Anaf, W. Corrosion Process of Glass. 2010

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CeROArtNumro 6 (2010)Horizons

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Willemien Anaf

Study on the formation ofheterogeneous structures in leachedlayers during the corrosion process ofglass

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Study on the formation of heterogeneous structures in leached layers during the corrosion (...) 2

CeROArt, 6 | 2010

Willemien Anaf

Study on the formation of heterogeneousstructures in leached layers during the

corrosion process of glassIn the first place, I want to thank my promotor Olivier Schalm and my co-promotors Marc

David, Kristel De Vis and Joost Caen for the constructive comments and help. A lot of

gratefulness goes to Koen Janssens for the use of the Scanning Electron Microscope. Finally,

a lot of gratitude goes to all the other people that have supported me during my master thesis.

Introduction

1 One of the most striking phenomena in glass corrosion under natural conditions is thetransformation of a material that is homogeneous to a scale down to 0.5 m into a leached layerthat contains heterogeneities of about 1 to 5 m or even larger. Examples of heterogeneitiessuch as lamellar structures (Brill 1961; Newton 1971; Cox and Ford 1989; Rmich 1999;

Domnech-Carb et al. 2001; Sterpenich and Libourel 2001; Salviulo et al. 2004; Dal Biancoet al. 2005; Silvestri et al. 2005; Domnech-Carb et al. 2006), phosphate precipitations(Freestone 1985) or oxidized manganese inclusions (Mller et al. 1986; Newton and Davison1989; Perez y Jorba and Bettembourg 1991; Pinto 1991; Schreiner 1991; Cox and Ford 1993;Knight 1996; Barbey et al. 1997; Krawczyk-Brsch et al. 1997; Rmich 1999; Janssens etal. 2000; Domnech-Carb et al. 2001; Watkinson et al. 2005) have been reported in thepast. However, almost none of these publications mention that such phenomena cannot beexplained with the currently accepted theories describing glass corrosion (Douglas and El-Shamy 1967; Doremus 1979; Scholze 1988; Bunker 1994). Therefore, the objective of thepresent study is to elucidate the formation of heterogeneous structures in (historical) glassin relation to the currently accepted theories describing corrosion processes. Experiments

in which heterogeneous structures were generated under laboratory circumstances will bepresented. The experimental results will be discussed and included in a new approach of thecorrosion process that starts with the molecular structure of glass.

Background information

2 The currently accepted corrosion theories assume that glass is a homogenous matrix in whichmobile cations are present. As a consequence of the corrosion process, the cations in theglass matrix are leached out while protons from the environment penetrate into the glass.The mobility of these cations is related to the chemical composition of the glass matrix andis described by the diffusion coefficient. This corrosion model is based on the continuousrandom network(CRN) of Zachariasen and Warren (Zachariasen 1932; Warren and Loring

1935; Vogel 1971). In the field of conservation science it is probably the most referredglass structure. However, presently the most accepted description of the glass structure is themodified random network(MRN) of Greaves (Greaves 1991). The MRN-model describes

glass as a mixture of two networks: a covalent immobile SiO2-rich network and a network ofchannels formed by network modifiers such as alkali and alkaline earth ions. The channelscan be considered as percolation pathways with high ion mobility. Therefore, glass is nothomogeneous at the nanometre scale. Fig. 1 gives a two-dimensional overview of a glassmatrix according to the MRN-model. The model has been successfully applied to describeseveral physical properties of glass such as electrical conductivity, glass fracture, thermalexpansion coefficient, etc. (Greaves 1991; Baker et al. 1995; Clari et al. 2007). According


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to the authors knowledge, the MRN-model has never been used to explain glass corrosion.The present study uses this model as a starting point.

Fig. 1: Two-dimensional representation of the Modified Random Network

Robinet 2006

3 It is well known that glass composition has a significant influence on the corrosion sensitivityof glass. This can to some extent be explained using the MRN-model. The amount of network

modifiers determines if a glass matrix contains less or more channels. The interconnectionof the channels increases with the amount of network modifiers. Therefore, a higher amountof network modifiers causes a denser network of finite clusters of interconnected channels,resulting in a significant decrease in the average activation energy for alkali-hopping (Gedeonet al. 2008). This implies an increase in ion mobility and thus a higher corrosion sensitivity.Some of the channels are in contact with the glass surface and are able to interact directly withthe ambient environment. Other channels are isolated and have no contact with the surface.

