon‐hydrogen gas mixtures. Their wide industrial effort results from that the can be deposited with slowly modified coating machines for classical hard coating (e.g. TiN or CrN). A new generation DLC films are the hydrogen‐free ta‐C films (ta‐C = tetrahedral bounded amorphous carbon) with a between two and three‐times higher hardness and with a resulting higher wear resistance under extreme condition than classical DLC films. They have excellent emergency running properties at lubrication break down. Their industrial application is more difficult due to that they cannot deposited with modified coating machines for classical hard and DLC coating and a new technology with corresponding equipment was not available up to now. The laser controlled, pulsed arc deposition technology (Laser‐Arco®) of the Fraunhofer IWS Dresden has this potential. In kind of a Laser‐Arc‐Module‐source the ta‐C film deposition can be integrated in every industrial used deposition machine.     

An electrodeposition method of calcium phosphate coatings on titanium alloy

Calcium phosphates coatings were deposited onto titanium alloy discs via en electrodeposition method. Titanium alloy discs were blasted with calcium phosphate particles, then etched in a mixture of nitric and fluoric acids and rinsed in demineralized water. The titanium alloy disc (cathode) and platinum mesh (anode) were immersed in a supersaturated calcium phosphate electrolyte buffered at pH 7.4 and connected to a current generator. The microstructure, chemical composition and crystallinity of the electrodeposited coatings were studied as function of time 10–120 min, temperature 25–80°C, current density 8–120 mA/cm², magnesium and hydrogen carbonate amounts (0.1–1 mM). Uniform calcium phosphate coatings were obtained in 30 min but coating thickness increased with deposition time. Raising the temperature of electrolyte resulted in more uniform coatings as ionic mobility increased. Low current density was preferable due to hydrogen gas evolving at the cathode, which disturbed the deposition of calcium phosphate crystals on titanium. The amounts of magnesium and hydrogen carbonate ions affected both the homogeneity and morphology of the coatings. This study showed that the electrodeposition method is efficient for coating titanium with osteoconductive calcium phosphate layers.     

Al-Zn coatings for the corrosion protection of steel

Aluminum coatings have been reported to be the most suitable for replacing toxic cadmium for the protection of steel and titanium alloys against corrosion. The relatively poor galvanic corrosion protection of aluminium coatings, however, has led to a search for a more effective coating. To this end, pure aluminium and controlled-composition Al-Zn alloy coatings were ion plated onto steel substrates. Over a range of coating conditions the aluminium and the Al-Zn alloy coatings have very similar columnar structures. They were equally successful in protecting the underlying steel. However, a simulation of the coating damage by masking the steel substrate during plating showed the galvanic corrosion protection of Al-2.5%Zn alloy coatings to be superior to that of aluminium. It is probable that this very effective sacrificial corrosion protection means that the structure of the coating is relatively unimportant and that excellent galvanic corrosion protection can be provided by low density columnar structure coatings of Al-Zn alloys.     

Plasmagestützte Beschichtung von Bauteilen bei niedrigen Temperaturen

The deposition of wear resistant coatings is possible nowadays at low temperature by the Plasma Assisted CVD process using metall organic precursors. Thus a coating of temperature sensitive materials like aluminium, magnesium and polymer at low temperature is realised. The wear resistant coatings TiCN and ZrCN were deposited on light metals at a temperature below 160°C. The mechanical properties of the layers show the potential of the coatings for parts with wear and friction. The surface hardness, the abrasive wear and the friction value are improved compared to the properties of substrate material and steel. Transparent BCN‐coatings can be used as scratch resistant coatings on polymers like polycarbonate. The layers offers good transmission by high hardness.     

Processing,microstructure and properties of ultrasonically processed in situ MgO–Al2O3–MgAl2O4 dispersed magnesium alloy composites

AZ91 alloy matrix composites are synthesized by in situ reactive formation of hard MgO and Al₂O₃ particles from the addition of magnesium nitrate to the molten alloy. The evolved oxygen from decomposition of magnesium nitrate reacts with molten magnesium to form magnesium oxide and with aluminium to form aluminium oxide. Additionally, these newly formed oxides react with each other to form MgAl₂O₄ spinel. Application of ultrasonic vibrations to the melt increased the uniformity of particle distribution, avoided agglomeration, and decreased porosity in the castings. Ultrasound induced physical phenomena such as cavitation and melt streaming promoted the in situ chemical reactions. Well dispersed, reactively formed hard oxides increased the hardness, ultimate strength, and strain-hardening exponent of the composites. Presence of well-dispersed hard oxide particles and stronger interface resulting from cavitation-enhanced wetting of reactively formed particles in the AZ91 alloy matrix improved the sliding wear resistance of the composites.