Submitted by Rosana Amâncio (rosana.amancio@ufcg.edu.br) on 2018-07-27T13:48:39Z No. of bitstreams: 1 MISLENE PEREIRA LINS -DISSERTAÇÃO PPGCNBio 2015.pdf: 7222188 bytes, checksum: 9441b1d0282367ee9dacbecdcd6873d8 (MD5) / Made available in DSpace on 2018-07-27T13:48:39Z (GMT). No. of bitstreams: 1 MISLENE PEREIRA LINS -DISSERTAÇÃO PPGCNBio 2015.pdf: 7222188 bytes, checksum: 9441b1d0282367ee9dacbecdcd6873d8 (MD5) Previous issue date: 2015-04-16 / CNPq / A eletrodeposição de um simples metal ou de suas ligas é atualmente de grande importância nas diversas áreas de engenharia e tecnologia. Dessa forma, as técnicas eletroquímicas para obtenção de revestimentos pelo processo de eletrodeposição são amplamente estudadas. Pelo processo de eletrodeposição podem ser obtidos filmes finos de óxidos metálicos com propriedades bem específicas para determinado uso. Através da utilização de métodos eletroquímicos é possível avaliar o comportamento relacionado a corrosão de um metal ou sua liga. Neste trabalho investigou-se os parâmetros operacionais para eletrodeposição da liga Ni-PW utilizando-se glicina como agente complexante. Para este estudo realizou-se um planejamento experimental 23, com composto central. As variáveis estudadas foram densidade de corrente, pH do banho eletrolítico e temperatura do banho. A liga Ni-P-W foi depositada sobre substrato de cobre de área superficial total de 8 cm2. A composição da liga foi obtida por meio da utilização de energia dispersiva de raios-X. A morfologia foi obtida por meio de microscopia eletronica de varredura. Foi feito medidas de difratometria de raios-X e de microdureza Vickers. No estudo de corrosão foram utilizadas as medidas de polarização potenciodinâmico linear realizados em NaCl 3,5%. As análise de composição química mostraram que as ligas obtidas apresentaram elevadas porcentagens de Ni e P e traços de W. As análises de morfologia das ligas obtidas mostram revestimentos com superfície homogênea e morfologia nodular bem definida para depósitos com maior porcentagem de P. Ligas com uma menor porcentagem de P apresentaram nódulos de tamanhos variados, e uma elevada quantidade de trincas. Os depósitos obtidos apresentaram comportamento amorfo. Os ensaios de corrosão mostraram que os revestimento obtido com densidade de corrente de 70 mA/cm2, pH 6,5 e temperatura de 63,5 oC apresentou os melhores resultados para resistência a polarização e corrente de corrosão. / The electrodeposition of a simple metal or alloy is currently of great importance in many areas of engineering and technology. Thus, electrochemical techniques to obtain coatings by electrodeposition process are widely studied. By electrodeposition process there can be obtained thin films of metal oxides with very specific properties for specific use. Through the use of electrochemical methods it is possible to evaluate the corrosion related behavior of a metal or its alloy. In this study we investigated the operating parameters of Ni-P-W alloy plating using glycine as a complexing agent. For this study was made an experimental design 23 with central composite variables studied were current density, the electrolytic bath pH and bath temperature. The Ni-P-W alloy was deposited on copper substrate of total surface area 8 cm2. The composition of the alloy was obtained by using energy dispersive X-ray (EDX). The morphology of the Ni-PW electroplated alloy was obtained by Scanning Electronic Microscopy (SEM). Measurements of X-ray diffraction and Vickers microhardness were made. The linear potentiodynamic polarization (LPP) corrosion measurements were carried out in NaCl 3.5% in the study of corrosion. Chemical composition analysis showed that the obtained alloys showed high percentages of Ni and P and low of W. The analysis of the obtained alloys shows coatings with homogeneous surface and well defined nodular morphology for deposits with the highest percentage of P. Alloys with a lower percentage of P showed varying sizes of nodules, and a high percentage of cracks. The deposits obtained showed amorphous behavior. The corrosion tests showed that the coating obtained with current density 70 m/cm2, pH 6.5 and temperature of 63.5 °C showed the best results for the polarization resistance and corrosion current.

