Rozprawy doktorskie na temat „Ni-P alloy coatings”

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.

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.

碩士
國立聯合大學
材料科學工程學系碩士班
99
In the study, the ternary Ni-Ru-P alloy coatings are fabricated by magnetron dual-gun co-sputtering technique. The chemical composition variation of the coatings in terms of sputtering parameters, including input power, process temperatures and Ar gas flow rate are investigated. The Ni-Ru-P coatings with a Ru content <38.9 at.% remain an amorphous/nanocrystalline feature under a vacuum annealing temperature up to 500oC. On the other hand, Ni(Ru) and Ni-P precipitation phases form as annealing temperature is raised to 550oC. With Ru content >52.7 at.%, the as-fabricated Ni-Ru-P coating shows crystallized Ni + Ru + Ru2P mixed phases. Such phase distribution for high Ru-content ternary Ni-Ru-P is stable under annealing temperature up to 600oC. The crystallized Ni + Ru + Ru2P phases are also responsible for the slight increase in surface roughness. The hardness for low Ru contents as-deposited films distributed around 7.2 to 8.1 GPa. The coatings with crystallized Ru and Ru2P phases possess a higher hardness value of 10.4 GPa. Limited oxide penetration less than 20 nm at Ni29.5Ru64.6P5.9 coating surface is confirmed. The Ni + Ru + Ru2P phases distribution resulted from high content Ru co-sputtering is beneficial to oxidation resistance. The introduction of high Ru concentration significantly strengthens the mechanical and anti-oxidation behaviors of Ni-P-based coating. The Ru can improve the corrosion resistance of binary Ni-P coating from the electrochemical analysis. The effect of W, Al and Ru elements in Ni-P-based coating on their mechanical properties and characteristics are discussed.

碩士
健行科技大學
機械工程系碩士班
103
Ni-Mo-P alloy coatings were deposited on AA5083 aluminum alloy by electroless deposition for wear and corrosion properties. we hope Ni-Mo-P alloy coatings more hard and smooth then before by vacuum heat treatment . The AA5083 aluminum alloy is widely used for many application in automotive , marine , aircraft body sheet due to its excellent combination of strength, corrosion resistance . Research step : 1. Ni-Mo-P and Ni-P coatings were deposited on AA5083 aluminum alloy by electroless deposition . 2. Different temperature and time variables in vacuum heat treatment. 3. The coatings are deposited for characterizations of microhardness , wear and corrosion test . Coating''s hard is strength by vacuum heat treatment , but find some pits on coatings surface , this properties not conducive in corrosion test. Electroless Ni-Mo-P were deposited in pH 6.8 60 min 83 5 . Ni-Mo-P coatings due to its excellent combination of corrosion resistance in 200 15min vacuum heat treatment.

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.

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 Ni-P alloy coatings are widely studied due to their superior mechanical and tribological properties. Ni-P coatings are also considered to be a viable alternative to the chromium (Cr) coatings which utilize environmentally hazardous and toxic carcinogenic electrolytic solutions. The current work focuses on strategies to enhance the corrosion resistance performance of electrodeposited Ni-P coatings primarily by incorporation of foreign additives (carbon nanotubes (CNTs) and graphene) and by engineering of the Ni-P micro-texture and phase fraction (crystalline and amorphous phases). Nickel-phosphorus (Ni-P) coatings were electrodeposited over mild steel substrate using DC power source in conventional two electrode electrochemical setup. As-deposited Ni-P coatings were subjected to phase, microstructural and morphological characterizations using x-ray diffraction, electron microscopy and electron backscatter diffraction techniques. The corrosion analysis was accomplished by using electrochemical impedance spectroscopy (EIS) and potentiodynamic polarisation techniques (Tafel plot) in 3.5 wt.% NaCl solution. Key observations are: (a) in the work on the incorporation of CNTs and Graphene in Ni-P coatings, it was observed that an optimum volume fraction of the additives yielded high corrosion resistance performance. This was essentially due to the smooth compact and defect free surface morphology, (b) in the work on the correlation between micro-texture and corrosion behaviour of Ni-P coatings as a function of phosphorous content, it was observed that the phosphorous concentration range where the nano-crystalline region (along with the minor amorphous phase fraction) was dominant a slight alteration in texture determines the corrosion rate. With increase in the amorphous region, the galvanic coupling between the anodic amorphous phase and cathodic crystalline phase determined the corrosion behaviour. A mixture of amorphous and crystalline phases with lower fraction of the amorphous phase enhanced the corrosion rate due to increased galvanic coupling. For higher addition of phosphorus, large fraction of amorphous phase evolved which significantly reduced the galvanic coupling leading to higher corrosion resistance behaviour, (c) in the work on the effect of deposition temperature (bath temperature of 15˚C, 20˚C, 25˚C, 35˚C) on the evolution of correlation between texture and corrosion behaviour of Ni-P coatings, it was observed that the coating deposited at 15°C and 25°C yielded the maximum and minimum corrosion rate respectively. Analysis of the coating texture revealed that the higher corrosion rate for the 15°C coating was due to low fraction of low energy low angle grain boundaries (LAGBs), higher strain within the grains, and (101) growth texture. Lower corrosion rate, on the other hand, for the 25°C coating was due to low energy (001) growth texture, low average strain within the grains, and high fraction of LAGBs, (d) in the work on the effect of deposition current density on the evolution of correlation between texture and corrosion behaviour of Ni-P coatings, it was observed that the Ni-P coating (deposited using 60 mA.cm-2) that exhibited the lowest corrosion rate was characterized by the presence of lower energy surface texture, lower grain size, narrow grain size distribution and a relatively higher fraction of low energy Σ3 coherent twin boundaries. A higher corrosion rate for coating deposited using 5 mA.cm-2 was due to higher energy surface texture and larger grain size distribution.

