Dissertations / Theses on the topic 'Corrosion removal'

The purpose of this thesis study is to assess the feasibility of using a fiber sorbent module system to remove t-butyl mercaptan (TBM), a common odorant, from pipeline grade natural gas. Odorants such as mercaptans are added to natural gas for safety reasons, but their combustion products are corrosive and decrease the lifetime of the turbines in which they are combusted. Therefore, it is desirable to remove the odorants to extend this lifetime. A TBM removal system attached to a 840 MW natural gas-fueled combined cycle power plant unit such as the one at Plant McDonough-Atkinson (Smyrna, GA) must process gas at a flow rate of approximately 180,000 standard cubic feet per minute. A single 85 MW GE 7EAQ gas turbine has a flow rate of approximately 15,000 standard cubic feet per minute, and will serve as the basis for a system design and process analysis study. The concentration of odorants in natural gas is typically 10 ppm or less. For the purposes of this study, the upper limit of 10 ppm TBM will be used. Zeolite 13X was selected as the model adsorbent for this study due to its high sorption capacity for mercaptans and its ease of incorporation into both fibers and pellets. Design calculations were performed to optimize and determine the feasibility of fiber modules for TBM removal, as well as assess their advantages over conventional pellet packed beds. An understanding of how critical parameters such as heat and mass transfer resistances, pressure drop, and capital and operating costs are affected by design specifications such as sorbent and bed dimensions, allows an optimal design for the needs of the model turbine to be found. Based on these design equations, a fiber sorbent module configuration that selectively and continuously removes TBM from natural gas is developed

Chemical systems containing oxidants are widely used at various stages in semiconductor processing, particularly for wet cleaning and polishing applications. This dissertation presents a series of studies related to oxidative removal of materials in the Front-End-Of-Line (FEOL) and Chemical Mechanical Planarization (CMP) processes during IC fabrication. In the first part of this study, stripping of photoresists exposed to high dose of ions (1E16 As/cm²) was investigated in activated hydrogen peroxide systems. Stripping of photoresists (PR) exposed to high dose (>1E15/cm²) ion beams is one of the most challenging steps in FEOL processing. This is due to unreactive crust layer that forms on the resist surface during ion implantation. The use of hydrogen peroxide systems activated by metal ion or UV light, for disrupting crust formed on deep UV resist to enable complete removal of crust as well as underlying photoresist was investigated. A systematic evaluation of variables such as hydrogen peroxide and metal ion concentration, UV intensity, temperature and time was conducted and an optimal formulation capable of attacking the crust was developed. A two step process involving pretreatment with activated hydrogen peroxide solution, followed by treatment with sulfuric acid-hydrogen peroxide mixture (SPM) was developed for complete removal of crusted resist films. In the second part of this study, electrochemically enhanced abrasive removal of Ta/TaN films was investigated in solutions containing 2,5 dihydroxy benzene sulfonic acid (DBSA) and potassium iodate (KIO₃). This method known as Electrically-assisted Chemical Mechanical Planarization (ECMP) is generating a lot of interest in IC manufacturing. Ta/TaN films were abraded at low pressures (<0.5 psi) on a polyurethane pad under galvanostatic conditions. The effect of variables including pH, KIO3 concentration, and current density has been explored. In the optimized formulation, tantalum and tantalum nitride removal rates of ~170 A⁰/min and ~200 A⁰/min, respectively have been obtained at a current density of 1 mA/cm². The use of benzotriazole as a copper inhibitor was required to obtain Ta to Cu selectivity of 0.8:1. Additionally, the nature of the oxide film formed on tantalum during the electrochemical abrasion process was characterized.

In the current study, we analyze the effectiveness of an organosilane compound, 3-mercapto-propyl-tri-methoxy-silane (abbreviated PropS-SH), in the corrosion protection of fire-gilded bronzes. Firstly, the coating was applied on as-gilded bronze. Subsequently, it was also applied on pre-patinated bronze, because the substrate on which protective coatings are applied in real conservation interventions are corroded artifacts (cleaning procedures never remove all the corrosion products). Aiming to obtain results that simulate the situation of real artifacts, a dropping test that simulates outdoor exposure in runoff conditions (unsheltered areas of monuments) was employed in order to prepatinate the gilded bronze samples, which are the substrate for applying the protective coating. The preparation of the samples by applying the protective coating was performed in collaboration with the Corrosion Studies Centre “Aldo Daccò” from Ferrara University. After the artificial exposure cycles the samples underwent investigations through a variety of spectroscopic methods including SEM, Raman, FIB, AAS and color measurements. In order to evaluate the possible removal of the organosilane coating, protected samples were subjected to laser cleaning tests and characterized by SEM/EDS so as to assess the changes in composition and morphology of the treated surfaces. The laser cleaning treatment was performed at the Institute of Applied Physics “Nello Carrara” (CNR Sesto Fiorentino (FI)). The morphology and chemical composition of the samples was observed before and after the operation in order to obtain information about the fluence and type of laser which are best suited to the removal of this type of coating.

