Brass components are widely used in drinking water distribution systems as valves, faucets and other fixtures. They can be corroded by "dezincification," which is the selective leaching of zinc from the alloy. Dezincification in potable water systems has important practical consequences that include clogged water lines, premature system failure and leaks, and release of contaminants such as lead. Brass failures attributed to dezincification are known to occur at least occasionally all over the world, and have emerged as a significant problem in the U.S. recently due to the use of inexpensive high zinc brass fittings in cross-linked polyethylene (PEX) plumbing systems. As PEX systems gain popularity and leaded brass is recognized as an important source of lead in potable water systems, it is important to examine dezincification corrosion in more detail. An in-depth literature review revealed that conventional wisdom about dezincification was no longer adequate in explaining failures observed in modern water systems. Little research has been conducted since the landmark work of Turner et al. nearly half a century ago. The potential role of chloramines, phosphate inhibitors, and modern understanding of water chemistry need evaluation. The role of physical factors including stirring, heating and galvanic connections are also potentially influential. A mechanistic study of zinc solubility and corrosion of copper: zinc couples provided insight to factors that might mitigate and exacerbate zinc leaching from brass. Zinc solubility and corrosion was reduced by higher pH and bicarbonate, but was enhanced by higher chloride. Hardness ions including Mg⁺² and Ca⁺² had little effect. Alloys with higher zinc content had a greater propensity for dezincification corrosion. Stirring and galvanic connections caused brass to leach more metals and have higher weight loss. Heating may contribute to corrosion scale accumulation. A comprehensive examination of dezincification as a function of water chemistry used numerous techniques that include measurement of galvanic currents, metal leaching, and weight loss. In general, as would be predicted based on results of the study of solubility and corrosion of pure zinc, chloride emerged as an aggressive ion whereas bicarbonate was beneficial to brass corrosion. Hardness had little impact, and phosphates, silicates and Zn+2 inhibitors had a significant short-term benefit but little long-term benefit. The relationship between dezincification corrosion, lead leaching from brass, and water chemistry was investigated in Chapter 5. Surprisingly, lead and zinc leaching from a range of brasses were found to be negatively correlated. Hence, use of brasses that minimize dezincification problems might increase lead leaching. This thesis represents a comprehensive analysis of factors that are influential for dezincification and lead leaching from brass in premise water distribution systems through literature reviews, mechanistic investigations, bench-scale experiments, and case studies. Results can be used by water utilities, plumbing engineers, manufacturers and home owners to better prevent, recognize, and mitigate brass and dezincification corrosion problems. / Master of Science

Les mécanismes de dissolution sélective des alliages de Cu dans l'eau du robinet et la solution de transpiration ont été étudiés. La spectroélectrochimie d'émission atomique a été utilisée. La première partie de la thèse portait sur le mécanisme de dissolution de Cu. La plupart des espèces de Cu (II) sont solubles et sont libérées dans l'eau, laissant derrière eux un film de Cu2O. Une analyse cinétique suggère que le mécanisme de dissolution implique la dissolution simultanée du Cu et la formation du film. La deuxième partie a étudié la dissolution de Cu-42Zn et Cu-21Zn-3Si-P. Un processus de dissolution en deux étapes a été proposé: une première étape d'une croissance rapide de la couche dézincitée et une deuxième étape où la croissance de la couche dézincitée était plus lente. La troisième partie s'est concentrée sur l'effet du contenu de Zn sur la dissolution des alliages de Cu-Zn. Le mécanisme de dissolution a été clarifié. Pour la phase ?: une étape initiale dans laquelle Cu et Zn sont oxydés de manière congruente, mais seulement Zn2+ a été libéré dans l'eau, Cu formant un film Cu2O et une deuxième étape où le Cu2+ a été libéré dans l'eau. Pour la phase ?', la deuxième étape est identique à la phase initiale. L'augmentation de la teneur en Zn entraîne une extension temporelle du stade initial et retardent la libération de Cu2+. La partie finale a porté sur l'effet de la libération de Sn on Cu provenant des alliages Cu-Sn. L'effet amélioré de la libération de Sn sur Cu a été identifié. Cependant, l'augmentation de la teneur en Sn n'a pas augmenté monotoniquement l'efficacité de libération de Cu des alliages de Cu-Sn, ce qui était dû à la passivité de Sn. / The selective dissolution mechanisms of Cu alloys in tap water and perspiration solution were investigated. Atomic emission spectroelectrochemistry (AESEC) was used to obtain the elemental dissolution kinetics. The first part of the thesis focused on the dissolution mechanism of Cu. Most Cu(II) species