Experiments

4 Several experiments were designed in order to obtain specific features that cannot be explainedby the classic glass corrosion theories. In the past, several attempts were performed to

artificially produce leached layers with lamellar structures (Aerts 1998; Rmich et al. 2003)or to introduce external ions into the leached layer (Aerts 1998; Watkinson et al. 2005). Thepresent study is based on similar experiments. Glass samples were immersed in a metal-richsolution. As a result of a concentration gradient between glass and environment, a migrationof the metal ions into the glass is expected. A selection of the performed experiments will beexplained in the following paragraph.

Samples

5 Two different glass samples were used in the experiments. The first one was a corrosionsensitive model glass (type M1.0, Fraunhofer Institut fr Silicatforschung, Wrzburg) with


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a composition of 59.0% SiO2, 21.6% K2O and 19.3% CaO. From one sheet of model glass,small pieces of around 1 cm x 0.5 cm were cut by means of a diamond saw. The thicknessof the samples was 0.7 mm. Afterwards, the samples were fire-polished and saved in a boxwith silica gel until the beginning of the experiments. The second glass type was an historical

piece of 17th century window glass from a private collection. The historical glass had a more

complex composition (60.5% SiO2, 19.4% CaO, 8.0% K2O, 3.0% MgO, 2.7% Al2O3, 2.0%

P2O5, 1.6% Fe2O3, 1.5% Na2O, 0.6% MnO, 0.4%TiO2, 0.2% Cl) and showed clear signs of pitcorrosion. Pieces of 1 cm x 1 cm were cut by means of a glass cutter. The thickness of thesample was 2 mm.

Description of the experiments6 Table I gives an overview of the different solutions in which the glass samples were immersed.

The solutions were made by dissolving the proper amounts of metal chloride in deionisedwater. The initial pH was adjusted by addition of HCl. The beakers were sealed off in orderto prevent evaporation. Due to ion exchange, an increase in the pH of the solution close tothe surface was expected. Thiswas reduced in two different ways. On one hand, the solutionsin the 20 ml beakers were continuously homogenized by placing the beakers on a shakingplatform. To prevent the samples from moving, they were glued with acid-free silicon to the

bottom of the beaker. The solution in the 200 ml beaker was manually stirred with a cleanglass bar (1 to 2 times a day). After immersion, all glass samples were taken out of the beakersand left to dry in ambient air.

Table I: Overview of the experiments to generate features in leached layers that cannot beexplained with the currently accepted theories describing glass corrosion.

Analytical techniques7 The mass of the samples (dry condition) was measured before and after the corrosion

experiments with a balance with a precision of 0.001 gram (A&D HF-300G). The increasein acidity was empirically measured with a pH meter (Sentron Argus), which was calibratedbefore each measurement. After the experiments the surface structure of the samples wasobserved with a binocular optical microscope with reflected and transmitted light (OlympusBX41). To study the cross-sections, several glass splinters were embedded in a block of resin(Technovit 2000 LC), oriented perpendicular to the original glass surface. The surface ofthe resin was polished with corundum papers and fine diamond pastes down to 1 m. Thecross-sections were examined with an optical microscope. Finally, the embedded sampleswere analysed by means of a JEOL 6300 Electron Microprobe system equipped with a digital,thin-window energy dispersive Si(Li) Xray detector of Princeton Gamma Tech (PGT).


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Results

Penetration of copper ions in the leached layer

8 Experiment 1 (see Table I) resulted in a leached layer of about 20 m thickness in whichsmall amounts of copper and chlorine were present. In the near-surface zone, the leached layershowed cracks perpendicular to the glass surface. On the surface a blue copper precipitation

was present, probably due to a fast but local increase of the pH of the solution (Fig. 2). Atthe initial pH it was indeed possible to completely dissolve all the metal salts used in theexperiments. However, when corrosion proceeded, the pH of the solution increased, especiallyin cracks and close to the surface. This resulted in the precipitation of compounds of the type

Cu(Cl,OH)2.nH2O. As a consequence, the amount of mobile Cu2+ cations in solution droppedas well. It can be concluded that even when shaking the solution, local pH-increases have tobe taken into account. Although the precipitation was already visible after one week, a smallamount of copper had migrated into the leached layer as can be seen in the X-ray spectra(measured after 3 months of immersion). Remarkable was also the migration of Cl--ions (Fig.

3). The incorporation of Cl--ions has already been mentioned in other publications (e.g.,Mderet al. 1998). To maintain the electrical neutrality in the glass after incorporation of anions, two

possible mechanisms can be considered: (1) a cation migrates together with the anion into theglass; (2) ion exchange takes place with an anion present in the glass. The last mechanism isless plausible as there are normally no mobile anions present in the glass. As a consequenceof the formation of a leached layer, a decrease in mass was expected. However, in this casethe mass of the glass sample increased by 1 wt%, probably due to the copper compoundprecipitation on the glass surface.