This master’s thesis is focused on corrosion resistance of nickel-phosphorus coatings on magnesium alloy AZ91. In the theoretical part is summarized current knowledge about magnesium alloys and electroless deposition of Ni-P coatings including ongoing reactions. Theoretical part also lists all substances contained in the nickel bath and their specific use there. In the second half of theoretical part are discussed corrosion and immersion tests. Theoretical part is ended by review aimed towards the research in areas of immersion tests. Experimental part describes individual steps of pretreatment on magnesium alloy and then deposition of the Ni-P coating. Composition and morphology of deposited Ni-P coating and magnesium alloy were studied using energy dispersive spectroscopy. Experiment part also contains list of experiments trying to figure out ideal thickness of low-phosphorus coating which is able to protect magnesium alloy from corrosion. Master’s thesis is ended with the list of immersion tests and results which outcomes from them.

Cílem této diplomové práce jse najít nejnižší možnou tloušťku nikl-fosforového povlaku, který může být galvanicky pokoven mědí bez defektů na horčíkové slitině, nikl-fosforového nebo měděného povlaku. V teoretické části jsou shrnuty poznatky o hořčíkových slitinách a jejich korozi. Navíc se teoreticá část zaměřuje na popis procesu bezproudého niklování a elektrochemického pokovování mědí a jejich porovnání. Na konci teoretické části je shrnut současný výzkum o elektrochemickém pokovování hořčíkových slitin. V experimentální části byl popsán proces přípravy povlaků Ni-P a Cu na horčíkové slitině AZ91. Na jedné vrstvě a dvojité vrstvě Ni-P povlaku byla provedena elektrodepozice mědi. Navíc byl diskutován vliv předůpravy před samotnou elektrodepozicí mědi. Za účelem zjištění korozních vlastností vzorků byl vykonán potenciodynamický test. Následně byly připraveny metalografické výbrusy jednotlivých vzorků a pomocí světelného a rastrovacího elektronového mikroskopu byla provedena charakterizace. Na konec bylo zjištěno prvkové složení jednotlivých povlaků pomocí EDX analýzy.

The aim of this diploma thesis was summary of all steps and knowledge necessary to deposition of quality Ni-P coatings deposited on wrought magnesium alloys AZ31 and AZ61. There is the treatise about wrought magnesium alloys AZ31 and AZ61. Thesis includes its phase composition in the theoretical part. There are given its possible processing methods too. Next, there is desribed the mechanism of deposition of Ni-P coatings, components required to electroless deposition and factors affecting the quality and properties of these coatings. The theoretical part is ended by serie of reviews. Authors of these reviews deal with pretreatment of substrates, preparation, characterization and measuring of mechanical, structure and corrosion properties of deposited coatings. The optimalization of pretreatment, parametres and composition of nickel bath suitable for magnesium alloys is described in experimental part. The microstructure, present interlayer between substrate and Ni-P coating and chemical composition of deposited coatings was observed and measured by optical and electron microscopy. The mechanical characterization of Ni-P coatings was performed by microhardness tester.

Superfícies de silício (100) foram inicialmente pré-ativadas em uma solução diluída de ácido fluorídrico contendo PdCl2. Após essa etapa, filmes finos de Cu-Ni-P foram quimicamente depositados utilizando-se um banho químico contendo 15g/l NiSO4.6H2O; 0.2 g/l CuSO4.5H2O; 15 g/l Na2HPO2.H2O e 60 g/l Na3C6H5O7.2H2O na temperatura de 80ºC onde foi adicionado NH4OH até que o pH da solução atingisse 8,0. Foi observado que as porcentagens estequiométricas de Ni e Cu variaram substancialmente no intervalo de 1 a 3min, e se tornaram praticamente estáveis em 50% e 35%, respectivamente, quando o tempo de deposição foi superior a 3min. Além disso, a porcentagem de P permaneceu quase constante em torno de 17-18% para todos os tempos de deposição. A distribuição de alturas nas imagens FE-SEM resultou bimodal para tempos na faixa de 1 e 3min onde a predominância do modo de maior altura aumentou substancialmente para o tempo de 3min. Tal fato serviu para corroborar a evolução da morfologia superficial de grãos menores com diâmetros na faixa de 0,02 a 0,1µm, predominantemente compostos de Ni, para grãos maiores, na faixa de 0,1 a 0,3µm e predominantemente compostos de Cu. Após um recozimento a 100oC durante 10min em ambiente 20%O2+80%N2, observou-se uma mudança na morfologia superficial em que os aglomerados de fósforo (Po) desapareceram enquanto que os grãos que compunham a imagem não mudaram substancialmente de tamanho após o recozimento. Apesar do desaparecimento dos