are soluble and are released into tap water, leaving behind a Cu2O film on the surface. A kinetic analysis suggests that the dissolution mechanism involves simultaneous Cu dissolution and film formation. The second part investigated the dissolution behavior of Cu-42Zn and Cu-21Zn-3Si-P. A two-stage dissolution process of dezincification was proposed: a first stage of a rapid growth of the dezincified layer and a second stage where the growth of dezincified layer was much slower. The third part concentrated on the effect of Zn content on the dissolution of Cu-Zn alloys, by investigating the dissolution behavior of alloys with various Zn content (0-45 wt%). The two-stage dissolution mechanism was further clarified. For α phase: an initial stage in which Cu and Zn are oxidized congruently, but only Zn2+ was released into water, Cu forming a Cu2O film, and a second stage where Cu was released into water in the form of Cu2+. For β' phase, the second stage is the same to the initial stage. The increase of Zn content in the alloy results in a time extension of the initial stage and retard Cu2+ release. The final part focused on the effect of Sn on Cu release from Cu-Sn alloys. The enhanced effect of Sn on Cu release was identified. However, the increase of Sn content didn’t monotonically increase the Cu release efficacy of Cu-Sn alloys, which was due to the passivity of Sn.

Avzinkningshärdiga och blyfria mässingslegeringar används i stor utsträckning för att ersätta blyinnehållande mässingslegeringar som används för dricksvattensapplikationer. På grund av det begränsade antalet korrosionsstudier av dessa legeringar är syftet med denna studie att belysa hur vattensammansättning, temperatur och exponeringstid kan påverka legeringarnas korrosionsegenskaper. Tre avzinkningshärdiga mässingslegeringar studerades i kranvatten; två blyfria mässingslegeringar (CW511L och CW724R) och en blyinnehållande mässingslegering (CW602N) som betraktades som ett referensmaterial. En kombination av elektrokemiska, mikroskopiska och ytanalystekniker användes för att utforska korrosionstyp, mekanismer samt korrosionshastighet. Även om samtliga legeringar visade godkända egenskaper i avzinkningstestet enligt ISO 6509-1:2014 var målet att bedöma deras korrosionsbeteende i kranvatten. Vattenkemin justerades för att undersöka effekten av pH, kloridkoncentration och alkalinitet hos de tre mässingslegeringarna under kortvarig exponeringstid (24 timmar). Vattnets korrosivitet varierade beroende på mässingslegeringens sammansättning. Det visade sig att CW511L var känsligare för höga kloridkoncentrationer (44.7 mg/L) och hög alkalinitet (310 mg/L) än för lågt pH (6.9). Det motsatta observerades dock för både CW724R och CW602N. Testvattnets aggressivitet påverkades också av temperaturen när den ökades från 22 °C till 50 °C under exponering i 24 timmar. Medan ingen tydlig avzinkning upptäcktes observerades en kombination av både allmän och lokal korrosion i varierande utsträckning mellan de olika legeringarna. Initieringen av det lokala korrosionsangreppet varierade både med testvattnets kemi och med legeringssammansättningen. Medan CW724R och CW602N bägge uppvisade hög känslighet för lokal korrosion i vattnet med högst pH (8.2), var CW511L mer känslig i det vatten med lågt pH (6.9) vid 50 °C. Effekten av exponeringstid undersöktes i vattnet med högst pH (8.2) för de tre mässingslegeringarna upp till 72 dagar. Korrosionshastigheten baserad på viktminskning visade en förväntad hög korrosionshastighet som minskade med kontinuerlig exponeringstid, vilket ledde till en låg korrosionshastighet för alla tre mässingslegeringarna efter 72 dagar. De blyfria mässingslegeringar uppvisade ur detta perspektiv goda korrosionsegenskaper som är konkurrenskraftiga med mässing som innehåller bly. / Dezincification resistant (DZR) and lead-free brass alloys continue to be widely applied replacing lead containing brasses in the drinking water sector. Due to the limited number of corrosion studies of these alloys in tap water, the present thesis was initiated with the aim to understand how the water type, its temperature and exposure duration can affect the corrosion behavior. Three DZR brass alloys were studied in order to evaluate their corrosion behavior in tap water of varying characteristics. The alloys included were two lead-free brasses (CW511L and CW724R) and a leaded brass alloy (CW602N) considered as a reference material. A combination of electrochemical, microscopic and surface analytical techniques were adopted to explore the corrosion form, mechanisms and corrosion rate. While these alloys passed the dezincification test as per ISO 6509-1:2014, the aim was to assess their corrosion performance in tap water. The influence of water chemistry parameters including pH, chloride concentration and alkalinity on the corrosion resistance of the three DZR alloys was investigated in short-term exposures (24 h). Depending on the brass alloy, the corrosivity of the test waters varied. The results show grade CW511L to be more sensitive in tap water of higher chloride concentration (44.7 mg/L) and alkalinity (310 mg/L) compared with low pH (6.9). However, opposite results were obtained for both CW724R