Fig. 2: Backscattered image of the model glass after experiment 1.


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Fig. 3: X-ray spectra: bulk glass (black), model glass after experiment 1 (grey).

Penetration of manganese ions into the leached layer

9 The immersion of glass samples in manganese solutions received special attention because

several historical fragments were reported to contain inclusions of Mn4+-oxy-hydroxides(Newton and Davison 1989; Domnech-Carb et al. 2001; Watkinson et al. 2005). Both inexperiment 2 and 3, a brown manganese-rich deposition appeared on the glass surface aftera few days of immersion. Analogous to the Cu-experiment, this was probably caused by alocal increase of the pH. After 3 months of immersion, the cross-sections of the model glasssamples showed irregular leached layers. Within the leached layers a heterogeneous networkof manganese- and calcium-rich cracks was formed (Fig. 4-5). The source of the calcium

could only be the glass itself since there was no Ca2+ present in the original solution. Thehigher concentration of MnCl2 in experiment 3 had caused a more explicit pattern of Mn-richcracks with clear vertical fissures, interconnected by horizontal fissures (Fig. 5). With lightmicroscopy the manganese precipitations appeared as dark brown, irregular inclusions in theglass.

Fig. 4: Backscattered and X-ray image of the model glass after experiment 2.


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Fig. 5: Backscattered image of the model glass after experiment 3.

10 After immersing a model glass in a strongly acidic MnCl2-solution (experiment 4), a thickleached layer was formed. The glass surface showed a cracked pattern. The cracks probablyoriginated during the drying period (dehydration of the glass) (Rmich 1999; Prochazka 2007;Robinet et al. 2007; Geisler et al. 2010). Remarkable was the formation of a heterogeneous

lamellar structure in the leached layer. After 15 days however, no manganese had migratedinto the structure, but some chlorine and calcium enrichments were visible. The enrichmentsfollowed the lamellar structure (Fig. 6). However, the high amount of too many uncontrollableexperimental parameters did not allow for a selection of a possible cause for the formation ofthe lamellar structure. Nevertheless, it can be supposed that external ions are not necessaryfor the formation of a lamellar structure. As reported before (Aerts 1998), the formation of alamellar structure is also not dependent on cyclic changes in temperature and humidity. It isprobably caused by a reorganisation of the glass structure itself.


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Fig. 6: Backscattered and X-ray image of the model glass after experiment 4.

The experiment demonstrates that lamellar structures can be generated under laboratory conditions. (Prolongedexposure to the electron beam has led to additional cracks in the leached layer as can be seen in the X-ray images.)

Penetration of lead ions into the leached layer

11 After experiment 6, the pH of the solution had slightly increased up to 3.5, probably due to an

ongoing leaching process. A comparison of the sample mass before and after the experimentconfirmed this assumption, as the mass had decreased by 1.2 w%. SEM-images of the cross-section clearly showed an increased amount of lead in the already existing corrosion pit,following a specific structure. Around cracks, the Pb-amount was remarkably larger. In thebulk glass, no significant amount of Pb was measured (Fig. 7). To investigate whether thePb was already present in the corrosion pits before the artificial corrosion experiment, thespectrum of the pit after artificial corrosion was compared with a reference sample withoutartificial corrosion. This made clear that the Pb had indeed migrated into the leached layer ofthe corrosion pit during artificial alteration (Fig. 8).

12 The results of experiment 5 were similar to those of experiment 6 (both historic glass samples).Therefore, only experiment 6 has been treated in the present article.

Fig. 7: Backscattered and X-ray image of the historical glass after experiment 6.


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Fig. 8: X-ray spectra: reference sample (black), historical glass after experiment 6 (grey).

General remarks on the experimental results

13 The experiments once more demonstrate that the migration of external ions in glass is possible.The migration is limited to the leached layer because of a higher ion mobility in this layer(Grambow and Mller 2001; De Rosa et al. 2003; Tourni et al. 2008; Conradt 2008). Thecircumstances determine to a significant extent the thickness and value of the leached layer.First of all, the mobility of the external ions is important: only mobile ions can migrate into theglass. As the mobility of the external ions can be related to the pH of the aqueous environment,this can be indicated as the reason why the migration of external ions was limited in the modelglass experiments: the metal ions were quickly deposited on the glass surface and could notmigrate into the leached layer anymore. Precipitation reactions thus reduce the mobility. Theexposure time is also a possible parameter: the migration of external ions into the glass is likelyto be much slower than the leaching process. However, cracks in the leached layer certainlypromote the migration.

