IMPLEMENTATION OF A NEW NANOCOATING FOR

ACTIVE METAL PROTECTIONProjet Collectif 2011-2012

Galinier KimBorgna ThomasGraujean JohanDuronsoy SimonMania MélanieSallet Pauline

Tuteurs : Marion FrégonèseBernard Normand

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SummaryINTRODUCTION ..........................................................................................................

What is adhesion ? .....................................................................................................

I - ACTUAL PROTECTION ...........................................................................................

1-What is phosphatation ? ......................................................................................... a-Phosphatation process b-Chemestry of phosphatation2-What is chromatation ? ........................................................................................... a-Overview of the chromatation b-Chemistry of phosphating c-Corrosion resistance

II - IMPLEMENTATION OF A NEW NANOCOATING FOR ACTIVE METAL PROTECTION ...............................................................................................................

1-Vanadium Coating .................................................................................................... a-Introduction b-Electrochemical measurement c-Formation of the coating d-Talking about VCC Corrosion Resistance… e-Conclusion2-Montmorillonite in an epoxy matrix .................................................................. a-Introduction about Montmorillonite b-Different processes c-Future works and optimization of the solution d-Conclusion• 3-Conversion coating with phytic acid .................................................................. a-Introduction b-Experimental Procedure of The Article c-Measurements d-Results and discussion e-Conclusion of their study f-Explanation of the mechanisms

CONCLUSION ..............................................................................................................

Quelques mots sur l’organisation du groupe ............................................................

Remerciements............................................................................................................

References ...................................................................................................................

Annexes ........................................................................................................................

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Introduction

Steel is used for many of his advanta-geous properties but a main issue re-mains: it corrodes easily.

There is a common way and good solu-tion to protect steel from oxidation and embrittlement due to corrosion which is galvanization.

Basically, galvanization is a zinc coating on a steel substrate. It is deposed on steel through a bath of molten zinc. The zinc diffuses into the steel and we obtain a gradient of concentration of zinc inside and on the top of the steel layer. The adhesion of zinc on steel is ensured by an intermetallic compound formed between zinc and iron. Figure 1 shows the surface of such a metal sheet with a zinc coating.

Galvanization is a cathodic protection with the zinc working as the sacrificial anode. The value of the corrosion poten-tial of zinc is considerably lower than iron’s, thus zinc corrodes preferenti-ally to it.The zinc therefore serves as a sacrificial anode, so that it cathodically protects exposed steel. Moreover, zinc produces a powdery white oxide which can also protect steel from corrosion in the scratches. We can see it as the effect of passivation. Besides, zinc presents a very low corrosion rate compared to steel

which is due to this layer of oxide. To sum up, zinc protects steel through galvanization using two different ways: it is passivated and corrodes very slowly, and it protects steel in setting up a ca-thodic protection.

Galvanizing is also favored as a mean of protective coating because of its low cost, ease of application and comparati-vely long maintenance-free life.

This process is used, mainly for the auto-motive industry which is the main client of Tata Steel. They use this process to prevent the oxidation of their metal sheets. Although galvanizing will inhibit attack of the underlying steel, rusting will be inevitable, especially due to natu-ral acidity of rain. Galvanized steel can last for many years if other means are maintained, such as paint coatings and additional sacrificial anodes. Therefore these sheets will receive other coatings of polymers to prevent other problems like UV irradiations or to create an esthe-tic coating like painting or polish.

The first organic coating is called e-coat (electrocoat) and is deposed by cataphoresis. Cataphoresis is a coating method mainly used in the automobile industry. The body of the car is bathed into a bath of charged organic coatings. This is a water-soluble painting. A cur-rent circulates into the bath between the cathode and the anode thanks to those charged particles of painting in suspen-sion in the bath. The car is used as an anode and the molecules of organic coa-ting which are carrying a charge will go to the body and depose on it. The strong advantage of the method is that there is a good distribution of the painting on the

Figure 1 : Surface of a galvanized steel [ARC-2012]

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car body surface : even in the holes and in the corners. The painting is deposed uniformly and homogeneously on the surface. This process only lasts a few minutes. Figure 2 shows the principle of this technic.

Moreover there will be other layers de-posed on this e-coat. They all have their functionality: base-coat, clear-coat, pri-mer surfacer … They can protect against UV radiation or just serve in the esthetic brightness. Figure 3 shows the different layers that are deposed on the metal gal-vanized sheet.

