Tribocorrosion is a term used to describe the material degradation due to the combination of electrochemical and tribological processes. Due to a synergetic effect, the material loss can be larger than the sum of the losses due to wear and corrosion acting separately. In this thesis, the synergy of wear and corrosion was investigated for different types of material, namely the Ti-6Al-4V alloy, the SS316L stainless steel coated with a thin film of Diamond Like Carbon (DLC), and the SS301 stainless steel coated with a thin film of chromium silicon nitride (CrSiN). / A tribocorrosion apparatus was designed and constructed to conduct wear experiments in corrosive media. Sliding ball-on-plate configuration was used in this design, where the contact between the ball and the specimen is totally immersed in the test electrolyte. The specimen was connected to a potentiostat to control its electrochemical parameters, namely the potential and the current. Electrochemical techniques were used to control the kinetics of corrosion reactions, and therefore it was possible to assess separately the role of corrosion and wear in the total degradation of material, and to evaluate the synergy between them. / For Ti-6Al-4V, it was found that the corrosion and tribocorrosion depend strongly on the structure of the material. The alpha-equiaxed microstructure with fine dispersed beta-phase exhibited the best corrosion resistance. The corrosion resistance was found to decrease when the basal plane was preferentially aligned parallel to the surface, which is attributed to a low resistance to charge transfer in the oxide films formed on this plane. On the other hand, when wear and corrosion were involved simultaneously, the oxide layer protecting the substrate against dissolution was mechanically destroyed leading to a high corrosion rate. It was found that the hardness was the most important factor determining the tribocorrosion behavior of the Ti-6Al-4V alloy; samples with high hardness exhibited less mechanical wear, less wear-enhanced corrosion, and less corrosion-enhanced wear. / For DLC coatings, it was found that interface engineering plays a crucial role in the tribocorrosion behavior of DLC films. DLC films with nitrided interface layer (SS\N3h\DLC) were shown to have very poor tribocorrosion resistance; the DLC film delaminated from the substrate after 50 cycles of sliding wear at 9 N load in Ringer's solution. It should be mentioned that a previous study performed at Ecole Polytechnique de Montreal [4] has shown that the same coating resisted 1800 cycles of dry wear at 22 N without delamination. This demonstrates clearly the effect of corrosion on the wear resistance of DLC films. The use of a-SiN:H bond layer between the SS316L substrate and the DLC film improved significantly the tribocorrosion behavior of the coating. This layer acts as a barrier against corrosion reaction; the polarization resistance was 5.76 GO.cm2 compared to 27.5 MO.cm2 and 1.81 MO.cm2 for the DLC-coated SS316L with nitrided interface layer and the bare substrate, respectively. / For CrSiN coatings, it was also shown that nitriding treatment of the substrate prior to deposition reduces significantly the tribocorosion resistance of the CrSiN-coated SS301 substrates. This is attributed to the peculiar morphology of the nitrided surface prior to deposition. The high relives at the grain boundaries of the substrate may be the reason for the generation, during sliding wear, of defects in the film, which makes the infiltration of the liquid easier, and consequently leads to the destruction of the CrSiN film.

An electrochemical investigation of the corrosion of iron and Fe18Cr based stainless steel alloys was undertaken with particular emphasis on the nucleation and growth of surface films. Chronoamperometry was shown to be a sensitive technique to investigate the initial stages of film formation and growth. In a variety of acidic (pH < 7), alkaline and alkaline cyanide electrolytes, providing dissolution of the substrate metal could occur rising current transients, similar to those reported in electrocrystallisation studies, were observed when the electrode was stepped to the appropriate potential. This indicated that at these potentials the surface film formed via the nucleation and growth of discrete nuclei. A significant aspect of this study was visual evidence of this nucleation and subsequent growth of the film provided by scanning electron microscopy which supported the electrochemical data and interpretation thereof. Existing electrocrystallisation models were used to evaluate the experimental rising current transients. While these models gave an indication as to the prevailing nucleation and growth mechanism, they were found to be inadequate in describing anodic oxide formation on an oxidising substrate. A qualitative model was proposed. In acidic electrolytes, rising chronoamperometric transients were observed for Fe, Cr and Fe18Cr at passive potentials and for FexCr (x = 16,18, 20,23% Cr) and alloys 444, 4732, 4733, 304L and 316L at transpassive potentials. The transients were shown to be sensitive to variations of potential, temperature, electrolyte and alloy composition. A systematic investigation of the influence of temperature (20 0 C - 1200 C) on the chronoamperometric, cyclic voltammetric and rotating ring - disc electrode behaviour of Fe in O.5M and 1.0M NaOH was also undertaken. In alkaline electrolytes, the formation of a duplex surface film was proposed, with x-ray photoelectron spectroscopy indicating that the protective base layer consisted of FeO while Fez03 and FeOOH constituted the upper layer. Base layer formation was favoured with increasing temperature and increasing hydroxide ion concentration of the electrolyte. Addition of OAM NaCN to O.5M and 1.0M NaOH had a marked effect on the electrochemistry of the system, with CN- inhibiting surface film formation, particularly of the upper layer. A mechanism for the oxidation of Fe in alkaline and alkaline cyanide electrolytes was proposed. / Thesis (Ph.D.)-University of Natal, 1994.

No description available.