and CW602N. The corrosivity of the test water was also affected by the temperature when increased from 22°C to 50°C during 24 h of immersion. While no dezincification features were observed on the surfaces, a combination of general and localized corrosion was observed to a largely variable extent between the alloys. The extent of initiation of localized corrosion varied with test water and alloy composition. While CW724R and CW602N showed similar high susceptibility to localized corrosion in the alkaline (pH 8.2) tap water, CW511L was more prone to pitting corrosion in tap water of low pH (6.9). The effect of exposure duration was explored in the alkaline test water for the three brasses up to 72 days. Corrosion rates based on weight loss showed an expected initial high corrosion rate which declined with continuous immersion, leading to low and similar corrosion rates for all three brass alloys after 72 days. Thus, at given test conditions, the lead-free brasses showed good corrosion behavior being competitive to the performance of lead containing brass. Therefore, lead-free brass alloys are good candidates to substitute lead-containing brasses in tap water applications.

Non-uniform corrosion of copper and brass in potable water systems poses both economic and environmental problems associated with premature plumbing failures and release of metals. With respect to copper pitting corrosion, it was found that forensic testing (i.e., in pipe-loops) is the only investigative technique that can closely mimic conditions found in real water systems and produce unambiguous results; and, if used in combination with electrochemical techniques, it may also provide some mechanistic insights into the pitting process. Using pipe-loops, it was demonstrated that copper pitting in aggressive water qualities (i.e., chlorinated, high pH and low alkalinity) is deterministic and reproducible. Additionally, the effects of various chemical and physical factors on pitting were investigated. Overall, increased flow velocity and frequency, increased chlorine residual and decreased hardness were found to accelerate pitting; whereas increased phosphate and silica were found to decelerate pitting. Several mitigation strategies for copper pitting in aggressive water were further investigated, and experimental data were interpreted utilizing electrochemical theory to evaluate specific effects on the initiation and propagation phases of pitting. Surprisingly, it was found that decreased chlorine may delay pit initiation, however, even relatively low levels of chlorine may eventually initiate and propagate pits. Increased alkalinity appears to decelerate pit growth, but does not prevent pit initiation. NOM can delay pit initiation and propagation, although the potential for DBP formation in chlorinated waters makes inhibition by NOM an unfavorable alternative. At sufficient dosages, phosphate and silica corrosion inhibitors may completely stop pitting, consistent with the success of several field trials. At very low dosages, phosphate and silica may actually accelerate pinhole failures, so these inhibitors should not be under-dosed. While brass alloys exist that can limit dezincification problems, they are not always utilized in potable water applications due to high costs, and so dezincification is a re-emerging issue in some countries, including the US. Little research has been conducted in the past several decades regarding the effects of water chemistry, and almost no work has addressed the roles of physical factors associated with real plumbing systems. Thus, a comprehensive review of these topics was conducted. To better understand the effects of some factors associated with specific plumbing installations on dezincification and other brass corrosion types, a series of pipe-loop studies was carried out. It was confirmed that increased oxidant delivery rates to cathodic surfaces, either via increased oxidant concentration or increased flow velocity, can increase corrosion rates. Several key differences were observed with respect to corrosion of brass located in copper plumbing tube systems as opposed to plastic. When copper tubes contribute copper ions to water, brass corrosion becomes more selective for zinc; but if galvanic connections are made between the copper tubes and brass, selectivity for zinc is reduced while overall corrosion rates are accelerated. As opposed to copper tubing, plastic maintains oxidant (e.g., free chlorine) levels, and may thereby increase brass corrosion and build-up of corrosion by-products. Finally, it was found that increased temperature can significantly increase lead leaching from brass. Following recent outbreaks of brass dezincification failures, NSF/ANSI Standard 14 has been revised to require that all NSF 14-listed brass is dezincification resistant, as certified by satisfactory results from an accelerated test method (ISO 6509). Various brasses were tested using this method as well as a longer-term jar method utilizing real potable water. Results of the two tests were in good agreement with respect to dezincification, specifically; but some inconsistencies were observed with respect to uniform corrosion and lead leaching. / Ph. D.