However the problem that we have to solve is the one of adhesion between the organic coating (like painting) and an inorganic coating (like our zinc-galvani-zation coating). In fact, the surface of galvanized steel can not adhere with an organic layer without a pretreatment enhancing the adhesion between those two layers. We could use a blasting or a sandblasting to improve

the adherence of zinc, the roughness of the surface after it would provoke a much better adherence of the paint. But those solutions would brittle the zinc coating and lead to a strain hardening in the material. It could create cracks on the surface which would engender the opposite effect.

The current solution in this case is to use what we call a conversion coating, which improves the adhesion between organic coating and zinc. Current practice is pre-dominated by the pretreatment of steel surfaces with a layer of inorganic phos-phate coating. This is phosphatation. This process consists in spraying (or bathing) phosphoric acid and phosphate salts on the surface. This conversion layer can greatly reduce the rate of corrosion pro-cesses and enhance the painting-grip. However, in the long term, the interfacial degradation of the conversion coating causes coating failure.

Moreover it’s not ecologically friendly and a new solution has to be found to replace it. We’ll have to take into account the ecological dimension of this new layer. Other solutions of conversion coating have also been explored like chromata-tion but there are the same problems of pollution because these conversion coa-tings are prepared with hexavalent chro-mium, which is carcinogenic.

The aim of this discussion is also to find, in different documents, a new conver-sion coating avoiding uses of non-envi-ronmental-friendly processes. This layer has to enhance the adherence between the e-coat and the zinc substrate in or-der to help Tata-Steel developing a bet-ter conversion coating.

In this report, we are first of all going to present the notion of adhesion which is

Figure 2 : Principe of Cataphoresis [SAI- 2012]

Figure 3 : The different layers on a metal sheet for automotive application

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fundamental for our project as we aim to find a layer able to adhere on the zinc substrate and the upper organic coating.We are then going to inventory the two main techniques used in the industry to realize a conversion coating, that is to say the chromatation and the phospha-tation, tending to disappear in the next few years. Then we will describe the alternative techniques that we have found and that have kept our attention.To conclude, a description of the mani-pulations we are currently leading will be done.

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What is Adhesion ?

• Introduction:

Adhesion turned out to be one of our main research fields. Indeed, in addi-tion to the corrosion inhibition effect, our coating will also have to assure the adhesion between the e-coat and the galvanized steel. To ensure adhesion, the creation of an in-terphase between these two materials is compulsory (the same way, an interphase is created between the zinc and the steel through galvanization). An interphase can be described as a mixed layer where the concentration of the components is slowly varying. At the interface, both ma-terials have a different molecular struc-ture. Therefore we observe different pro-perties at the interface than the ones we have in the bulk material. The interface efficiency will be measured by the practical adhesion which repre-sents the needed energy to separate the two materials (in J/cm²).

Because of the wide range of interfa-cial adhesion observable, many theories were developed to describe the pheno-mena.

• Several mechanisms of adhesion

1- Mechanical adhesion The mechanical theory, also called the Mechanical Interlocking Theory, is the oldest explanation for adhesion. The

theory essentially described that mecha-nical interlocking of the adhesives and the flow into the irregularity of the subs-trate surface is the source of adhesion.Mechanical adhesion is possible because of the existence of porosities in one or both basic materials; it can be described by an interpenetration of both materials in the porosities of the other one. The adhesives have to flow into the pores and interstices of the materials to establish mechanical embedding.The mechanical adhesion is ensured by the application of a pressure at the po-lymers’ surface in order to increase the contact surface between the two mate-rials.Mechanical adhesion isn’t a suitable solution for our project because of the weak practical adhesion shown by our materials, but also the too weak porosity of our substrate to ensure a good pene-tration of the coating. [AUF-2005]

2-Electrostatic TheoryThe Electrostatic Theory describes that an electrical double layer is produced at any interface and the consequence Coulombic attraction largely accounts for adhesion and resistance to split-up. [DUN-2002]

3-Diffusive adhesionThe diffusive adhesion occurs when in-terdiffusion between the coating and the substrate can appear. This mechanism of adhesion most commonly appears between a polymer and a metal where the physical entanglement is common. To obtain a diffusive adhesion, the coa-ting and the substrate must be thermo-dynamically compatible, typically when the molecules of both materials are mo-bile or soluble in each other.