The effect of crack tip strain rate (CTSR) on environmentally assisted cracking was studied for alloys AA-7075 (Al-Zn-Mg-Cu) and AA-8090 (Al-Li-Cu-Mg) in the artificially aged condition. Fatigue pre-cracked double cantilever beam (DCB) specimen were employed with the crack plane parallel to the rolling plane. The cracking behaviour under monotonic and cyclic loading conditions was investigated in aqueous sodium chloride solutions with and without additions of sodium chromate as a corrosion mhibitor. CTSR values were described in terms of K-rate ∆K/∆t (ie. dK/dt) as a measured average over the loading period of a fatigue cycle. This allowed a comparison with CTSR's of monotonically increasing load or constant load tests. At frequencies ≤1 Hz, the load was applied with a triangular wave form. A high frequency of 30 Hz was obtained by sinusoidal loading. Expressed as K-rate, CTSR values were varied over 7 orders of magnitude from 10⁵MPa√m/s to 10² MPa√m/s. Stress intensities investigated were mainly around region II values with respect to SCC K-log(da/dt) behaviour. At low K-rates, real time crack velocities (da/dt) measured under monotonic slow loading or constant load conditions were comparable to crack velocities obtained with cyclic loading experiments. As the K-rate was increased from low values, typical of constant load experiments, the real time crack velocities decreased. This was caused by plasticity induced crack growth retardation effects and a decrease in crack tip film rupture events during the unloading part of a cycle. The crack propagation rate decreased until minimal crack advance increments per cycle were dictated by mechanical parameters acting on a hydrogen embrittled crack tip region. Under monotonic loading conditions region II crack velocities were not influenced by an increase in K-rate which was explained with a mass transport controlled cracking process. Tests with alloy 7075 at intermediate K-rates and a high R-ratio of 0.78 allowed a crack tunnelling mechanism to operate. This overcame the plasticity induced crack growth retardation and, therefore, cracks propagated at the same rates as during low K-rate tests where no retardation phenomena were encountered. Scanning electron microscope investigations revealed a striated intergranular fracture surface of alloy 7075 if tested at K-rates above the transition value to K-rate independent crack propagation rates. Individual striations could be matched on opposing fracture surfaces and the striation spacing corresponded to the average crack propagation increment per cycle. The striations, therefore, were formed as part of the crack advance during every fatigue cycle. At the lower K-rates no striations were present but micro tear ridges could be found on the intergranular fracture facets indicating that dissolution processes alone did not cause the intergranular crack advance. Alloy 8090 did not reveal significant changes in fractography over the entire K-rate range investigated, except at the highest K-rates where small interlocking steps could be detected on some opposing transgranular fracture surfaces. In general, however, the crack path at all K-rates was mainly intergranular with dimpled fracture facets. Alloy 8090 exhibited a high resistance to SCC with fatigue pre-cracked DCB specimen. Therefore, to obtain crack velocity values with low K-rate monotonic loading tests very long test durations would have been necessary. It is concluded that the transition from intergranular SCC to intergranular CF occurs at a critical K-rate. Below the critical K-rate crack velocities are not increased by cyclic loading. Instead crack growth retardation effects can result in lower real time crack velocities than those typical for constant load tests at comparable stress intensities but much lower K-rates. / Applied Science, Faculty of / Materials Engineering, Department of / Graduate

Aim of this study is to improve corrosion resistance of magnesium alloy AZ91 by conversion coatings. Influence of alloy microstructure on conversion coating growth and corrosion resistance was evaluated. Properties of pure magnesium and magnesium alloy AZ91 as well as the influence of alloying elements on properties of this alloy are described in theoretical part. Recent results of corrosion protection by conversion coatings on AZ type magnesium alloys are summarised in recherché part. Practical part focuses on preparation of hexavalent chromium based conversion coating and phosphate-permanganate based conversion coating on as cast AZ91 magnesium alloy, these coatings were subsequently applied on annealed AZ91 magnesium alloy. Corrosion protection of the coatings prepared on as cast and annealed alloy was evaluated by potentiodynamic measurements and testing in neutral salt spray. Furthermore the influence of plasma activation on phosphate-permanganate coating surface was studied.

Sulfur adsorbed on metallic and oxide surfaces, whether originating from gaseous environments or segregating as an impurity to metallic interfaces, is linked to the deterioration of alloy performance. This research dealt with investigations on the interactions between sulfur and iron or iron alloy metallic and oxide surfaces under ultrahigh vacuum conditions. Sulfur was either intentionally dosed from a H2S source on an atomically clean metal surface, or segregated out as an impurity from the bulk to the metal surface by annealing at elevated temperatures.

No description available.

No description available.

No description available.

A computer model for diffusion-controlled internal precipitation was used to simulate the corrosion behavior of Ni-based superalloys in carburizing atmospheres. The model is based on Crank-Nicholson finite difference solution of the diffusion equation. The code also includes the ternary cross diffusion effect due to substitutional alloying elements that are preferentially oxidized. The model can treat two sets of boundary conditions corresponding to the presence or absence of a protective oxide scale. It accounts for internal precipitation of corrosion products whenever thermodynamic solubility limits are exceeded. Up to four different carbides can be treated simultaneously. The solubility product is computed for each reaction and the amount of carbon that reacts is removed from the diffusion process. Under non-protective conditions, the predictions of model were compared to carburization profiles obtained experimentally in H₂-CH₄ environment tests. Results are presented for the formation of Cr, Mo, Ti, W, and Nb carbides in Ni-based superalloys. The predicted corrosion profiles are in qualitative agreement with experimental data. / Master of Science