Discussion

14 The experimental results, combined with an extensive literature study, could give aninteresting input for a new approach of the corrosion process in which the MRN-model isconsidered as a basis.

15 The chemical deterioration of glass can be described as any combination of three simultaneous

partial primary processes: (1) ion exchange, (2) hydration and (3) hydrolysis (Fig. 9) (Bunker1994, Silvestri et al. 2005; Pollard and Heron 2008). The primary corrosion processes arestrongly coupled to each other and can take place in conditions where the glass is exposedto an aqueous environment. Besides, secondary corrosion processes such as the formation ofprecipitations, also have to be taken into account. Each process will be separately describedin the following paragraphs. It should be noted that subtle differences in micro-environment,internal stress or the fraction of channels in contact with the surface can lead to completelydifferent corrosion patterns, even when the glass originates from the same object and whenthey were buried close to each other.


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Fig. 9: Overview of the different primary corrosion processes.

Ion exchange

16 In an acidic (aqueous) environment the concentration of H+ is higher than the OH--

concentration. Therefore, the attack on the glass is dominated by the attack of H

+

-ions, causinga leaching process. The diffusion-directed ion exchange occurs between the protons of the

aqueous environment and the mobile network modifiers (Na+, K+, Ca2+) in the channels thatare in contact with the glass surface. Inside such a channel, ion exchange transforms a channel

filled with network modifiers (i.e., M+-channels) into a channel filled with protons (i.e., H+-

channels). Therefore, deteriorated glass contains M+-channels and H+-channels, with a much

higher ion mobility in H+-channels than in M+-channels. From a macroscopic point of view,this inter-diffusion process causes the formation of a leached layer, poor in alkali and alkalineearth ions. The interface between the leached layer and the bulk glass is sharp and thereforeclearly distinguishable, as can be seen in Fig. 2, 4, 5, 6 and 7. As the corrosion progresses,the interface moves further into the glass.

Hydration

17 Hydration describes the diffusion of molecular water into the glass. The rate of water diffusionis mainly determined by the size of the voids present in the glass network. When the voids arelarge compared to the size of the water molecule, a rapid diffusion is possible. The smallerthe openings in the structure, the slower the water diffusion will be. When the voids are toosmall for the penetration of water molecules, they can react with the network by breaking Si-O-Si-bonds (hydrolysis) and thus open the structure (Bunker 1994). According to Sterpenichand Libourel (2006) water diffusion is not restricted to the leached layer, forming a gradualtransition between hydrated and non-hydrated glass.


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18 In the present study a new hypothesis is proposed in which water is considered as apredominant agent in the formation of a lamellar structure. In the experiments, it is alreadysuggested that external ions probably do not play a role in the initial formation of a lamellarstructure. Besides, it is known that diffusion processes coupled to precipitation reactionstend to create chaotic patterns. Of late, Scott (2005) interrelated heterogeneous morphologiesin the corrosion layer of metal artefacts with self-organising systems. He mentioned fractalgeometries and layered or banded structures. An example of such patterns are Liesegang

bands. In the literature, a few studies shortly cite Liesegang bands in the perspective of theformation of lamellar structures during glass corrosion (Dal Bianco et al. 2005; Scott 2005;Weber 2005; Schreiter et al. 2007). However, none of the studies gives a clear explanationof the occurring process. The present study hypothesizes the following: water is able todiffuse into the glass, but once it reacts with the silicate network, it is trapped (formationof Si-OH-groups). This results in a depolymerisation of the silicate network and the channelstructure probably disappears. By the combination of water diffusion and water entrapment,the conditions for reaction-diffusion are fulfilled and a certain pattern, such as a lamellarstructure, can arise. It is assumed that the amount of molecular water varies in the differentlayers of the lamellar structure, which could be linked to variations in ion mobility. As aconsequence of this, external ions will preferentially migrate into the layers with the highest

ion mobility.

Hydrolysis

19 The last primary corrosion process, hydrolysis, dominates in alkaline environments. OH --

anions will, together with H2O, attack the SiO2-rich islands of the glass network, causinga depolymerisation of the glass structure. In an advanced stage of deterioration, hydrolysiscan cause a dissolution of the silicate network whereby the original glass surface will finallydisappear. A condensation reaction whereby the formed Si-OH groups polymerize againforming Si-O-Si bonds, can also take place. This reaction is accompanied by the release ofmolecular water. Successive hydrolysis and condensation reactions create a more open glassstructure, enhancing the diffusion rates of water and other (external) ions.