碩士
健行科技大學
機械工程系碩士班
103
This study used electroless plating process to prepare Ni-P-Cu composite coating on AA7075 aluminum alloy surface after anodizing treatment. The Stress-Corrosion Cracking (SCC) charactenrstics for the coating in 3.5%NaCl aqueous solution via slow strain rate test was also studied. The surface morphology, element composition and surface hardness of the coatings were analyzed by SEM, EDS and Vicker’s hardness tester. The corrosion and wear-corrosion resistance of electrolessplating Ni-P-Cu composite coating in 3.5% NaCl aqueous solution was evaluated, and also analyzed by electrochemical polarization measurement. Experimental results indicated that electrolessplating Ni-P-Cu composite coating has high hardness, good corrosion resistance, particularly owing to the anodizing treatment of aluminum alloy. The anodizing treatment of AA7075 aluminum alloy substrate efficiently improved the adhesion, surface morphology and hardness of the electroplated Ni-P-Cu composite coating. The results also indicated that the anti-SCC of the coating is potentiodynamic polarization significantly increased in 3.5% NaCl aqueous solution.

碩士
清雲科技大學
機械工程研究所
98
The purpose of this study is to evaluate the corrosion and wear-corrosion resistance properties of electroless Ni/nano-TiO2 and Ni/CNT plated nano-composite coatings on AA5083 alloy in 3.5 wt.% NaCl solution. The nano-composite coatings were prepared by electroless plating method that the nano-TiO2 (15 nm) and Carbon nano-tube (CNT, 5nm) particles were added into the eletroless Ni plating solution with a low and a high concentration of 1 g/L and 10 g/L for comparison, respectively. The corrosion resistance properties of the nano-composite coatings were examined by both potentiodynamic polarization and immersion corrosion test. The experimental results indicated that both Ni/nano-TiO2 and Ni/CNT nano-composite coatings exhibited an uniform and a compact surface morphology, not only improving the corrosion and wear-corrosion resistance of the AA5083 Al-Mg alloy but also superior to the electroless Ni-P coating. Both the corrosion and wear-corrosion resistance of the nano-composite coatings were enhanced significantly at high concentration of 10 g/L, in addition that the CNT added was superior to the nano-TiO2 added electroloss plating solution.

碩士
清雲科技大學
機械工程所
100
The present study used electroless plating techniques by adding nano-TiO2 in the plating solution with various concentrations of 1 g/L, 5 g/L, 10 g/L and 15 g/L to form Ni-P/nano TiO2 composite coatings on the 70Cu-30Zn brass alloy substrate. The corrosion resistance behavior was evaluated by potentiodynamic measurement and the susceptibility of the stress corrosion cracking (SCC) was evaluated by slow strain rate test (SSRT) in 0.1 M NaF solution. The surface morphology, element analysis and surface microhardness of the electroless Ni-P composite coatings were observed and analyzed by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and vicker’s microhardness tester. Experimental results indicated that the electroless Ni-P plating coating had a beneficial effect to enhance the hardness as well as corrosion and SCC resistance of brass alloy in 0.1 M NaF solution. When the nano-TiO2 particles added this beneficial effect was significantly raised with increasing the concentrations of nano TiO2 up to 15 g/L. The improved SCC resistance was attributed to the electroless Ni-P/nanoTiO2 composite coatings preventing the formation of an unstable Cu2O passive film for brass alloy in fluoride solution. This unstable passive film could be destroyed by strain and F- attack during slow strain rate tensile test, and resulting in dezincification dissolution and an intergranular stress corrosion cracking (IGSCC) of the brass alloy.