Les ruptures imprévisibles de composants de robinetterie gaz constituent une problématique majeure de la sûreté du réseau de GrDF. Actuellement, la prévention des risques de rupture repose sur la réalisation de tests accélérés de sensibilité à la corrosion sous contrainte (CSC), préalablement à la mise en service des composants de robinetterie en laiton. Il s'agit d'éviter des accidents, au caractère potentiellement très dommageable, du fait de l'inflammabilité des gaz transportés. Or, dans certains cas, des endommagements prématurés de composants de robinetterie sont toujours constatés. Les limites du test de sensibilité actuel SROB 100 NF ont été démontrées par le CETIM ; définir un nouveau test accéléré, plus représentatif des endommagements constatés en service sur les éléments de robinetterie, et conduisant à des résultats reproductibles est donc crucial. Ce test devra être facilement adaptable sur site industriel afin de permettre aux industriels fabricants de valider la conformité des lots de pièces vis-à-vis de leur sensibilité à la CSC. Ainsi, les travaux de thèse reposent sur une démarche intégrant d'une part, la compréhension des mécanismes de CSC affectant les pièces en laiton α,β’ CuZn40Pb2 (CW617N) et d'autre part, la capacité à reproduire les endommagements observés en service, de manière accélérée. Grâce aux résultats obtenus, l'étude permet d’envisager l'industrialisation d’un nouveau test en milieu nitrate, à pH 11 sous polarisation anodique. La reproductibilité de l'endommagement obtenu et sa représentativité vis-à-vis des dommages observés en service comme le caractère discriminant du test vis-à-vis des états métallurgiques les moins résistants ont été démontrés. / The unpredictability of ruptures which occur in the gas transfer valves of the French gas network (GrDF), though sporadic, is a major security issue. Currently, the risk prevention is performed through accelerated tests (SROB100 NF) on gas transfer valves to determine their susceptibility to stress corrosion cracking (SCC). The goal behind this test protocol is to avoid serious accidents due to the flammability of the gas being transported. However, in some cases, premature ruptures of gas transfer valves are still being recorded. The limits of the current test protocol SROB 100 NF have been highlighted by the CETIM and therefore, to define a new accelerated test, more reproducible and representative of the damage observed during the service life of the pipework element is crucial. This new protocol has to be easily integrated into the current industrial set-up to allow for quick confirmation of the conformity of the pieces with regards to their susceptibility to SCC. To this end, the current study had a two-pronged approach. First, to understand the SCC mechanisms affecting brass specimen - α,β’ brass CuZn40Pb2 (CW617N); second, to reproduce the damage observed in real time, in an accelerated manner. In conclusion, the results of the study have paved the way for the industrialization of a new test in nitrate solution, at pH 11 under constant anodic polarization. This new test has proven to be reproducible and produces damage characteristics similar to those observed during service life. This study has also brought into evidence the discriminating characteristic of the test, allowing the identification of the metallurgical states of the alloy that are the least resistant to SCC.

In new low-lead and lead-free brass alloys, it is not understood how the corrosion properties,such as dezincification, are related to material composition as well as annealing temperatureand duration. This study aims to fill this knowledge gap by mapping sixteen annealingconditions and three different brass alloy compositions to their respective microstructure anddezincification performance. It was found that high dezincification depth was a result ofannealing temperatures at 300°C – 400°C, which promoted precipitation of intermetallicAlAs-particles along grain boundaries, twins and lead particles as well as precipitation of β-phase along grain boundaries. Their presence was correlated to high micro additions ofaluminium or iron in the material composition. An additional compositional factorcontributing to precipitation of high amount of β-phase was low copper/zinc-ratio.