aglomerados, a concentração de fósforo ainda apresentou valor semelhante ao valor de antes do recozimento (~17-18%). As análises de difração de raios X (XRD) indicaram o aparecimento de um pico de difração alargado ao redor de 22,6º característico de óxido de fósforo (P2O5) com estrutura vítrea amorfa significando que o fósforo em estado puro foi transformado na sua forma oxidada. Por outro lado, picos substancialmente menos intensos de NiO, Ni3P e Si5P6O25 foram observados. Verificou-se também para os filmes recozidos em N2+O2 que a resistividade aumentou para todos os tempos de deposição e o poder termoelétrico medido resultou quase independente do tempo de deposição e, portanto, foi quase independente da espessura do filme para as diferentes temperaturas medidas na faixa de 40 a 120ºC. / Silicon surfaces (100) were initially pre-activated in a diluted hydrofluoric acid solution containing PdCl2. After this step, Cu-Ni-P thin films were chemically deposited using a chemical bath containing 15g/l NiSO4.6H2O; 0.2 g/l CuSO4.5H2O; 15 g/l Na2HPO2.H2O e 60 g/l Na3C6H5O7.2H2O at the temperature of 80°C where NH4OH was added until the pH of the solution reached 8.0. It was observed that the stoichiometric percentages of Ni and Cu varied substantially for deposition time in the range of 1 to 3min, and became practically invariant at 50% and 35%, respectively, when the deposition time was greater than 3min. In addition, the percentage of P remained almost constant at around 17-18% for all the deposition times. The distribution of heights in the FE-SEM images resulted bimodal for times in the range of 1 and 3min where the predominance of the higher average height mode increased substantially for the time of 3min. This fact allowed one to corroborate the superficial morphology passing from smaller grains with diameters in the range of 0.02 to 0.1µm, predominantly composed of Ni to larger grains in the range of 0.1 to 0.3µm with Cu predominant composition. After an annealing at 100°C for 10min in a 20%O2+80%N2 environment, the phosphorus (Po) agglomerates disappeared while the size of the grains did not change substantially after the annealing. Despite the disappearance of the agglomerates, the phosphorus concentration still remained unchanged (~ 17-18%). X-ray diffraction (XRD) analysis showed a broad diffraction peak around 22.6º, which is characteristic of an amorphous vitreous structure (P2O5). In addition, substantially less intense peaks showing small amounts of NiO, Ni3P and Si5P6O25 were observed. It was also verified for the N2+O2 annealed films that the resistivity increased for practically all the deposition times and the measured thermoelectric power was almost independent of the deposition time and, therefore, was also independent of the film thickness for the various temperatures in the range from 40 to 120ºC.

The goals of this project are study Cu free back contact alternatives for CdS/CdTe thin film solar cells, and to research dry etching for CdTe surface preparation before contact application. In addition, an attempt has been made to evaluate the stability of some of the contacts researched. The contacts studied in this work include ZnTe/Cu2Te, Sb2Te3, and Ni-P alloys. The ZnTe/Cu2Te contact system is studied as basically an extension of the earlier work done on Cu2Te at USF. RF sputtering from a compound target of ZnTe and Cu2Te respectively deposits these layers on etched CdTe surface. The effect of Cu2Te thickness and deposition temperature on contact and cell performance will be studied with the ZnTe depositions conditions kept constant. C-V measurements to study the effect of contact deposition conditions on CdTe doping will also be performed. These contacts will then be stressed to high temperatures (70-100 degrees C) and their stability with stress time is analyzed. Sb2Te3 will be deposited on glass using RF sputtering, to study film properties with deposition temperature. The Sb2Te3 contact performance will also be studied as a function of the Sb2Te3 deposition temperature and thickness. The suitability of Ni-P alloys for back contacts to CdTe solar cells was studied by forming a colloidal mixture of Ni2P in graphite paste. The Ni-P contacts, painted on Br-methanol etched CdTe surface, will be studied as a function of Ni-P concentration (in the graphite paste), annealing temperature and time. Some of these cells will undergo temperature stress testing to determine contact behavior with time. Dry etching of CdTe will be studied as an alternative for wet etching processes currently used for CdTe solar cells. The CdTe surface is isotropically etched in a barrel reactor in N2, Ar or Ar:O2 ambient. The effect of etching ambient, pressure, plasma power and etch time on contact performance will be studied.