Figure 4 : Scheme of an interface [AUF-2005]

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This type of adhesion is mostly known for the welding processes, where the wel-ding material must diffuse in both sides to join the materials and form a link between them. [AUF-2005]

4-Adsorption theoryThis theory states that surface forces are involved in adhesion, and also that polar molecules are oriented in an ordered way so that the surface molecules of the coating and the substrate are in contact. The main types of bonds are described in the table below.Adhesion forces are cohesion forces of the materials, they are governed by inter-atomic bonds (also called strong chemi-cal bonds: ionic, covalent and metallic) and inter-molecular links (weak physic bonds like hydrogen or Van der Walls bonds). In our case, the major interac-tions will be inter-molecular ones as we are studying multi layer adhesion.

This mechanism of adhesion is the most common one, the practical adhesion is very high but the adhesion quality highly depends on the surface state of the ma-terials (the interaction distance are very small so the surface atoms are the ones who play a major role in this mecha-nism). [DUN-2002]

Therefore, the surface state has to be improved by a pre-treatment.

• Surface pre-treatment

Because of the importance of adsorp-tion, pre-treatments are often used in the industry. Several types of pre-treat-ments are used depending on the types of materials (metal/metal or polymer/metal in our case).All the types of treatments are used to:- Generate a specific topography on the surface of the substrate (it will improve the mechanism of mechanical adhesion).- Protect the surface before the bonding process.- Remove the impurities on the metal’s surface. These impurities might form weak bonds and it would increase the direct contact between the substrate and the coating’s molecules (It will favor the formation of ionic or covalent bonds).Pre-treatments can be physical, thermal or chemical. [AUF-2005]

During our mission, it’s really important to understand that we are seeking to replace the phosphatation/chromatation conversion coating by another process more eco-friendly.One of the main challenges that we have to take up is to find an eco-friendly layer that has at least the same adhesion pro-perties than actual ones.

Figure 5 : The main types of bonds and their energy

Type Bond Energy (kJ/mol)

Primary bonds

Ionic 600-1100

Covalent 60-700

Metallic 110 - 350

Donor Acceptor bonds

Bronsted acid-base interactions Up to 1000

Lewis acid-base interactions Up to 80

Secondary bonds

Hydrogen bonds

involving fluorine Up to 40

excluding fluorine 10-25

Van der Walls bonds

Permanent dipole-dipole interactions 4-20

Dipole induced dipole intercation Less than 2

Dispersion London Forces 0.08 - 40

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I-1-What is Phosphatation ?

I-1-a -Phosphatation process

Phosphating is the most widely used metal pretreatment process for the sur-face treatment and finishing of ferrous and non-ferrous metals. Due to its eco-nomy, speed of operation and ability to afford excellent corrosion resistance, wear resistance, adhesion and lubrica-tive properties, it plays a significant role in the automobile, process and appliance industries. [NAR-2007] It serves as a conversion coating in which a dilute so-lution of phosphoric acid and phosphate salts is applied via spraying or immer-sion. This solution chemically reacts with the surface of the part being coa-ted to form a layer of insoluble, crystal-line phosphates. Phosphate conversion coatings can also be used on aluminum, zinc, cadmium, silver and tin.

The presence of a phosphate coating on a metal substrate normally serves one or both of two major functions:- increasing the corrosion resistance of the substrate by comparison with an otherwise identical metal substrate that has no such conversion coating, an in-crease that may be measured either with or without a subsequent paint or similar protective coating. - serving as a strongly adherent «car-rier» for an externally applied lubricant material that facilitates mechanical cold working.

Phosphating is a process of depositing a conversion coating onto steel and gal-vanized steel to prepare the surface to receive a liquid, powder, or electrodepo-sited coating. The phosphate deposit is referred to as a conversion coating be-cause it converts the surface of the vir-

gin steel (no oxide present) to a roughe-ned amorphous or crystalline phosphate composite. A phosphate deposit can en-hance a paints and coatings application in essentially three ways:- Serving as a barrier to keep atmosphe-ric oxygen and moisture from attacking the base metal.- Acting as a dielectric film that electri-cally insulates the substrate from the paint or other coating, slowing the pro-cess of galvanic corrosion.- Providing a rough surface for mechani-cal gripping of the paint or other coating for an improved bond.

These are the reasons why phosphata-tion is so widely used nowadays, howe-ver it will soon be banned because its process and products are considered as toxic. Therefore, Tata Steel is looking for a new conversion coating that will bring the same properties as phosphatation does (or chromatation as we will see fur-ther down) but without the environmen-tal issues.