Outdoor bronzes exposed to the environment form naturally a layer called patina, which may be able to protect the metallic substrate. However, since the last century, with the appearance of acid rains, a strong change in the nature and properties of the copper based patinas occurred [1]. Studies and general observations have established that bronze corrosion patinas created by acid rain are not only disfiguring in terms of loss of detail and homogeneity, but are also unstable [2]. The unstable patina is partially leached away by rainwater. This leaching is represented by green streaking on bronze monuments [3]. Because of the instability of the patina, conservation techniques are usually required. On a bronze object exposed to the outdoor environment, there are different actions of the rainfall and other atmospheric agents as a function of the monument shape. In fact, we recognize sheltered and unsheltered areas as regards exposure to rainwater [4]. As a consequence of these different actions, two main patina types are formed on monuments exposed to the outdoor environment. These patinas have different electrochemical, morphological and compositional characteristics [1]. In the case of sheltered areas, the patina contains mainly copper products, stratified above a layer strongly enriched in insoluble Sn oxides, located at the interface with the uncorroded metal. Moreover, different colors of the patina result from the exposure geometry. The surface color may be pale green for unsheltered areas, and green and mat black for sheltered areas [4]. Thus, in real outdoor bronze monuments, the corrosion behavior is strongly influenced by the exposure geometry. This must be taken into account when designing conservation procedures, since the patina is in most cases the support on which corrosion inhibitors are applied. Presently, for protecting outdoor bronzes against atmospheric corrosion, inhibitors and protective treatments are used. BTA and its derivatives, which are the most common inhibitors used for copper and its alloy, were found to be toxic for the environment and human health [5, 6]. Moreover, it has been demonstrated that BTA is efficient when applied on bare copper but not as efficient when applied on bare bronze [7]. Thus it was necessary to find alternative compounds. Silane-based inhibitors (already successfully tested on copper and other metallic substrates [8]), were taken into consideration as a non-toxic, environmentally friendly alternative to BTA derivatives for bronze protection. The purpose of this thesis was based on the assessment of the efficiency of a selected compound, to protect the bronze against corrosion, which is the 3-mercapto-propyl-trimethoxy-silane (PropS-SH). It was selected thanks to the collaboration with the Corrosion Studies Centre “Aldo Daccò” at the Università di Ferrara. Since previous studies [9, 10, 11] demonstrated that the addition of nanoparticles to silane-based inhibitors leads to an increase of the protective efficiency, we also wanted to evaluate the influence of the addition of CeO2, La2O3, TiO2 nanoparticles on the protective efficiency of 3-mercapto-propyl-trimethoxy-silane, applied on pre-patinated bronze surfaces. This study is the first section of the thesis. Since restorers have to work on patinated bronzes and not on bare metal (except for contemporary art), it is important to be able to recreate the patina, under laboratory conditions, either in sheltered or unsheltered conditions to test the coating and to obtain reliable results. Therefore, at the University of Bologna, different devices have been designed to simulate the real outdoor conditions and to create a patina which is representative of real application conditions of inhibitor or protective treatments. In particular, accelerated ageing devices by wet & dry (simulating the action of stagnant rain in sheltered areas [12]) and by dropping (simulating the leaching action of the rain in unsheltered areas [1]) tests were used. In the present work, we used the dropping test as a method to produce pre-patinated bronze surfaces for the application of a candidate inhibitor as well as for evaluating its protective efficiency on aged bronze (unsheltered areas). In this thesis, gilded bronzes were also studied. When they are exposed to the outside environment, a corrosion phenomenon appears which is due to the electrochemical couple gold/copper where copper is the anode. In the presence of an electrolyte, this phenomenon results in the formation of corrosion products than will cause a blistering of the gold (or a break-up and loss of the film in some cases). Moreover, because of the diffusion of the copper salts to the surface, aggregates and a greenish film will be formed on the surface of the sample [13]. By coating gilded samples with PropS-SH and PropS-SH containing nano-particles and carrying out accelerated ageing by the dropping test, a discussion is possible on the effectiveness of this coating, either with nano-particles or not, against the corrosion process. This part is the section 2 of this thesis. Finally, a discussion about laser treatment aiming at the assessment of reversibility/re-applicability of the PropS-SH coating can be found in section 3 of this thesis. Because the protective layer loses its efficiency with time, it is necessary to find a way of removing the silane layer, before applying a new one on the “bare” patina. One request is to minimize the damages that a laser treatment would create on the patina. Therefore, different laser fluences (energy/surface) were applied on the sample surface during the treatment process in order to find the best range of fluence. In particular, we made a characterization of surfaces before and after removal of PropS-SH (applied on a naturally patinated surface, and subsequently aged by natural exposure) with laser methods. The laser removal treatment was done by the CNR Institute of Applied Physics “Nello Carrara” of Sesto Fiorentino in Florence. In all the three sections of the thesis, a range of non-destructive spectroscopic methods (Scanning Electron Microscopy with Energy Dispersive Spectroscopy (SEM-EDS), μ-Raman spectroscopy, X-Ray diffractometry (XRD)) were used for characterizing the corroded surfaces. AAS (Atomic Absorption Spectroscopy) was used to analyze the ageing solutions from the dropping test in sections 1 and 2.