Superfícies de silício (100) foram inicialmente pré-ativadas em uma solução diluída de ácido fluorídrico contendo PdCl2. Após essa etapa, filmes finos de Cu-Ni-P foram quimicamente depositados utilizando-se um banho químico contendo 15g/l NiSO4.6H2O; 0.2 g/l CuSO4.5H2O; 15 g/l Na2HPO2.H2O e 60 g/l Na3C6H5O7.2H2O na temperatura de 80ºC onde foi adicionado NH4OH até que o pH da solução atingisse 8,0. Foi observado que as porcentagens estequiométricas de Ni e Cu variaram substancialmente no intervalo de 1 a 3min, e se tornaram praticamente estáveis em 50% e 35%, respectivamente, quando o tempo de deposição foi superior a 3min. Além disso, a porcentagem de P permaneceu quase constante em torno de 17-18% para todos os tempos de deposição. A distribuição de alturas nas imagens FE-SEM resultou bimodal para tempos na faixa de 1 e 3min onde a predominância do modo de maior altura aumentou substancialmente para o tempo de 3min. Tal fato serviu para corroborar a evolução da morfologia superficial de grãos menores com diâmetros na faixa de 0,02 a 0,1µm, predominantemente compostos de Ni, para grãos maiores, na faixa de 0,1 a 0,3µm e predominantemente compostos de Cu. Após um recozimento a 100oC durante 10min em ambiente 20%O2+80%N2, observou-se uma mudança na morfologia superficial em que os aglomerados de fósforo (Po) desapareceram enquanto que os grãos que compunham a imagem não mudaram substancialmente de tamanho após o recozimento. Apesar do desaparecimento dos aglomerados, a concentração de fósforo ainda apresentou valor semelhante ao valor de antes do recozimento (~17-18%). As análises de difração de raios X (XRD) indicaram o aparecimento de um pico de difração alargado ao redor de 22,6º característico de óxido de fósforo (P2O5) com estrutura vítrea amorfa significando que o fósforo em estado puro foi transformado na sua forma oxidada. Por outro lado, picos substancialmente menos intensos de NiO, Ni3P e Si5P6O25 foram observados. Verificou-se também para os filmes recozidos em N2+O2 que a resistividade aumentou para todos os tempos de deposição e o poder termoelétrico medido resultou quase independente do tempo de deposição e, portanto, foi quase independente da espessura do filme para as diferentes temperaturas medidas na faixa de 40 a 120ºC. / Silicon surfaces (100) were initially pre-activated in a diluted hydrofluoric acid solution containing PdCl2. After this step, Cu-Ni-P thin films were chemically deposited using a chemical bath containing 15g/l NiSO4.6H2O; 0.2 g/l CuSO4.5H2O; 15 g/l Na2HPO2.H2O e 60 g/l Na3C6H5O7.2H2O at the temperature of 80°C where NH4OH was added until the pH of the solution reached 8.0. It was observed that the stoichiometric percentages of Ni and Cu varied substantially for deposition time in the range of 1 to 3min, and became practically invariant at 50% and 35%, respectively, when the deposition time was greater than 3min. In addition, the percentage of P remained almost constant at around 17-18% for all the deposition times. The distribution of heights in the FE-SEM images resulted bimodal for times in the range of 1 and 3min where the predominance of the higher average height mode increased substantially for the time of 3min. This fact allowed one to corroborate the superficial morphology passing from smaller grains with diameters in the range of 0.02 to 0.1µm, predominantly composed of Ni to larger grains in the range of 0.1 to 0.3µm with Cu predominant composition. After an annealing at 100°C for 10min in a 20%O2+80%N2 environment, the phosphorus (Po) agglomerates disappeared while the size of the grains did not change substantially after the annealing. Despite the disappearance of the agglomerates, the phosphorus concentration still remained unchanged (~ 17-18%). X-ray diffraction (XRD) analysis showed a broad diffraction peak around 22.6º, which is characteristic of an amorphous vitreous structure (P2O5). In addition, substantially less intense peaks showing small amounts of NiO, Ni3P and Si5P6O25 were observed. It was also verified for the N2+O2 annealed films that the resistivity increased for practically all the deposition times and the measured thermoelectric power was almost independent of the deposition time and, therefore, was also independent of the film thickness for the various temperatures in the range from 40 to 120ºC.