I-1-b-Chemistry of phosphating

All conventional phosphating solutions are dilute phosphoric acid based solu-tions of one or more alkali metal/heavy metal ions, which essentially contain free phosphoric acid and primary phos-phates of the metal ions contained in the bath. When a steel panel is introduced into the phosphating solution a topoche-mical reaction takes place in which the iron dissolution is initiated at the microa-nodes present on the substrate by the free phosphoric acid present in the bath. Hydrogen evolution occurs at the micro-cathodic sites.

I-ActuAl protectIons

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Fe + 2H3PO4 -->Fe(H2PO4)2 + H2

The formation of soluble primary fer-rous phosphate leads to a concurrent local depletion of free acid concentra-tion in the solution resulting in a rise in pH at the metal/solution interface. This change in pH alters the hydrolytic equi-librium which exists between the soluble primary phosphates and the insoluble tertiary phosphates of the heavy metal ions present in the phosphating solution, resulting in the rapid conversion and de-position of insoluble heavy metal tertiary phosphates. In a zinc phosphating bath these equilibria may be represented as:

Zn(H2PO4)2 -->ZnHPO4 + H3PO4 , Primary phosphate Free acid

3ZnHPO4 --> Zn3(PO4)2 + H3PO4 . Tertiary phosphate Free acid

A certain amount of free phosphoric acid must be present to repress the hydrolysis and to keep the bath stable for effective deposition of phosphate at the microca-thodic sites. Hence, depending upon the working temperatures and the concen-trations of the constituents in the bath, the free phosphoric acid content must be chosen to maintain the equilibrium condition. Too much of phosphoric acid not only delays the formation of the coa-ting, but also leads to excessive metal loss.

Figure 6 : Phosphatation mechanism [GUE-2005]

Phosphatation is the process which is mostly used by Tata Steel factories; it will be a matter of model for us as we seek to find a conversion coating with the same efficiency but more eco-friendly.

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I-2-What is Chromatation ?

I-2-a-Overview of the chromatation

Chromatation is a chemical conversion treatment which consists of immersing or spraying a substrate in/with a solution containing predominantly hexavalent chromium CrVI.The concerned substrates are metals and their alloys (electrolytic zinc, alumi-nium, silver...). Here we are working with galvanized zinc.This method is used primarily in order to obtain high corrosion resistance, and adhesion (often for paint application). In addition to these two properties we can also mention an esthetic aspect, because the chromatation causes the formation of various colors layers which depend on the particular nature of the substrate, electrolyts...

I-2-b-Principle of the method

The first thing is to “treat” the substrate surface which has to be chromated. In-deed, this surface needs to be free from defects (fats...) and as smooth as pos-sible in order to improve adhesion and uniformity of the future conversion layer. Then, the most used method consists in immersing the subject which needs to be chromated in a solution consisting main-ly of hexavalent chromium salts, activa-ting and reducing anions and an acid. We can find a multitude of formulation for the chromating solution. Zinc at the surface begins to oxidize it-self (up to 2 µm of its surface), generally under the action of the acid initially pre-sents in solution, according to the reac-tion: Zn --> Zn2+ + e-.Along with this oxidation, reduction of a part of CrVI into CrIII occurs. The CrVI form can vary with the local values of the pH solution (eg : 2CrO4

2- + 16H+ + 6e---> 2Cr3+ + 8H20). There is also the reduction of protons (which comes from the acid)

according to the reaction 2H+ + 2e---> H2. This reaction consumes between 5 and 15% of the electrons produced during the dissolution of zinc. These reactions in-creasing the local pH (acidity decreasing mainly due to the protons reduction) pro-mote the precipitation of chromium com-plexes, which contributes to the forma-tion of the layer. However, the reactions involved are complex. We can include an example of reaction of a complexe, that we can find in the literature:

Cr3+ + OH- + CrO42--->Cr(OH)CrO4.

This is the quantity of protons in the solu-tion which determines the speed of film formation, because it’s this same quan-tity which determines the reactions kine-tics. For example, below a critical value of pH (depending on the solution com-position), the reaction products are not sufficiently soluble and stay in solution rather than participate in the formation of the layer. Above this critical value, zinc is passive and blocks the reactions. There are external means in order to accelerate the reactions, such as raising the temperature of the chromatation solution. The composition of the layers obtained depends on the composition of the solution used to chromate the plates. Various results are presented in the table below and give an idea of the influence of the rate hexavalent chromium (in the solution), of the layer thickness and of the film surface density on the color of the layer which is obtained. [GIG-2004] We can use the XPS analysis to deter-mine the chemical composition of the conversion layer. At the end of the chromata-tion process, we obtain a relatively soft, amorphous gel, rich in water and porous, promoting the adhesion of organic mate-rials such as paints. Be careful, because if the gel hardens by drying, a drying at too high temperature can cause a loss of film properties due to dehydration of

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Figure 7 : Influence of Cr(IV) concentration in the bath, of film’s thickness and surfacic weight on the chromatation

color [GIG-2004]

the film and the apparition of cracks. The film becomes more and more hydropho-bic which makes the grip of a new layer impossible. Generally, this kind of gel doesn’t support temperature increases (above 120°C). The addition of silica is such a way to ensure hydration within the film.