碩士
國立聯合大學
材料科學工程學系碩士班
97
Binary Ni-Al alloy coatings were fabricated by magnetron co-sputtering technique with multi targets of pure Ni and Al metals. The chemical composition variation of the coatings in terms of sputtering input power modulation and substrate deposition temperature variation was investigated. The Ni-Al coatings with Al contents ranged from approximately 2.7 to 62.9 at.% could be manipulated through multi-gun sputtering. The as-deposited Ni-Al coatings possessed crystalline and nano-crystalline microstructures with respect to deposition input powers, substrate temperatures, and working pressures. Significant crystallization feature of disordered Ni(Al) (γ) and ordered AlNi3 (γ′) , Al3Ni (ε), and Al3Ni2 (δ) phases were observed for the Ni-Al coatings with the variation in sputtering input powers and substrate deposition temperatures. The phase evolution analysis of Ni-Al coatings indicated the good thermal stabilities for the coatings under both as-deposited and post annealed states. A thermodynamic quasi-equilibrium state formed at as-deposited state for the Ni-Al coating was confirmed. The dependency of surface morphologies and grain sizes on the variation of input powers, substrate deposition temperatures was intensively discussed. Through nano-indentation analysis, the coatings with Ni(Al) and AlNi3 microstructure feature exhibited a higher hardness. The formation of Ni(Al) and AlNi3 phases was the strengthening mechanism for Ni-Al coatings under high energy input during sputtering. The variation in hardness was attributed to the crystallite size and microstructure evolution. In order to figure out the effect of Al in properties for Ni-based coatings, the Ni-P and Ni-P-Al coating systems were compared with Ni-Al binary coating. The microstructure, phase evolution, and related properties of the Ni-P, Ni-P-Al, and Ni-Al coatings were discussed.

碩士
清雲科技大學
機械工程研究所
95
This thesis uses electroplating process to prepare Ni-P-Al2O3 composite coating on 7075 Aluminum Alloy surface by means of adding different concentrations of alumina powder (0 g/L to 50 g/L) to Ni plating solution, analysis mechanical properties in addition to evaluate the corrosion and wear-corrosion resistance of electroplating Ni-P-Al2O3 composite coating in 3.5% NaCl solution, also discussing with related micro-structural analysis results. Experimental results indicated that electroplating Ni-P-Al2O3 composite coating high hardness and wear-corrosion resistance, and the hardness of coatings increase with the coating content of alumina powder particles. Moreover, experimental result found that the concentration of adding 25 g/L alumina powder the electroplating Ni-P-Al2O3 compound coating on 7075 Aluminum Alloy substrate had the excellent corrosion resistance characteristics in 3.5% NaCl solution.

碩士
健行科技大學
機械工程系碩士班
104
This study using electroless-plating techniques to deposit the Ni-P-Cu/Graphene composite coatings on AA6061 aluminum alloy substrate after pre-treatment including thermal oxidation or anodizing evaluates the structure, mechanical properties of the composite coatings as well as their corrosion and wear resistance in 0.5M H2SO4 solution. The corrosion resistance behavior of the composite coatings was performed by using electrochemical polarization measurements. The surface morphology and elemental analysis and surface hardness of the composite coatings before and after all tests are analyzed by scanning electron microscopy (SEM) and X-ray energy dispersive analyzer (EDS). The surface hardness of the specimens was measured by a Vickers′ micro-hardness tester. It is hoped that the effect of the thermal oxidation or anodizing pre-treatment on the surface structure, corrosion and wear resistance of the composite coatings could be evaluated. The results indicated that AA6061 aluminum alloy after anodizing oxidation increases its surface hardness as well as the electroless Ni-P-Cu/Graphene composite coatings. Moreover, these composite coatings could present the well corrosion and wear protection ability to the aluminum alloy substrate. Because the graphene has a good lubrication ability such that the Ni-P-Cu/Graphene composite coating has the best corrosive wear resistance property especially as the alloy substrate after anodizing pre-treatment.

碩士
國立臺北科技大學
製造科技研究所
101
The main purpose of this study is to investigate the effects of various process parameters electrodeposited Ni-W-P alloy on the surface treatment using. The modified Watts bath consisted of nickel sulfate, phosphorous acid and Sodium tungstate solution. The Alpha-Step profilometer, FESEM, XRD were employed for observation and analysis of material microstructure in order to determine the critical factor which inference the coating hardness, such as element content and microstructure of the coating. The experimental results showed that coating hardness, heat-resistant, wear resistance and corrosion resistance is better than nickel, Ni-W alloy and Ni-P alloy. Increasing current density had obvious effect on the coating tungsten content. The hardness of the coating was increased, but the electroplated efficiency was lower, and the roughness of increased the coating surface. The phosphorus content in coating became higher with the raise in the added amount phosphorous acid, which electroplated efficiency was lower. The use of pulse plating increased tungsten content in coating, and reduced internal stress and improved electroplated efficiency. In addition raising the pH value in solution caused increases in internal stress, the coating surface cracks, and lowered electroplated efficiency. With annealing at appropriate temperature, the Ni-W-P alloy coating hardness reached 900~1100HV, which increased the wear resistance, and became a potential candidate for replacing hard chromium coating.