The plasmachemical removal process of corrosion layers is based on a reduction effect of RF hydrogen low-pressure plasma, and it is used for archaeological objects. Incrustation layers on artifact surface become brittle and porous due to plasma processing. The structure and composition of corrosion layers is changed. Therefore, it is much easier to recover the original surface of the plasma treated artifacts in contrary to those treated by conventional ways. Moreover, we can save time on invasive and thus dangerous mechanical removal of corrosion layers as for example sanding is. After plasma treatment, we can observe fine details of the original surface and memory of tools used during its manufacturing. These details are important information on the origin and manufacturing methods of the artifacts. The plasma reduction process leads to the removal of impurities from cavities as well, and a function of mechanical components of archaeological object can be restored. Moreover, chlorides can be easily removed from the corrosion layers and thus any significant post-corrosion is protected. Each archaeological object is original and it has its own “corrosion history”. First, the object had been exposed to the atmosphere for a long time. Then, it had been often placed in a tomb or grave or it otherwise got into the soil or sea. Thus, each archaeological object was exposed to different corrosion stress (humidity, composition of corrosive environment, etc.). Due to these facts, any universal way of a corroded object treatment is very difficult or even impossible to propose. In this work, the problem was solved using model samples of common metals which were treated at various plasma treatment conditions. Archaeological objects made of iron are the most common artifacts, and the typical corrosion products on iron are akaganeite, rokuhnite, and szomolnokite. These three corrosion products were created on the model samples in laboratory and then, the plasmachemical reduction was applied for their removal. The experiment was done in a Quartz cylindrical reactor with capacitive coupled RF plasma created using outer electrodes. We used discharge power from 100 W to 400 W in a continuous or pulsed regime (duty cycle of 75 %, 50 % and 25 %). Flowing plasma was created in pure hydrogen at pressure of 150200 Pa. Sample temperature was monitored by a thermocouple, and it did not exceed 200C during all these experiments. This temperature is regarded as a limit temperature for metallographic changes of archaeological iron. Higher temperature can cause destruction of archaeological iron objects. The optical emission spectroscopy of OH radical was used for the process monitoring. We focused on the monitoring of OH-radicals generated in the plasma, which are characteristic species formed by this process. Each corrosion product has a different time evaluation of generated OH-radicals, which is closely related to the degradation of a given corrosion product. Corrosion layers were analyzed before and after the plasmachemical reduction by SEM-EDX. We have found that the plasmachemical reduction is not very suitable for the szomolnokite corrosion product, which is degraded with difficulty and at high applied powers, only. However, very good removal efficiency was obtained for the rokuhnite and akaganeite corrosion.

This diploma thesis builds on my bachelor thesis, which was focused on the application of low-pressure hydrogen plasma and argon-hydrogen plasma on layers of corrosion products. According to results of the experiments, an appropriate temperature for plasma chemical treatment of lead samples was detected. However, the process of corrosion removal through plasma chemical treatment needs to be further optimized to prevent potential damage to the original historical artefacts. Optimization of the treatment process is therefore the main subject of this work’s research. The model samples with artificial corrosion layers with dual composition were prepared. These samples were put to desiccator with sand and organic acid. The samples corroded in environment of acetic acid or formic acid with the aim of creating the corrosion, which would be at least partially simulated with corrosion on the original artefacts. The process of corrosion lasted for eleven months. After that, the samples were dried out under reduced pressure, put to the protecting foil with humid and oxygen absorbers. In contrast with my bachelor thesis where the continuous regime was chosen for the treatment, the pulse regime with three different condition settings is used. Process of experiment was monitored by OES, surface of samples was analyzed by SEM, EDX, XRD methods. Results from experiments with model samples were used for treatment of original artefacts with missing documentation, so their eventual damaging was acceptable.

The purpose of this study was to simulate the liquid flow rate distribution in the etching modules and find the optimal setup in order to achieve a distribution as homogenous as possible. The commercial software Matlab 2015a has been employed for all the numerical simulations. The optimization has been carried out varying several parameters, i.e. spray cross sections of the nozzles, the oscillation parameters, the rotating angle of the nozzles within etching module 1 and the nozzle arrangement inside the modules. Furthermore, the optimization has been carried out separately along the two directions of the modules. The results achieved computationally have been validated via experimental procedures. During this study a specific experimental setup has been developed in order to be able to compare experimental and computational results. The validation process has shown that the computational method matches the experimental results to a good extent. The experimental liquid distribution in etching module 2 widely matches the simulations to a quantitative extent, while the one in etching module 1 provides the same qualitative but different quantitative results.