I-2-c-Corrosion resistance

In general, chromatation can decrease the phenomenon of white rust of zinc, and red rust of steel.The conversion layer created during the chromatation improves corrosion resis-tance of galvanized steel. It acts as a barrier and a passive layer, which slows the dissolution of zinc. The lifetime of the zinc layer is increased. In addition, the chromate layer is a cathodic cor-rosion inhibitor. It blocks the cathodic sites, where the oxygen reduction at the metal surface occurs. Finally, the chro-mate ions, soluble in the chromate layer, provide self-healing effect. When there is a crack for example, the hexavalent chromium is redissolved in contact with moisture and then get out of this crack in order to reduce in the cavities where the underlying metal is oxidized. The re-dox reaction between zinc and chromium continues and compounds formed fill the film.The current-voltage curves of zinc-iron coating non-chromated and chroma-

ted in NaCl (3.5%) are presented below. [GIG-2004]

We can also say, in general, the addition of alloying elements in the zinc coating improves the corrosion resistance.

However, the use of the chromatation and so the hexavalent chromium tend to be deleted because they are harmful for the environment an health. [GIG-2004][RON-2011]

It was understood, the aim is to find different solutions without hexavalent chromium which is harmful for the en-vironment and people. Systems based on trivalent chromium are those that are most comparable to systems based on hexavalent chromium. However, the presence of chromium gives always the same conclusions in terms of harm-fulness. Substituents more or less inte-resting are emerging but are still at the research laboratory. The most studied is the molybdate (same column as the chromium in the periodic classification), but does not seem to be as effective as chromium-based solutions.

As for the phosphatation, chromatation is the most widely used process because of its efficiency, but it tends to disappear because of environmental laws restric-tions.Following this study, we are now going to present several solutions that seemed to be pertinent for us and have interested the company. These studies will pre-sent each method, their advantages and weaknesses.

Figure 8 :Current-voltage curves of inc-iron coating non chromated and chromated in NaCl (3.5%) [GIG-2004]

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II-1-a-Introduction

The vanadium conversion coating as chromate replacement has also been studied. Indeed, the vanadium coating seems to be more eco-friendly and to have an anti-corrosion efficiency close to that of the chromate coating.Many other conversion coatings for re-placement (like molybdate or titanate) have been considered but the vanadium solution has been studied more deeply because of the high solubility of the va-nadate crystalline oxides. Due to these different properties, many studies have been led concerning coatings on alumi-num or magnesium; these studies have shown that vanadate oxides are both anodic and cathodic corrosion inhibitors. Zhongli Zou et.al studied the influence of vanadate as corrosion inhibitors on gal-vanized steel.During their studies, the substrates were commercial electro galvanized steel plates with a zinc deposit of 60 g.m-2 of zinc on both side. Samples are then de-greased and immerged in a bath contai-ning vanadium compound (NaVO3). After immersion, samples have been washed (with distilled water) in order to eliminate any residual salt that could deteriorate the surface state and dried with com-pressed air. The main advantage of this solution is the facility of establishment in an indus-trial field: the deposit has to be made at room temperature and for only 60 se-conds.This kind of process is close to the one used for chromatation.

II-1-b-Electrochemical measurement

The electrochemical properties of three kinds of samples have been measured:- An untreated galvanized steel sample- A chromate treated sample- A vanadate treated sampleEach of these samples has been Tafel tested with scan rate of 5mVs−1 from −1.3 to −0.7V (vs. OCP -Open Circuit Potential) into a 3.5% NaCl solution at pH 6.8.