Magnesium and its alloys are extensively used for various industries such as aerospace, automobile and electronics due to their excellent properties such as low density, high strength and stiffness and electromagnetic shielding. However, the wide spread applications of these alloys are limited due to the undesirable properties such as poor corrosion, wear and creep resistance and high chemical reactivity. These alloys are highly susceptible to galvanic corrosion in sea water environment due to their high negative potential (-2.37 V vs SHE). The effective way of preventing corrosion is through the formation of a protective coating, which acts as a barrier between the corrosive medium and the substrate. Many surface modification methods such as electro/ electroless plating, conversion coating, physical and chemical vapour depositions, thermal spray coating etc., are available currently to improve the corrosion resistance of Mg alloys. Of these methods, the electroless nickel plating has gained considerable importance because of its excellent properties such as high hardness, good wear and corrosion resistance. The properties of binary electroless nickel coating have been further improved by the addition of a third element such as cobalt, tungsten, tin and copper etc. It has been reported that the addition of tungsten as the third element in the Ni-P improves the properties such as hardness, wear and corrosion resistance, thermal stability and electrical resistance. Magnesium alloys are categorized as a “difficult to plate metal”, because of their high reactivity in the aqueous solution. They react vigorously with atmospheric oxygen and water, resulting in the formation of the porous oxide/ hydroxide film which does not provide any protection in the corrosive environment. Further, the presence of this oxide film prevents the formation of a good adhesive bond between the coating and the substrate. The surface treatment process for removal of the oxide layer is very much essential before plating the Mg alloy. Currently two processes such as zinc immersion and direct electroless nickel plating are adopted to plate Mg alloys. Etching in a solution of chromate and nitric acid followed by immersion in HF solution to form a conversion film is necessary for direct electroless nickel (EN) plating of Mg alloy. However, strict environmental regulations restrict their usage because of hazardous nature. Expensive palladous activation treatment is a well-known process as a replacement for chromate-HF pretreatments for Mg alloys. It has been reported that EN plating has been carried out over Mg alloys by using conversion coating followed by HF treatment. Formation of an intermediate oxide layer by electrolytic methods is also one of the ways these toxic pretreatments can be avoided. Microarc oxidation (MAO) is an environment friendly surface treatment technique which provides high hardness, better corrosion and wear resistance properties for the Mg alloys. EN coating has been prepared on MAO layer for improving the corrosion resistance. These MAO/EN composite coatings have been prepared using chromic acid and HF pretreatment process. As the replacement for the chromate-HF pretreatment, SnCl2 and PdCl2 sensitization and activation procedures respectively were adopted over MAO layer for the deposition of Ni-P coating. From the above reported literature, it can be inferred that for the activation of inert MAO layer to deposit electroless nickel coating, the hazardous chromate/HF and highly expensive PdCl2 activation processes were followed. Therefore, there is a need for identifying an alternative simple and cost effective pretreatment process for the deposition of electroless nickel. It is well known that borohydride is a strong reducing agent that has been used for the deposition of Ni-B coatings. In the present study, an attempt has been made to utilize borohydride in the pretreatment process for the reduction of Ni2+ ions over the MAO interlayer, which provides the nucleation sites for the deposition of Ni-P coating. Ni-P and Ni-P/Ni-W-P duplex coatings were deposited from stabilizer free carbonate bath on AZ31B Mg alloy to improve the corrosion resistance of the base substrate. The conventional chromate and HF pretreatment processes were followed for the deposition of electroless nickel coating. In order to improve the corrosion resistance of the duplex coating, post treatments such as heat treatment (4 h at 150°C) and chromate passivation were adopted. EDX analysis of AZ31B Mg alloy showed the presence of 2.8 wt.