Several aesthetic, health, and plumbing quality issues can arise during new construction or renovation of premise plumbing. There has been little research done on many of these concerns and therefore few guidelines or regulations are in place to protect the health of the consumer or the integrity of the plumbing infrastructure. This work examines common construction practices including: 1) effect of residual construction debris, 2) shock chlorination of new plumbing lines, and 3) lead leaching propensity of new brass ball valves. During installation of plumbing systems, residual chemicals and debris including copper brass particles and flux, can be left in plumbing lines following construction and installation. This debris is considered undesirable from health, aesthetic, and corrosion perspectives. Soldering flux is of particular concern due to its corrosive nature. Experiments were conducted to determine the effects of residual solder flux, PVC glue, and metallic debris and to quantify flushing velocities and durations to effectively remove them from a new plumbing system. A flushing velocity of 3 fps for 30 minutes is needed to remove water soluble flux, while petroleum based flux still persists after extensive flushing at 7 fps. Currently a practice known as shock chlorination, whereby super chlorinated water is used for disinfection, is used in water mains after installation or repair as specified in the ANSI/AWWA C651 Standard. This practice is now starting to be required by some building codes in premise plumbing for new construction. Water mains are typically made of concrete where as premise plumbing using copper or PVC piping. Copper pipe is susceptible to attack by high chlorine, and this reaction will also remove the chlorine residual. There is concern about potential damage to copper from free chlorine and that in some systems targeted residuals of chlorine might not be obtained. Experiments did not detect serious damage to copper pipe, but in some waters it was not possible to meet targeted residual levels of chlorine. The addition of orthophosphate corrosion inhibitor or adjustment of pH can sometimes reduce the chlorine decay rate. Extremely high and persistent lead leaching in a brand new building at the University of North Carolina (UNC) traced to leaded bronze ball valves, prompted an extensive forensic evaluation how existing standards (National Sanitation Foundation Section 8) could allow for installation of products that could create a human health hazard due to high lead. Diffusion of lead from within the device to water in the pipe, high velocity, microbial activity and other factors caused more leaching in practice than would be expected based on NSF testing and normalization factors applied to certify a valve as safe. Moreover, use of flux during soldering of joints, increased lead leaching by orders of magnitude relative to results of NSF testing without flux.
Master of Science

O processo de moldagem de pós injeção é utilizado para a fabricação de peças de geometrias complexas e com alto volume de produção. Em aplicações ortodônticas e médicas, nas quais são requeridas elevadas durezas e resistências à corrosão, o aço inoxidável 17-4 PH é utilizado aplicando-se aquela técnica de conformação. A atmosfera de sinterização é responsável pelo controle das reações químicas que ocorrem durante a densificação do material e são fundamentais para a qualidade final do produto. O objetivo deste trabalho foi avaliar a influência da atmosfera de sinterização na dureza e resistência à corrosão deste tipo de aço. A remoção dos ligantes primários foi realizada por meio de extração química utilizando-se um solvente com menor impacto ambiental, que se mostrou adequado a tal fim. A extração térmica posterior dos ligantes foi realizada pelo aquecimento nas temperaturas de 250°C e 450°C sendo, posteriormente, a temperatura elevada a 900°C, para o início da sinterização. Utilizou-se atmosferas de Nitrogênio, Vácuo e Hidrogênio, com temperaturas de sinterização de 1250°C e 1330°, com tempos de patamares de 30 e 60 minutos. Verificou-se que as densidades atingidas nas atmosferas de Hidrogênio e Vácuo são semelhantes e se adequaram às especificações requeridas pela norma, enquanto a atmosfera de Nitrogênio resultou em características inferiores. As durezas e as resistências à corrosão obtidas com o uso das atmosferas de Hidrogênio e Vácuo foram também superiores as das amostras sinterizadas em atmosfera de Nitrogênio.
The powder injection molding process is used to manufacture parts with complex shapes, with high production demand. In orthodontic and medical applications, in which high hardness and corrosion resistance are required, 17-4 PH stainless steel is used by applying this forming technique. The sintering atmosphere is responsible for controlling the chemical reactions that occur during material densification and is critical to the ultimate product quality. This research study aims at evaluating the influence of the sintering atmosphere on the hardness and corrosion resistance of this type of steel. The removal of the primary binder was carried out by chemical extraction applying a solvent with less environmental impact, which has proved to be suitable for this purpose. The subsequent binder thermal extraction was held by heating at temperatures of 250°C and 450°C and, therefore, at temperature of 900°C, to initiate sintering. Nitrogen, vacuum and hydrogen atmospheres were used with sintering temperatures at 1250°C and 1330°, with 30 and 60 minute-step time. It was verified that the densities achieved in hydrogen and vacuum atmospheres are similar and suitable by the regulations, whereas the nitrogen atmosphere resulted in lower performance. The hardness and corrosion resistance obtained with the use of hydrogen and vacuum atmospheres were also higher than those obtained for samples sintered in the nitrogen atmosphere.