Figure 10 : Polarisation Curves [ZHO-2011]

Figure 10 shows the typical polarization curves obtained.It can be observed that both of the ano-dic (by blocking the action of H+ ions at the surface) and cathodic (by preventing the dissolution of ferrous ions) reac-tions have been significantly inhibited for the two treated plates. The effect of the vanadate coating is more significant on the anodic part of the curve than on the cathodic part.Thanks to the extrapolation of the Tafel curves, the corrosion intensities have also been calculated. The results show that the icor is 21 times lower with the vanadate coating than with the witness sample. This experiment also shows that vanadium conversion coating is as effi-cient as the chromium one (the polariza-

II-1-Vanadium Coating

II - ImplementAtIon of A new nAnocoAtIng for ActIve metAl protectIon

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tion curves are similar).It has been suggested that the protec-tion assured by the vanadium is due to the formation of a barrier that blocks the pores of the metal where the reduction of oxygen happens. The barrier layer avoids the dissolution of the metal by limiting the reduction of oxygen.

II-1-c-Formation of the coating

Many chromate-free coating approaches have been developed around the idea that it is necessary to form an oxide film that is insoluble over a wide range of pH and environmental conditions.On this basis, certain transition metal chemistries have not received in-depth consideration as chromate conversion coating replacements. Vanadium may be in this category due to the high solubi-lity of crystalline vanadium oxides.Des-pite the versatility of vanadium inhibition, there are relatively few coating chemis-tries in which vanadium or its compounds is the primary film-forming agent.Thus, coating development approaches focused on oxide precipitation and so-lubility exclude an important aspect of vanadium chemistrynamely, the ability of hydrolyzed vanadium species to behave as a sol, which rapidly condenses and polymerizes to form a hydrated amor-phous oxide.While the use of sol-gel coating methods as chromate conversion coating replace-ments is not new, many results show that stimulating gelation of transition metal sols in aqueous solutions at the solu-tion-metal interface using supplemental ingredients can lead to new conversion coatings with desirable properties.An essential part of the VCC (vanadium conversion coating) formation pro-cess is gelation of a hydrated vanadium oxide. The formation of pentavalentva-nadium oxides by condensation and po-

lymerization has been described quite thoroughly,and elements of this process appear to be operating in VCC formation. Vanadium oxide gel formation involves olation of octahedrally coordinated VO(OH)3(OH2)2. All the OH ligands lie in the equitorial plane of the molecule giving rise to highly anisotropic rates of poly-merization. Rapid polymerization occurs along the equitorial plane of these mole-cules leading to the formation of long rib-bon structures in the resulting gel. Ribbon-like structures are not evident in any of the VCC characterization conduc-ted so far, but the reaction rates for this process are sufficiently high to account for film formation in the time frames ob-served in these experiments.The ability to trigger the olation reaction during VCC formation appears to depend on the interplayamong the speciation of soluble vanadate ions, pH of the coating bath, and changes in the solution pH at the solution-metal interface. At millimolar concentrations of V5+, the predominant species in solution is VO2

+ when the pH is lower that 1.7 to 1.8. This species does not react to produce condensed vanadium oxides (Figure 10).

For this reason, vanadium oxide gels do not form spontaneously in the coating bath. Upon contact of the metal surface

Figure 11 : Equilibrium speciation of soluble V5+ ions in aqueous solutions at millimolar concentra-

tions [GUA-2004]

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with the coating bath, activationoccurs due to dissolution of the air-formed oxide film by the low pH and action of F–. Pro-ton reduction causes the interfacial pH to increase slightly.

This pH increase triggers formation of VO(OH)3 by hydrolysis of VO2+:

VO2 +2H2O → VO(OH)3 +H+

At pH values close to 2, coordination of VO(OH)3 changes from tetrahedral to octahedral by a water addition reaction (Figure 11):

VO(OH)3 +2H2O → VO(OH)3(OH2)2enabling spontaneous polymerization and formation of an amorphous surface film comprised of hydrated vanadium oxides. The resulting film morphology, as it has been characterized so far, is consistent with this type of a formation process. There is no evidence of crystalline com-pounds in the coating, and the presence of cracks in the VCCs suggests that the oxide is deposited in a highly hydrated form that is susceptible to dehydration after removal from the coating bath in much the same way that CCC (Chromata-tion Conversion Coating (chromates) are.

Results from the coating formation expe-riments and corrosion-resistance mea-surements show that coating formation

Figure 12 : Possible reaction processes involved in VCC formation.(a) Water addition to the pri-mary coordination sphere for VO(OH)3to form

VO(OH)3(OH2)2. (b) Olationreaction that leads to vanadium oxide gel formation. The octahedra in (b)

represent octahedrallycoordinated V 5+.

is critically dependent on the pH of the bath solutions.