博士
國立清華大學
材料科學工程學系
91
Electroless nickel (EN) deposit is frequently employed for many industrial applications due to its various excellent properties. The electroless Ni-P deposit can be strengthened by the precipitation of Ni-P compounds after heat treatment. Nevertheless, the hardness of Ni-P films degrades with excessive annealing. It is thus critical to increase the crystallization temperature so that the Ni-P deposit can withstand sufficient or even superior hardness at elevated temperatures. To enhance the thermal stability, the addition of a third element in the Ni-P coating to form a ternary Ni-P-based coating is put into practice. It is found that thermal stability of electroless Ni-P-W deposit can be enhanced by the co-deposition of W as compared to binary electroless Ni-P films. The ternary Ni-P-W alloy coating is also fabricated by rf magnetron sputtering technique with dual targets of Ni-P/Cu and pure W. A fixed P/Ni ratio and linear W content dependence on input power is revealed in the ternary Ni-P-W coating, indicating a well control in composition of the coating through sputtering technique. Thermal stability analysis shows that the introduction of W in the Ni-P coating by co-sputtering retards the Ni3P precipitation and retains the strengthening effect to a higher temperature of 550°C. Microstructure evolution indicates that all coatings in the as-deposited state show amorphous structure. The precipitation of Ni3P accompanied with W dissoluted Ni matrix is revealed to be the final product of the phase transformation in Ni-P-W coatings after thermal treatment. Results in microhardness test show that the surface hardness can be engineered by the controlling the composition and microstructure in the Ni-P-W coating. After heat treatment, the coating is strengthened by the precipitation of Ni-P compounds and solutioning of W in the crystallized Ni matrix. Quantitative analysis for the strengthening effect of the Ni-P-W coatings is performed based on Ni-P compound precipitation and Ni(W) matrix ratio. Both electroless Ni78.4P18.3W3.3 and sputtered Ni80.0P15.3W4.7 coatings exhibit a hardness around 1600 HK due to Ni3P precipitation and W solutioning hardening in Ni matrix to a W/Ni(W) ratio of approximately 12at.% after heat treatment. A higher microhardness of 1790 HK is measured in the sputtered Ni76.7P15.9W7.4 coating. Through quantitative analysis, the effect of strengthening in Ni-P-W ternary coatings under heat treatment can be clearly demonstrated. From surface analysis, the nodular nature of the electroless coatings is responsible for the rougher surface profile as compared to the sputtered coatings. With the co-sputtering of W, the early stage Ni-P compounds is suppressed, according to X-ray and surface morphology analysis. After heat treatment, the surface morphology and roughness of both electroless and sputtered Ni-P-W films remain identical to those in the as-deposited state, indicating a stable surface characteristic under thermal treatment.

碩士
國立聯合大學
材料科學工程學系碩士班
96
Electroplating Ni–P coatings had been used in various industrial applications due to its excellent corrosion and wear resistance, and mechanical and surface properties. After adequate heat treatment, Ni-P precipitation and Ni crystallization formed, leading to the increase of surface hardness upto 800Hv. For electroplating process, the current density is frequently increased to increase deposition rate. However the irregularity in edge region was significant subsequently, especially on sharp edge geometries. Non-homogeneity in composition and thickness distribution were the severest problem. In present study, the deposition parameters including current density and edge type were intensively discussed. The optimized composition and thickness distribution were obtained through the decrease in current density down to 75 mA/cm2 with a round or 45�a cut-off edge geometries. On the other hand, the addition of Al, as a third element, in Ni-P was also proposed to improve the mechanical property and thermal stability of the binary Ni-P coatings at elevated temperature. In this study, the ternary Ni-P-Al coatings were fabricated by sputtering technique with Ni-P/Al target designed by electroplating Ni-P on Al pure disk. Through phase identification, the coating with Al addition in the Ni-P material system exhibited a crystallization temperature of 475�aC, which was 75�aC higher than that of binary Ni-P coating. The phase transformation behavior was significantly affected by the composition of Ni-P-Al coating. Under high temperature and low Ar flow during sputtering process, the coating structure is crystalline. On the other hand, with low process temperature and high Ar flow, the structure is amorphous due to significant energetic particle impingement and less diffusion energy by substrate heating. Phase transformation through process heating and post heat treatment were also discussed. The coating deposited under higher process temperature forced the crystallization process and lowered the mechanical properties as compared to those under post annealing. In addition, with higher addition amount of Al element of 61at.% in Ni-P system, a thermal stability up to 600°C was observed.