A higienização das próteses parciais ou totais removíveis é fundamental para a durabilidade do tratamento e prevenção de patologias orais. O objetivo deste estudo foi avaliar o efeito de agentes higienizadores de prótese na cor, corrosão e rugosidade superficial do titânio c.p., ligas metálicas e resina acrílica termopolimerizável, simulando um período de 180 dias de higienização. Espécimes em formato de discos (12 mm x 3 mm) foram confeccionados em: titânio comercialmente puro (Tritan - Ti c.p.), liga de níquel-cromo-molibdênio-titânio (Vi-Star), liga de níquel-cromo (Fit Cast-SB Plus) e liga de níquel-cromo-berílio (Fit Cast-V). Cada disco fundido foi incluído em mufla previamente preparada por matrizes retangulares de teflon (38 mm x 18 mm x 4 mm), incorporando-se o disco metálico à resina acrílica termopolimerizável. Os corpos-de-prova (n=5) foram imersos em soluções dos agentes higienizadores: hipoclorito de sódio a 0,05%, Periogard, Cepacol, pastilha Corega Tabs, pastilha Medical Interporous e pastilha Polident 3 Minute. Como controle, foi utilizada a água deionizada. Foram realizados ensaios de estabilidade de cor por meio de espectrocolorímetro (Color-guide 45/0), resistência à corrosão por meio da análise visual da presença de manchas no metal e análise da alteração de massa (balança eletrônica analítica), e rugosidade superficial por meio de rugosímetro (Surftest SJ-201P). Além disso, foi realizada análise quantitativa de liberação de íons metálicos por meio de espectrometria de massa com plasma indutivamente acoplado (ICP-MS - ELAN DRC II). Os resultados de estabilidade de cor, alteração de massa e rugosidade foram submetidos à ANOVA e teste de Tukey (p< 0,05). Quanto à estabilidade de cor da resina acrílica termopolimerizável (E), houve diferença estatisticamente significante entre o titânio c.p. e as ligas. A resina associada ao Ti c.p. apresentou menor alteração de cor, enquanto que a resina associada à Fit Cast-SB Plus apresentou a maior alteração de cor (1,33 ± 1,11 e 5,06 ± 1,96, respectivamente). Com relação à presença de manchas no metal, o hipoclorito de sódio causou manchamento nos espécimes das ligas Vi-Star e Fit Cast-V. Quando avaliada a alteração de massa (g), o Cepacol e a pastilha Corega Tabs propiciaram maior perda de massa. Entre os metais, a amostra do Ti c.p. apresentou maior perda de massa. Quanto à rugosidade (Ra, µm) da resina, o Cepacol causou maior rugosidade, enquanto que a pastilha Corega Tabs e o Periogard propiciaram maior lisura no corpo-de-prova. A resina associada ao Ti c.p. e ao Fit Cast-SB Plus apresentaram maior rugosidade. Quanto à rugosidade do metal, os produtos de imersão não influenciaram nos resultados, mas a liga Fit Cast-SB Plus apresentou maior rugosidade após a imersão. A liberação de íons mais expressiva foi constatada nas ligas Vi-Star e Fit Cast-V após a imersão na pastilha Medical Interporous. Pode-se concluir que as ligas Vi-Star e Fit Cast-V podem ser consideradas seguras para a confecção de aparelhos protéticos removíveis, mas com a condição de não utilizar o hipoclorito de sódio a 0,05% ou a pastilha Medical Interporous para a higienização, pois causaram corrosão e maior liberação de íons, respectivamente.
The hygiene care of the removable partial and complete dentures is required for the longevity of the treatment and prevention of oral diseases. The aim of this study was to evaluate the effect of denture cleansers on color, corrosion and surface roughness of the commercially pure titanium, metal alloys and heat-polymerized acrylic resin, simulating a period of 180 days of hygiene. Disk-shaped specimens (12 mm x 3 mm) had been fabricated with commercially pure titanium (Tritan - Ti c.p.), nickel-chromium-molybdenum-titanium alloy (Vi-Star), nickel-chromium alloy (Fit Cast-SB Plus) and nickel-chromium-beryllium alloy (Fit Cast-V). Each cast disc was invested in the flasks previously prepared by Teflon rectangular matrices (38 mm x 18 mm x 4 mm), incorporating the metal disk to the heat-polymerized acrylic resin. The specimens (n= 5) had been immersed in the solutions: sodium hypochlorite 0.05%, Periogard, Cepacol, Corega Tabs, Medical Interporous and Polident 3 Minute. As a control, it was used deionized water. It was accomplished assays of color stability by means of a colorimeter (Color-guide 45/0), corrosion resistance by means of visual analysis of tarnishes on the metal and mass alteration analysis (analytical electronic balance), and surface roughness by means of a surface analyzer (Surftest SJ-201P). Besides, the quantitative analysis of metal ions release was accomplished by means of inductively coupled plasma mass spectrometry (ICP-MS - ELAN DRC II). Color stability, mass alteration and roughness results were submitted to ANOVA and Tukey test (p<0.05). Considering the color stability of the heat-polymerized acrylic resin (E), there were statistically significant difference between the titanium c.p. and the alloys. The resin associated with the Ti c.p. showed lesser color alteration, whereas the resin associated with Fit Cast-SB Plus showed the higher color alteration (1,33 ± 1,11 e 5,06 ± 1,96, respectively). In relation to the presence of tarnishes on the metals, the sodium hypochlorite caused tarnishes on specimens of the Vi-Star and Fit Cast-V alloys. When evaluated the mass alteration (g), Cepacol and Corega Tabs propitiated higher weight loss. Between the metals, the Ti c.p. samples showed greater weight loss. Considering the resin roughness (Ra, µm), Cepacol caused higher roughness, whereas Corega Tabs and Periogard propitiated greater smoothness on the specimens. The resin associated with the Ti c.p. and Fit Cast-SB Plus showed higher roughness. Considering the metal roughness, the immersion products did not influence on the results, but the Fit Cast-SB Plus showed greater roughness after immersion. The ionic release most significant was with the Vi-Star and Fit Cast-V alloys after immersion in Medical Interporous. It could be concluded that the Vi-Star and Fit Cast-V alloys can be considered safe for removable prosthesis finish, but with the condition of do not use sodium hypochlorite 0.05% or Medical Interporous tablet for hygiene, because they caused corrosion and greater ionic release, respectively.