In the context of this coating formation mechanism, if the coating bath is too acid, proton reduction may not be able to shift the pH enough to cause VO2+ hydro-lysis to any great extent.

This would inhibit VO(OH)3 formation and limit subsequent VCC formation. At bath pH values higher than 3, surface activa-tion of Aluminium becomes difficult due to the stability of the Aluminium oxide film, and the concentration of VO(OH)3 becomes too small for meaningful film formation.

In chromate conversion coating forma-tion, Fe(CN)6functions as a redox media-tor that cata lyzes chromate reduction on Aluminium. Fluoride serves to activate the surface by dissolving the air-formed oxide film permitting intense electroche-mical activity to occur. For the formation of corrosion-resistant CCCs, F– has a more significant effect than Fe(CN)6.

In VCC formation, Fe(CN)6 is the more critical ingredient. The mechanism for the formation of pentavalent vanadium oxides described above does not explicitly account for the critical role of Fe(CN)6 in VCC formation and therefore only des-cribes part of the formation process.

II-1-d-Talking about VCC Corrosion Re-sistance…On the basis of salt spray exposure tes-ting and EIS carried out in aerated 0.5 M NaCl solution, overallVCC corrosion resistance closely ap-proaches that of CCCs. VCC corrosion resistance appears to be degraded by immersion in the coating bath for times greater than about 3 min to 5 min. This may be due to the fact that once the alloy surface is passivated, the increase

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in interfacial pH that leads to film forma-tion diminishes, and the vanadium oxide network in the VCC is attacked by the aci-dic bath chemistry.Like CCCs and many thickened oxide layers on Al alloys, VCCs inhibit reduction reaction kinetics.

What’s more, VCCs increase resistance to pitting and suppress oxygen reduc-tion reactions. Simulated scratch cell experiments suggest that VCCs are also self-healing in a manner that closely re-sembles this characteristic in chromate conversion coatings.Vanadium conversion coating seems to be an efficient alternative to the chro-mate one, polarization curves are similar (icor is even lower with the vanadate coa-ting). The manufacturing process can be implemented at industrial scale (the de-position time is of the order of a minute).

II-1-e-Conclusion

The lack of references on the subject has prevented us from finding more informa-tion (only a few studies have been led on galvanized steel) and after consultation with Tata Steel, we decided not to keep this solution because of the cost entailed by a bath of vanadium.

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II-2-Montmorillonite in an epoxy matrix

II-2-a-Introduction about Montmorillo-nite

Organic coatings are widely used to pre-vent corrosion of metallic structures. Recently, montmorrillonite–layered sili-cate (clay) has attracted intensive re-search interest for the preparation of po-lymer–clay nanocomposites because its lamellar elements display high in–plane strength, stiffness, and high aspect ra-tios. [HUN-2011]It has been reported that the incorpora-tion of a small amount (1–5%) of layered clay in organic polymers leads to signi-ficant improvements in mechanical per-formance, thermal stability, and barrier properties of organic coatings.[TOT-2007] This barrier properties can help us to find a more environmentally accep-table solution to prevent steels corrosion.

In order to assure a good protection against corrosive species, a complete separation and dispersion of the indivi-dual monmorillonites layers inside the polymer matrix is necessary. Montmo-rillonite has a morphology of planes : The chemical structures of montmorillo-nite consist of two sheets of tetrahedral silica fused to an edge-shared octahe-dral-based sheet of either magnesium or aluminium hydroxide. Polymer matrix can penetrate inside the interplanar gal-lery.

Generally, the surface of the clay needs to be modified to improve its dispersibi-lity in the polymeric network.This struc-ture is naturally non-organophilic. In order to make it more organophilic, the Na+ and/or Ca2+ ions in the interlayer can be replaced by organic cations through a cation exchange reaction.

Figure 13 : Montmorillonite’s strycture : T stands for tetrahedral sheet, O stands for octaedral sheet

[VOL-2002]

The corrosion protection is related to the enhancement of the barrier properties of the coating.

II-2-b-Different processes

1- Proposed by [TOT-2007]

•aminotrimethylphosphonicacid(ATMP)is used to modify momontmorillonite (commercialized by Henkel Technolo-gies-Concorde Chimie, France )•montmorillonitefromTuyPhong-BinhThuan province inVietnam rinsed with distilled water.•Epoxyresin:Epikote828(commercia-lized by Ciba Co.)•CuringAgent:dimethylaminopropyla-mine (commercialized by Ciba Co.)

