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Non-Destructive Evaluation of Protective Coatings on AA2024-T3 Aluminum Alloy Used in Aeronautical Parts by Electrochemical Impedance Spectroscopy
Pages 121-128
Alain Robin, Luis Gustavo Pacheco and Júlio César Lourenço

DOI: http://dx.doi.org/10.6000/2369-3355.2016.03.03.4

Published: 21 December 2016

 

Abstract: The 2xxx aluminum alloys are largely used in aeronautical structural applications (fuselage, wings) due to their high mechanical strength/weight ratio, but have poor localized corrosion resistance. Their anticorrosive protection is generally ensured by multi-layered coatings based on inorganic and organic layers. The usual technique to evaluate the corrosion protection efficiency provided by the coatings is the salt spray test (ASTM B117). Nevertheless, though the test is employed worldwide, it presents some weak points, such as: it is a destructive test, subjectivity of test (only visual evaluation by the operator), low correlation between conditions of the test and real conditions, low reproductibility. The electrochemical impedance spectroscopy would be an alternative: non-destructive test, objectivity of the test (impedance measurement), the test can be performed in-situ.

In this work, uncoated and coated AA2024-T3 alloys were tested in solutions of NaCl 3.5wt% at room temperature. The coatings were: (a): chromating conversion coating; (b): (a) + epoxy primer; (c): (b) + top coat; (d): chromic anodizing coating; (e): (d) + epoxy primer; (f): (e) + top coat. The specimens of AA 2024-T3 divided into seven groups of duplicates (each group representing a superficial state, non protected or a type of coating) were submitted to electrochemical impedance spectroscopy at corrosion potential using frequencies in the 0.1 to 100 kHz range. To ensure reliability of the results, a design of experiment based on a saturated factorial design was applied involving two control variables (treatment of surface and alternating current frequency), one response variable (impedance modulus) and two blocks (samples and repetitions). Some simulations of surface degradation via standardized accelerated tests (salt spray test) and simulations of common defects in process or assembly operations in aircraft manufacture according to valid standards in the aeronautical industry were also made on coated AA2024-T3 specimens. These surfaces were also tested using electrochemical impedance spectroscopy under the same experimental conditions (3.5 wt% NaCl, room temperature, 0.1Hz-100kHz). The statistical analysis of results showed the effectiveness of the application of electrochemical impedance spectroscopy to assist in the quality control of processes of surface treatments in the aerospace sector. The synergic effect involving the care taken in the experimental conditions, the type of experimental design and the sampling size were important to validate the results facing violations of hypotheses in the analysis of variance method. Each coating on AA2024-T3 alloy, and also the bare metal, is characterized by an Impedance versus Frequency Bode curve, sort of fingerprint, which can be used to identify the coating and to evaluate easily and accurately its quality. The results have demonstrated promising and allow to establish strategies for implementation of the electrochemical impedance spectroscopy technique in surface treatment processes.

Keywords: AA2024 alloy, corrosion, EIS, non-destructive test, aeronautic industry.

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Focused Electron Beam Induced Processing Renders at Room Temperaturea Bose-Einstein Condensate in Koops-GranMat
Pages 50-55
Hans W.P. Koops

DOI: http://dx.doi.org/10.6000/2369-3355.2016.03.02.1

Published: 13 October 2016

 

Abstract: Focused Electron Beam Induced Processing allows to generate nanocrystalline materials with metallic conductivity and also nanogranular materials with metal crystals embedded in a fullerene matrix, which shows at room temperature 1000 times better conductivity than superconductors at 40 K due to a Bose Einstein Condensate. Resistors and field emitters carry > 50 MA/cm² current density and deliver up to 1 mA current by field emission, when having an enlarged foot point contact to normal metal like Gold. An explanation for the different characteristics is given. The reason for the generation of the Bose Einstein Condensate is explained, and applications are described.

Keywords: Field emission, Focused electron beam induced processing,GDSII-layout exposure control, x,-y,-t,-nested loop exposure control, 3-d e-beam printing, Super conductivity, Cooper pairs, Bose Einstein Condensate, Koops-Pairs, Applications.

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Effect of Nitriding Time on the Structural Evolution and Properties of Austenitic Stainless Steel Nitrided Using High Power Pulsed DC Glow Discharge Ar/N2 Plasma
Pages 62-74
S. Yang, M. Kitchen, Q. Luo, D.N. Ievlev and K.E. Cooke

DOI: http://dx.doi.org/10.6000/2369-3355.2016.03.02.3

Published: 13 October 2016

 

Abstract: A high power pulsed DC glow discharge plasma (HPPGDP) system was employed to perform fast nitriding of AISI 316 austenitic stainless steel in Ar and N2 atmosphere. In-situ optical emission spectroscopy and Infrared pyrometer measurements were used during the plasma nitriding to investigate the effect of dynamic plasma on the nitriding behaviour. SEM and EDX, XRD, Knoop indentation, and tribo-tests were used to characterise microstructures and properties of the nitrided austenitic stainless steel samples. HPPGDP produced high ionization of both Ar and N2 in the plasma that corresponded to dense ion bombardment on the biased steel samples to induce effective plasma surface heating and to form high nitrogen concentration on the biased steel surfaces, and therefore fast nitriding (> 10µm/hour) was achieved. Various phases were identified on the nitrided stainless steel samples formed from a predominantly a single phase of nitrogen supersaturated austenite to a multi-phase structure comprising chromium nitride, iron nitride and ferrite dependent on the nitriding time. All the nitrided AISI 316 austenitic stainless steel samples were evaluated with high hardness (up to 17.3 GPa) and exceptional sliding wear resistance against hardened steel balls and tungsten carbide balls.