Transparency is a fundamental feature to preserve on a stained-glass panel. The passage of light is the essence of this art form and, as so, a crucial piece of its original intention, both through the colored glass as through the paintings. Medieval stained-glass is characterized by a relatively high content of alkali and alkali-earth ion oxides, mainly potassium, calcium and sodium, and low contents of silica compared to contemporary glass. These ions are leached, and when in contact with the atmosphere a gel-layer (hydrated silica-rich surface) is formed, and consequently there is the formation of a corrosion crust. This is mainly composed by insoluble salts such as calcium carbonate (CaCO3), sulfate (CaSO4) and oxalate (CaC2O4), which are very difficult to remove from the glass surface. The methods that present higher efficiency for the removal of those crusts – like chelate agents (e.g. EDTA solutions), weak acids and ionic resins – are the same that may induce damage or long-term risks to the glass surface. The aim of this research was to develop a new product – an ionic liquid (IL) – for the removal of medieval stained-glass corrosion that is effective and harmless both for the stained-glass and for the user. To assure the complete removal of both corrosion and cleaning material (the ionic liquid) after the procedure, the IL was functionalized using a light emitting marker – intrinsically luminescent ionic liquid. It was our objective to have an IL with a dual function: having a binding site for metal cations (in this case, Ca2+), while exhibiting bright fluorescence. The effects on the surface of model glass of three different ILs, an EDTA solution and the effect of a high relative humidity (RH) environment are described and compared. A comparison between the efficiency of two ILs and an EDTA solution for the corrosion crusts removal was made using corroded archaeological stained glass samples. The tests performed confirmed the effectiveness of the cleaning material in removing the corrosion crusts, and also demonstrated that there were no detected alterations to the glass surface even when in direct contact with the ionic liquids for a long period of time.

碩士
中原大學
生物環境工程研究所
102
The antimicrobial activity of zirconia (ZrO2) nanoparticles was studied on bacterial strains of Escherichia coli and Staphylococcus aureus using two different syntheses: sol-gel method and simple hydrothermal process with commercial zirconia as reference. Sol-gel synthesized zirconia exhibited an antibacterial efficiency of 99.9% which is two folds higher than commercial zirconia. Agar well diffusion test on ZrO2 resulted to a significant inhibition zone of 19 and 22 mm for E. coli and S. aureus respectively. PANI-ZrO2 showed an effective area of inhibition of 14 and 18 mm on E. coli and S. aureus strains respectively. MIC and MBC experiments verified that 0.001 g/mL of ZrO2, PANI and PANI-ZrO2 is the lowest concentration needed to inhibit the growth of bacteria and kill 99.9% of initial bacteria inoculum 106 CFU/mL. Nanocomposite material containing PANI and ZrO2 was successfully synthesized and coated on iron substrate using epoxy resin. Coatings on iron substrates were further subjected to corrosion test by immersion to 3.5 and 7.5% NaCl solution for 1 month. Results showed that there was no rust formation for ZrO2 and PANI-ZrO2 coatings on the iron substrate since they are known to possess anti-corrosive property. Thus, ZrO2 and PANI-ZrO2 can be significantly used for anti-corrosion and antibacterial applications. The incorporation of ZrO2 on the polymer matrix of PANI increased the protective barrier against corrosion. PANI-ZrO2 nanocomposite and ZrO2 nanoparticles were studied for phosphate adsorption in 200 mg P/L phosphate solution. PANI-ZrO2 exhibited an estimated phosphate removal efficiency of 64.4% and 36.7% for pure ZrO2. Adsorption isotherm best fitted the Langmuir equation with R2 = 0.9532 and maximum adsorption capacity of 36.12 mg P/g for ZrO2. PANI-ZrO2 nanocomposite exhibited a maximum adsorption capacity of 32.37 mg P/g with R2 = 0.9496. Results confirmed that ZrO2 and PANI-ZrO2 composite have high affinity to phosphate ions and exhibits fast adsorption kinetics with high adsorption capacity which is essential for the treatment of waste effluents.