% of Al and 1.2 wt. % Zn with the balance of Mg for AZ31B Mg alloy. After the chromic acid and HF treatment, the magnesium content was reduced from 90.0 wt % to 54.9 wt%, which could be due to the incorporation of chromium on the surface layer. The surface showed about 17.8 wt. % of F. The alloy exhibited the roughness of about 0.29± 0.01µm after mechanical polishing. The roughness value was significantly changed after the chromic acid treatment processes. The maximum roughness of about 1.28±0.06 µm was obtained after the HF activation. XPS analysis confirmed the existence of chromium in +3 oxidation state after the chromic acid treatment. The Ni-P coating thickness of about 25 microns was obtained in 1 h and 15 min. In the case of duplex coatings, Ni-P plating was done for 45 min. to obtain approx. 17 microns thickness and Ni-W-P plating was done for 1.15 h to obtain a thickness of approx. 10 microns, resulting in a total thickness of 25 ± 5 microns. Ni–P coating exhibited nodular morphology with porosity. The size of these cluster nodules were of about 10 µm in diameter. On the other hand, the duplex coating exhibited a less nodular, dense and smooth appearance. From the compositional analysis it was found that Ni–P coating contained about 6 wt. % P. In the case of duplex coating, the P content was reduced to 3 wt % due to the incorporation of about 2 wt% of tungsten. In corrosion studies, the potentiodynamic polarization data obtained for bare Ni-P coating in 0.15 M NaCl solution exhibited a higher current of about 218 μA/cm2 as compared to the substrate due to the porosity of the coating. However, the Ni-P/Ni-W-P duplex showed 55 times improvement in corrosion resistance, vis-a-vis Ni-P due to the dense nature of the coating. The corrosion resistance of the coatings increased in the following order: Ni-P < bare alloy < duplex < duplex-passivated < duplex-heat treated passivated. In EIS study, the Nyquist plot obtained for the bare substrate and Ni–P coating showed the presence of inductance behavior at the lower frequency region due to the adsorption of electroactive species over the substrate through the porous oxide layer. However, the passivated and duplex passivated coatings exhibited only capacitive behavior due to their compact nature. From the above, it can be concluded that, direct deposition of Ni-P coating over the chosen Mg alloy using chromic acid and HF pretreatment process resulted in porous morphology, which affected the corrosion resistance of the coating. As an alternative strategy, the microarc oxidation conversion coating was developed on Mg alloy and characterized. The MAO coating was developed using silicate electrolyte at three different current densities (0.026, 0.046 and 0.067 A/cm2) for about 15 min. With respect to the MAO coating, an increase in the current density increased the pore diameter and decreased the pore density. The surface of the coating became coarser and rough. The cross-sectional morphology of the coating showed two district layers namely the dense and thin inner layer and a porous thick outer layer. The thickness of the coating increased with increase in current density. MAO coating prepared at an intermediate current density of 0.046 A/cm2 exhibited a higher thickness of about 12 µm and a further increase in current density showed a decrease in thickness, due to the greater rate of dissolution of Mg, relative to the rate of deposition. The surface roughness of the MAO coatings also increased with increase in current density. The Ra value increased from 1.39±0.06 to 3.52±0.17 µm with increase in current density. XRD peaks obtained for the Mg substrates corresponded predominately to magnesium. However, the coated specimens showed the presence of peaks corresponding to Mg2SiO4 along with Mg and MgO. The corrosion measurements for the bare substrate and MAO coatings were carried out in 3.5% NaCl medium (0.6 M). Based on potentiodynamic polarization studies, the MAO coating prepared at 0.046 A/cm2 exhibited a lower corrosion current density with a higher Rp value, which was about five orders of magnitude higher than the bare substrate, due to the dense nature of the coating. In EIS study, MAO coatings were fitted with the two time constants equivalent circuit containing outer porous layer and inner barrier layer. The barrier layer resistance values were higher than that of porous layer resistance, which indicated that the resistance offered by barrier layer was higher than the porous layer. The total resistance value obtained for the coating prepared at 0.046 A/cm2 were higher compared to the other coatings, which attested to its better corrosion resistance. The electrochemical noise measurement was carried out for longer immersion durations upto 336 h in 3.5% NaCl solution. The noise resistance value obtained for the base Mg alloy was about 100 Ω at 1h immersion, whereas for the MAO coating prepared at 0.04 A/cm2 a maximum value of about 34.8 MΩ was achieved and it was retained even after 96 h of immersion. Mott–Schottky analysis showed that the oxide layer on magnesium substrate acted as a n-type semiconductor, whereas the MAO coatings exhibited p-type semiconductor behavior. The MAO coating