Keywords: Pulsed Glow Discharge Plasma, Nitriding, Austenitic Stainless Steel, Structural Characterization, Tribological Properties.

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Formate-Free Metal-Organic Decomposition Inks of Copper Particles and Self-Reductive Copper Complex for the Fabrication of Conductive Copper Films

Yuki Kawaguchi, Ryuichi Arakawa and Hideya Kawasaki

DOI: http://dx.doi.org/10.6000/2369-3355.2016.03.02.2

Published: 13 October 2016

 

Abstract: Metal-organic decomposition (MOD) inks have been developed for printed electronics applications. Cu-based MOD inks prevent the oxidation of the metal during storage, as the Cu is already present in an oxidized form (i.e. a salt). However, usually hazardous formates such as Cu (II) formate have to be used as the copper salt in order to ensure thermal decomposition and self-reduction of the metal salt at moderate temperatures (less than 150 °C). In this study, a formate-free hybrid ink containing copper particles and a Cu/1-amino-2-propanol (AmIP)/acetate complex was developed for the fabrication of conductive copper films on flexible polymer substrates at low sintering temperatures. A hybrid ink with a weight ratio of 3:1copper particles to MOD ink produced a conductive copper film with close-packed copper particles and a low resistance of 7.3×10⁻5Ω cm after sintering at a temperature of 180 °C for 60 min under a N2 gas flow. Good oxidation resistance of the copper films was observed after exposure to air at 23 °C for two months.

Keywords: Metal-organic decomposition ink, Electrical conductivity, Sintering.

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Microwave Plasma CVD Grown Single Crystal Diamonds – A Review
Pages 75-99
Awadesh Kumar Mallik

DOI: http://dx.doi.org/10.6000/2369-3355.2016.03.02.4

Published: 13 October 2016

 

Abstract: Diamond offers a range of unique properties, including wide band of optical transmission, highest thermal conductivity, stiffness, wear resistance and superior electronic properties. Such high-end properties are not found in any other material, so theoretically it can be used in many technological applications. But the shortcoming has been the synthesis of the diamond material in the laboratory for any meaningful use. Although microwave plasma chemical vapour deposited (MPCVD) has been in practice since 1980s for the diamond growth but it is in the past 7-8 years that its potential has been realised by the industry due to capability of MPCVD to deposit diamond, pure and fast, for commercial uses. There are many CVD techniques for growing diamond but among them MPCVD can only make single crystal diamond (SCD) effectively. SCD grown by MPCVD is also superior to other forms of diamond produced in the laboratory. For example, SCD is necessary for the best electronic properties - often outperforming the polycrystalline diamond (PCD), the high pressure high temperature (HPHT) diamond and the natural diamond. In many applications the short lateral dimensions of the lab-grown diamond available is a substantial limitation. Polycrystalline CVD diamond layers grown by hot filament CVD solved this problem of large area growth, but the presence of grain boundaries are not appropriate for many uses. On the other hand, there is still limitation in the area over which SCDs are grown by MPCVD, only upto 10-15 mm lateral sizes could have been achieved so far, while there are recipes which rapidly grow several mm thick bulk SCDs. This lateral size limitation of SCDs is primarily because of the small seed substrate dimension. Although natural and HPHT diamonds may not be suitable for the intended application, still they are routinely used as substrates on which SCD is deposited. But the problem lies in the availability of large area natural SCD seeds which are extremely rare and expensive. Moreover, large diamond substrate plates suitable for CVD diamond growth have not been demonstrated by HPHT because of the associated high economic risk in their fabrication and use. Other than lateral dimension, purity of SCD is also very important for technological use. Natural diamond is often strained and defective, and this causes twins and other problems in the CVD overgrowth or fracture during synthesis. In addition, dislocations which are prevalent in the natural diamond substrate are replicated in the CVD layer, also degrading its electronic properties. HPHT synthetic diamond is also limited in size, and generally is of poorer quality in the larger stones, with inclusions being a major problem.

There will be much research interest in the next 10 years for the MPCVD growth of SCD. Purer and bigger SCDs will be tried to grow with faster and reproducible MPCVD recipes. Here the MPCVD growth of SCD is being reviewed keeping in mind its huge technological significance in the next decades or so. Discoveries of the commercial productions of silicon, steel, cement different materials have built modern societies but higher scales will be achieved with the advent of lab-grown diamond.

Keywords: Microwave plasma CVD, single crystal diamond, properties, application, review.

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