This PhD thesis presents an innovative poly(vinyl)alcohol-based film forming system, specifically devised to obtain a controllable and selective cleaning of ancient copper-based artifacts. Traditional cleaning procedures of metallic artifacts are commonly performed by mechanical and/or chemical methods. Unfortunately, both these methods present some limits, mainly related to poor selectivity, high invasiveness and scarce control over the cleaning procedures. The main advantage of the cleaning system presented here, consists in the simultaneous chemical and mechanical action, guaranteed respectively by the presence of a confined complexing agent specific for Cu(II) ions (EDTA, Rochelle salt, polyamines) and by the removal of the final film through a peeling action. The physico-chemical characterization of the cleaning system was carried out through different methods (gravimetry, thermal analysis, rheology and ATR-FTIR spectroscopy) in order to study the kinetics of films formation and their mechanical properties. Finally, cleaning tests were firstly performed on different artificially aged samples, then on real cases of study. Questa tesi di dottorato presenta un innovativo sistema filmante a base di polivinilalcol, sviluppato specificamente per ottenere una pulitura controllabile e selettiva su manufatti antichi in lega base-rame. Le tradizionali procedure di pulitura di manufatti metallici sono comunemente eseguite tramite metodi chimici e/o meccanici. Sfortunatamente, entrambi questi metodi, presentano alcuni limiti legati principalmente a scarsa selettività, elevata invasività e assenza di controllo sulle procedure di pulitura. Il principale vantaggio del sistema pulente qui presentato consiste nella simultanea azione chimica e meccanica, garantita rispettivamente dalla presenza di un agente complessante confinato, specifico per gli ioni Cu(II) (EDTA, sale di Rochelle, poliammine) e dalla rimozione del film finale tramite un'azione di peeling. La caratterizzazione chimico-fisica del sistema pulente è stata eseguita tramite diversi metodi (gravimetria, termoanalisi, reologia, spettroscopia ATR-FTIR) in modo da studiare le cinetiche di formazione dei film e le loro proprietà meccaniche. Infine, test di pulitura sono stati eseguiti inizialmente su provini invecchiati artificialmente e poi su casi studio reali.

Over the past decade, the objectives for coagulation based drinking water treatment processes have changed significantly. These changes are a result of stringent goals related to natural organic matter (NOM) removal to mitigate the formation of subsequent harmful and health-related disinfection by-products (DBPs) and the need to achieve adequate filtration performance to ensure sufficient particle removal for pathogen control. Another concern associated with coagulation optimization is the potential unintended consequences of a coagulant change on the distribution system, specifically related to lead release from lead pipe and solder materials. Optimizing these multi-objectives in a direct filtration treatment process presents significant challenges for source waters characterized by low levels of turbidity, alkalinity and organic matter content. Bench and pilot-scale experiments were conducted to evaluate the performance of ferric sulfate, polyaluminum chloride (PACl) and aluminum chlorohydrate (ACH) against aluminum sulfate (alum) using variable coagulation dosage and pH conditions for a direct filtration facility. Bench-scale experiments were conducted to optimize NOM removal during coagulation using traditional organic matter surrogates coupled with molecular size characterization techniques. Pilot-scale studies provided a snapshot of feasibility in terms of filtration performance for favourable bench-scale conditions and also identified optimal conditions for filtration performance. Results from pilot testing demonstrated that favourable conditions identified for increased potential NOM removals during bench-scale testing were significantly different than optimal filtration conditions identified during pilot studies; and, in fact, severely compromised direct filtration performance due to increased solids loading to the filters. Bench-scale experiments evaluated lead leaching from lead and lead:tin solder galvanically connected to copper under stagnant conditions using variable chloride-to-sulfate mass ratio (CSMR) conditions for alum, ferric sulfate and PACl. Although recent research identifies high CSMRs (>0.5) as the main mechanism of attack in distribution systems following coagulant changeovers, CSMR was not the primary catalyst for lead leaching following the coagulant changeover conditions evaluated in this study. Residual concentrations of iron and aluminum remaining following coagulation were the principal contributors. Positive correlations were revealed between particulate iron and particulate lead concentrations following stagnation demonstrating that the adsorption of lead to iron oxides is a viable hypothesis for lead release.

The presence of dirt, soil, aged polymers or corrosion patinas can hinder the readability of artworks; in these cases, non-invasive and controlled removal is essential. Nanostructured fluids (NSFs) - such as micellar solutions and microemulsions- allowed achieving this purpose, decreasing, at the same time, the drawbacks related to the use of solvents. In the last decades, several cleaning fluids have been developed; surfactants, in particular, have a crucial role in the NSFs’ formulations. For this reason, the research of innovative and highly performing amphiphiles represents one of the main goals in modern conservation science, in order to develop safer and greener systems. Two different NSFs were prepared with MPD surfactant and their interaction with soil and polymeric layers was evaluated through several techniques (CLSM, photographic observation, contact angle and surface tension measurements). Moreover, a comparison with a conventional nonionic surfactant (PDE) was made. MPD-based NSFs were found to be more effective in cleaning surfaces, also without mechanical action. Confining cleaning fluids in retentive matrices like gels represents one of the most powerful strategies to obtain greater control of the cleaning action. Two different pHEMA-based semi-IPNs were used as scaffold for a high selective agent (i.e., TEPA) able to remove corrosion products without affecting the protective cuprite layers. Changes in gels’ structure were evaluated by means DSC, TGA and SEM analysis before and after the interaction with the copper alloys; Cu(II) ion adsorption kinetics were used to assess the effect of the gels’ structure on the adsorption process. The pHEMA-based gels, classified as “rigid systems”, are not suitable for the treatment of bronze sculpture characterized by deep cavities and high reliefs. To overcome these limitations, TEPA was confined into a PVA-based film (HVPD) forming system. Thanks to its viscoelastic properties and its ability to combine a chemical action with a mechanical one, the HVPD represents a good option in these cases. The physico-chemical characterization was carried out to evaluate the effect of TEPA-addition on (1) the kinetics of the film formation, quantified through gravimetric and rheological measurements, and on (2) the final films’ properties, determined by DSC, ATR-FTIR and SEM analysis. 2D FTIR FPA Imaging confirmed the complete removal of corrosion products, the preservation of cuprite layers and the absence of residues on the mock-up surfaces after the treatment with both semi-IPNs and HVPDs. Finally, tests on real cases study are presented.