Secondary corrosion processes

20 The secondary corrosion processes can be divided into two main groups, i.e. (1) processes thattake place on the glass surface, and (2) processes that take place in the leached layer. The firstgroup contains processes in which leached cations that are still present on the glass surfaceinteract with products from the environment to which the glass is exposed. A well known

example is the interaction with gaseous pollutants such as CO 2 and SO2, causing secondary

corrosion products such as gypsum (CaCO3.2H2O) and syngenite (CaCO3.K2O.H2O) whichdestroy the transparency of the glass. Besides, solutes that do not originate from the glasscan precipitate on the surface (e.g., soluble corrosion products of surrounding stones). Thesecondary corrosion processes in the leached layer itself can be described as diffusionprocesses in combination with precipitation reactions. External ions such as manganese andphosphor can migrate into the leached layer and subsequently form heterogeneous structureswith different features. Observations have shown that manganese, for example, can give riseto planar shapes, tubular structures and dendrites (Schalm et al. 2010). These secondaryprecipitations are formed when saturation is reached. Furthermore, their formation is catalyzedby previous formed aggregates (Chopard et al. 1991; Schalm et al. 2010). In a lamellarstructure, the diffusion of (external) ions will be preferential in low density lamellae, creatinga specific heterogeneous pattern.


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Conclusion

21 The present study has shown the possibility of an artificial generation of heterogeneousstructures by immersing corrosion-sensitive and historical glass samples in a metal-richaqueous solution. The experiments have demonstrated that the migration of external ions inglass is possible. Under certain circumstances the external ions can create heterogeneities. Inone experiment, a lamellar structure has been artificially obtained. Despite the fact that many

parameters were uncontrolled in this particular experiment, some interesting information onthe formation of the lamellar structure could be deduced. The lamellar structure presumablyarose by a reorganisation of the glass structure itself as a result of strong hydration reactions.Therefore, (external) water plays an important role in the formation of a lamellar structure.

External ions such as Mn2+ are probably not necessary in the initial formation of this structure.However, differences in ion mobility in the layers could stimulate the migration of (external)ions in a certain heterogeneous pattern.

22 In order to conclude, the different corrosion processes were discussed starting from themodified random structure of glass. This new approach has the potential to clarify someobservations that cannot be explained by the currently accepted corrosion theories. Thepresented preliminary ideas could give rise to the development of a more subtle model of glasscorrosion.

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Pour citer cet article

Rfrence lectroniqueWillemien Anaf, Study on the formation of heterogeneous structures in leached layers during thecorrosion process of glass , CeROArt[En ligne], 6 | 2010, mis en ligne le 21 novembre 2010. URL :http://ceroart.revues.org/index1561.html

Willemien Anaf

Willemien Anaf achieved her Master in Conservation Studies (Artesis University of Antwerp,Belgium) in 2009. She specialized in the conservation of stained glass windows. During her studies,


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CeROArt, 6 | 2010

she took part in the Erasmus Exchange Program with the Academy of Fine Arts in Vienna (Akademieder bildenden Knste, Wien), where she worked for 5 months in the Institute of Science andTechnology in Arts (Naturwissenschaften und Technologie in der Kunst) under the direction of Prof.Dr. M. Schreiner. Currently she is working as a PhD-student at the University of Antwerp, Departmentof Chemistry, in the research group Environmental Analysis of Prof. R. Van Grieken. Her PhD-research emphasizes on the influence of particulate matter on the deterioration of cultural heritage.

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Rsum / Abstract

Le verre, corrod dans des conditions naturelles, montre souvent des htrognits dans lacouche lixivie, comme une structure lamellaire ou des inclusions de MnO2 ou Ca3(PO4)2. Laformation de ces htrognits nest pas encore bien comprise. Des structures de ce type ontt produites artificiellement en laboratoire en immergeant des chantillons de verre dans des

solutions riches en mtaux. Les rsultats exprimentaux ont t compars avec des thoriesdcrivant la corrosion du verre.Mots cls : corrosion,couche lixivie htrogne,canaux de percolation,verre

Glass that corrodes under natural conditions often shows heterogeneities in the leachedlayer, such as a lamellar structure or inclusions of MnO2 or Ca3(PO4)2. The formation ofthese heterogeneities is still not well understood. By means of experiments under laboratoryconditions, our aim was to artificially generate specific structures. Therefore, glass sampleswere immersed in metal-rich solutions. The experimental results were compared with theoriesdescribing glass corrosion from a molecular point of view.Keywords : heterogeneous leached layer,percolation channels,corrosion,Glass

ndlr : Artesis Hogeschool Antwerpen - Universiteit Antwerpen Contact: Eva Annys

Anaf, W. Corrosion Process of Glass. 2010

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