På grund av nya riktlinjer för användning av mässing i kontakt med dricksvatten har nya blyfria mässingslegeringar utvecklats. Det är därför av stort intresse att undersöka deras korrosionsegenskaper, såsom avzinkningshärdighet. Ett accelererat standardtest, SS-EN ISO 6509–1:2014, har använts för att bestämma avzinkningshärdighet hos mässingslegeringar. Eftersom detta standardtest utvecklades för bly-innehållande mässingslegeringar har det ännu inte fastställts huruvida denna metod också kan appliceras för fastställandet av avzinkningshärdigheten hos blyfria mässingslegeringar.  Syftet med detta examensarbete var att fylla denna kunskapslucka. Detta gjordes genom att undersöka hur avzinkningsegenskaperna för tre mässingslegeringar, varav två var blyfria och en bly-innehållande, påverkades genom att ändra standardtestets parametrar. Resultaten jämfördes sedan med deras beteende i kranvatten för att bestämma testresultatens tillförlitlighet. Det visade sig att majoriteten av de erhållna resultaten för de blyfria mässingslegeringarna var i överensstämmelse med de resultat som erhölls för den blyinnehållande mässingen. Slutsatsen som kunde dras var därför att standardtestet kan användas för att bestämma avzinkningshärdighet även av blyfri mässing samt att resultaten visar på samma rangordning gällande deras egenskaper i tappvatten. / Due to new regulations for the use of brass in contact with drinking water, new lead-free brass alloys have been developed. It is therefore of great interest to investigate their corrosion properties in terms of dezincification resistance. An accelerated standard test, SS-EN ISO 6509-1:2014 is used to determine the dezincification resistance of brass alloys. However, as this standard test was developed for leaded brass alloys, it has not yet been established whether this method also is suitable to assess the dezincification resistance of lead-free brass alloys.  This master thesis study aimed to expand this knowledge gap by investigating how the dezincification properties of three different brass alloys, two newly developed lead-free alloys and one lead-containing alloy, were affected by changing the parameters of the standard test. The results were compared with their behaviour in tap water to determine the reliability of the ISO test. Most of the obtained results of the lead-free brass alloys were in accordance with the results obtained for the leaded brass alloy. It could therefore be concluded that the standard test can be used to assess the dezincification resistance of brass alloys and also reflect their ranking at tap water conditions.

På grund av nya riktlinjer för användning av mässing i kontakt med dricksvatten har nya blyfria mässingslegeringar utvecklats. Det är därför av stort intresse att undersöka deras korrosionsegenskaper, såsom avzinkningshärdighet. Ett accelererat standardtest, SS-EN ISO 6509–1:2014, har använts för att bestämma avzinkningshärdighet hos mässingslegeringar. Eftersom detta standardtest utvecklades för bly-innehållande mässingslegeringar har det ännu inte fastställts huruvida denna metod också kan appliceras för fastställandet av avzinkningshärdigheten hos blyfria mässingslegeringar.  Syftet med detta examensarbete var att fylla denna kunskapslucka. Detta gjordes genom att undersöka hur avzinkningsegenskaperna för tre mässingslegeringar, varav två var blyfria och en bly-innehållande, påverkades genom att ändra standardtestets parametrar. Resultaten jämfördes sedan med deras beteende i kranvatten för att bestämma testresultatens tillförlitlighet. Det visade sig att majoriteten av de erhållna resultaten för de blyfria mässingslegeringarna var i överensstämmelse med de resultat som erhölls för den blyinnehållande mässingen. Slutsatsen som kunde dras var därför att standardtestet kan användas för att bestämma avzinkningshärdighet även av blyfri mässing samt att resultaten visar på samma rangordning gällande deras egenskaper i tappvatten. / Due to new regulations for the use of brass in contact with drinking water, new lead-free brass alloys have been developed. It is therefore of great interest to investigate their corrosion properties in terms of dezincification resistance. An accelerated standard test, SS-EN ISO 6509-1:2014 is used to determine the dezincification resistance of brass alloys. However, as this standard test was developed for leaded brass alloys, it has not yet been established whether this method also is suitable to assess the dezincification resistance of lead-free brass alloys.  This master thesis study aimed to expand this knowledge gap by investigating how the dezincification properties of three different brass alloys, two newly developed lead-free alloys and one lead-containing alloy, were affected by changing the parameters of the standard test. The results were compared with their behaviour in tap water to determine the reliability of the ISO test. Most of the obtained results of the lead-free brass alloys were in accordance with the results obtained for the leaded brass alloy. It could therefore be concluded that the standard test can be used to assess the dezincification resistance of brass alloys and also reflect their ranking at tap water conditions.