Lead is a known toxin, with the ability to accumulate in the human body from as early as fetal development. Lead exposure is known to cause a myriad of health effects which are more prominent among children. Health effects upon exposure can range from renal and heart disease or potentially cancer in adults to neurotoxicity in children. The continued presence of old lead service lines and plumbing in distribution systems as well as lead-containing solders and brass fixtures in homes may contribute lead to drinking water. Recent studies have highlighted the importance of a predictor known as the chloride-to-sulfate mass ratio (CSMR) in controlling lead release. A ratio above 0.5 – 0.6 theoretically increases the aggressiveness of lead leaching in galvanic settings, while a lower ratio controls lead corrosion. A switch in coagulant type could significantly alter the ratio. However, a coagulant switch could also trigger changes in finished water turbidity and organics, including disinfection by-product (DBP) precursors, as well as impact sludge production. Anecdotal evidence from an Ontario water treatment utility suggested the potential applicability of a newly formulated polymer, cationic activated silica (CAS), in improving DBP precursor removal when used in concurrence with a primary coagulant. No previous scientific research had been dedicated to testing of the polymer. The present research had three primary objectives: The first was to investigate the effect of conventional coagulation with six different coagulants on the chloride-to-sulfate mass ratio as it pertains to lead corrosion in two Ontario source waters of differing quality. Additionally, the effect of coagulant choice on pH, turbidity, and organics removal was investigated. The second objective was aimed at testing potential reductions in CSMR and organics that could be brought about by the use of two polymers, cationic and anionic activated silica (CAS and AAS, respectively), as flocculant aids. Finally, the performance of a high-rate sand-ballasted clarification process was simulated at bench-scale to gauge its performance in comparison with conventional coagulation simulation techniques. The first series of jar-tests investigated the effectiveness of CAS as a primary coagulant on Lake Ontario water. In comparison with the conventional coagulants aluminum sulfate and polyaluminum chloride, CAS did not offer any apparent advantage with respect to turbidity and organics removal. Testing of CAS and AAS as flocculant aids was also conducted. Results from a full factorial experiment focused on CAS testing on Lake Ontario water showed that coagulant dose is the most significant contributor to CSMR, turbidity, DOC removal, and THM control. Generally, improvements resulting from CAS addition were of small magnitude (<15%). Reductions in CSMR were attributed to the presence of the sulfate-containing chemicals alum and sulfuric acid in the CAS formulation. Testing of sulfuric acid-activated AAS on Grand River water showed that pairing of AAS with polyaluminum chloride provides better results than with alum with respect to DOC removal (39% and 27% respectively at 60 mg/L coagulant dose). Highest turbidity removals (>90%) with both coagulants were achieved at the tested coagulant and AAS doses of 10 mg/L and 4 mg/L respectively. CSMR reductions in the presence of AAS were also attributable to sulfate contribution from sulfuric acid. Bench-scale simulation of a high-rate sand-ballasted clarification process on Grand River water showed comparable removal efficiencies for turbidity (80 – 90% at 10 mg/L), and DOC (30 – 40% at 50 mg/L). Finally, six different coagulants were tested on the two source waters for potential applicability in CSMR adjustment in the context of lead corrosion. The two chloride-containing coagulants polyaluminum chloride and aluminum chlorohydrate increased CSMR in proportion to the coagulant dose added, as would be expected. Average chloride contribution per 10 mg/L coagulant dose was 2.7 mg/L and 2.0 mg/L for polyaluminum chloride and aluminum chlorohydrate, respectively. Sulfate-contributing coagulants aluminum sulfate, ferric sulfate, pre-hydroxylated aluminum sulfate, and polyaluminum silicate sulfate reduced CSMR as coagulant dose increased, also as would be expected. The highest sulfate contributors per 10 mg/L dose were pre-hydroxylated aluminum sulfate (6.2 mg/L) and ferric sulfate (6.0 mg/L). The lowest CSMR achieved was 0.6 in Lake Ontario water at a 30 mg/L dose and 0.8 in Grand River water at a 60 mg/L dose. Highest DOC removals were achieved with the chloride-containing coagulants in both waters (35 – 50%) with aluminum chlorohydrate showing superiority in that respect. DOC removals with sulfate-containing coagulants were less, generally in the range of 22 – 41%. Specificity of critical CSMR values to source water needs to be investigated. Additionally, long term effects of sustained high or low CSMR values in distribution systems need to be further looked into. Finally, the effect of interventions to alter CSMR on other water quality parameters influencing lead corrosion such as pH and alkalinity still represent a research deficit.