obtained at an intermediate current density showed a higher acceptor density and the flat band potential, which resulted in the better performance of the coating in corrosive environment. In another set of investigations, the Ni-P and Ni-P/Ni-W-P coatings were deposited on AZ31B Mg alloy with MAO coating as an interlayer. The MAO layer was activated by a simple borohydride pretreatment process. During the pretreatment process, the MAO coating was subjected to mild alkali treatment, immersion in the Ni-P plating solution and finally immersion in borohydride solution. During each pretreatment step, the sample was characterized for their surface morphology and composition. The surface morphology showed the distribution of spherical particles over the surface of MAO coating after immersion in the Ni-P plating solution. EDX analysis showed the presence of 2.4 wt. % of Ni, which confirmed that Ni ions were adsorbed over the surface of the MAO coating during the pretreatment process. XPS analysis carried out after immersion in the Ni-P plating solution indicated that Ni existed in +2 oxidation state. The surface became smooth and uniform with flake- like morphology after the borohydride treatment, which indicated that the surface was etched by the borohydride solution. EDX analysis showed the presence of 1.8 wt.% of Ni after borohydride reduction. XPS analysis confirmed the reduction of nickel to the zero oxidation state. Additionally, MAO/Ni-P and MAO/Ni-P/Ni-W-P duplex coatings were developed on MAO coating after a simple borohydride pretreatment. Ni-P and duplex coatings showed uniform and dense nodular morphology without any defects, which clearly indicated that the borohydride treatment provided a uniform and homogeneous active surface for the deposition of electroless nickel based coatings. Borohydride pretreatment process resulted in excellent bonding between MAO/Ni-P layers in the cross section. Based on potentiodynamic polarization studies, the corrosion current values obtained for MAO/ Ni-P and MAO/Ni-P/Ni-W-P duplex coatings were about 1.44 and 1.42 µA/cm2, respectively. The coating showed about 97 times improvement in corrosion resistance compared to the bare substrate, attesting to the dense nature of the coating. In EIS study, the single time constant equivalent circuit was used for fitting the spectra, which pertained to the coating /electrolyte interface. The single time constant could be attributed to the pore-free dense, uniform coatings developed over the MAO interlayer. For the MAO/Ni-P and MAO/Ni-P-Ni-W-P duplex coatings, the charge transfer resistance of about 15 and 11 kΩcm2 were obtained for duplex and Ni-P coatings, which reinforce the better corrosion protective ability of the coating. The above investigation confirms that MAO coatings have good corrosion resistance in the aggressive chloride medium. Consequently, they can serve as an ideal interlayer for the deposition of the electroless nickel coating. Even if the electroless nickel coating is found to fail in harsh environments, the MAO interlayer can protect the base substrate due to its higher corrosion resistance. It is also noteworthy that the borohydride treatment provides better adhesion between the MAO/Ni-P interlayer.

The dissertation thesis deals with the modification of the surface of advanced magnesium alloys with Ni-P based coatings. At the beginning of the theoretical part, the structures of the used magnesium alloys and the influence of individual alloying elements on their properties are characterized. In the following part of the thesis the current knowledge in the field of electroless deposition on metal substrates is summarized. The theoretical part of the thesis is closed with contemporary research study in the field of clarification and determination of possible mechanism of electroless deposition. For the subsequent investigation of the mechanism of electroless deposition on magnesium alloys, it was necessary to characterize the microstructure and composition of individual magnesium alloys in the first phase of the experimental part. The exact composition of elements was determined using glow discharge optical emission spectroscopy and scanning electron microscopy with EDS was used for composition of phases of magnesium alloys. Using scanning electron microscopy and detailed elemental analysis of the coated magnesium substrate, it was found that for optimal Ni-P coating deposition on magnesium alloys, acid pickling prior coating is required in a mixture of acetic acid and sodium nitrate. Using the XPS method, it was found that the phosphorus atom in the sodium dihydride-diphosphate reducing agent has a + V charge. 4 At the end of the experimental part scanning electron microscopy and detailed elemental analyses were used for monitoring of the Ni-P particles nucleation and growth in the first 120 seconds of the coating process.