1st step : ATMP modification of the clay : The clay (3.0 g) was dispersed in distilled water (300 ml) containing concentrated hydrochloric acid (0.5 ml) and ATMP (7.0 g). Then, the suspension was stirred at 70°C for 24 h to afford a white precipitate. Filtration of the precipitate and drying at 80 °C in a vacuum oven for 2 days.

2nd step : Incorporation of the nanocalys in the epoxy resin

This coating sharply differs from the precedent one as it is a composite material: it is an association of an organic matrix and nano-particules.

17

II-2-Montmorillonite in an epoxy matrix3rd step : Coating : applied by air spraying and drying (ambient temperature for 24 h)Final thickness 30±3 μm thick.

2- Proposed by [FED-2009]

• Epoxy Resin : 3,4-epoxycyclohexyl-methyl-3’,4’-epoxycyclohexancarboxy-late supplied by Dow Chemicals

• Photoinitiator : mixture of phosphatesulfonium salts, UVI 6990, supplied by Dow Chemicals, as solution in propy-lene carbonate (50 w/w%). This solution was added to the curable mixtures at a concentration of 4 w%.

•Montmorillonite: - Cloisite 30B purchased from Southern Clay Product Inc. (USA) (see Annex 1)OR - Cloisite Na+ purchased from Southern Clay Product Inc. (USA) containing alkyl ammonium quaternary ions (90 meq of quaternary alkyl ammonium ions per 100 g clay) bearing two hydroxyethyl groups linked to the nitrogen atom (see Annex 2)

•InordertomodifyCloisiteNa+,3-gly-cidoxypropyltriethoxysilane (γGPS)

1st step : nanoclay was washed with dis-tilled water for several times

2nd step for Cloisite 30B : 20 g of the clay were dispersed into 300 ml of water and vigorously stirred. After a few minutes, the dispersion was decanted and filtered. The treatment was repeated three times, until the pH of water was neutral. The washed nanoclay was then dried over-night in an oven at 80°C.

The different solutions that we find with this kind of process including clays are very long : 8 to 24 hours of process. This is too long to adapt to an industrial pro-cess.

II-2-c-Future works and optimization of the solution

Proposed by [NEM-2010]

A way to optimize the system is to add Montmorillonite organoclay and nano-glass flake into an epoxy resin by mecha-nical agitation and sonication (Sonication is the act of applying sound (usually ul-trasound) energy to agitate particles in a sample) process and to compare the two methods. Different analysis showed that nano-GF filled (nanoglass flake) specimens display better corrosion per-formance than the OMMT filled ones ( Montmorillonite organoclay).

In order to compare the two sys-tems, theDiglycidyl ether of bisphenol-A(DGEBA) epoxy resin was used and mixed with a reactive diluent. The OMMT (Montmorillonite organoclay) and the nano-GF(glass flakes) were added to the mixture (1 and 3 wt %). The suspension was kept at 60 degrees and stirred at 1200 rpm for 2h. Then, the mixtures were

Figure 14 : Structure of 3,4-epoxycyclohexyl-methyl-3’,4’-epoxycyclohexancarboxylate

Figure 15 : Structure of photoinitiator

Figure 16 : Structure of alkylammonium quater-nary salt

18

Figure 20 : Water absorption curves for different samples after certain time intervals [NEM-2010]

sonicated for 30 min and 1h, mixed with hardener in 1:1 ratio and then degassed under vacuum. The synthesized nano-composites were applied on CRS (Cold Rolled Steel) panels and finally cured at 60 degrees for a week with the use of UV. The final coating thickness was between 60 and 70 µm.

Different tests such as the electroche-mical impedance measurement, Opti-cal microscopy or pull-off adhesion test were made to study the two systems. The electrochemical impedance spec-troscopy data from specimens after 30 min of immersion in 5 wt% NaCl solu-tion show extremely high resistance for nanocomposite coatings. Other results show also that addition of nanoparticles improves the coating resistance and the samples with nanoglass flakes especial-ly show better barrier properties then the samples filled with nanoclay. The reason of this observation is that the ratio Area/Thickness of nanoglass flakes is better than the one of the clay epoxy nanocom-posite. The corroding agents are forced to travel a longer tortuous path to reach the substrate with the Nano-GF sample. Another reason is due to a lower water permeability of the glass than clay layers and a lower amount of water absorbed by GF-Epoxy nanocomposite compared with organoclay epoxy nanocomposite.

As told before, the polarisation resis-tance (Rp) for the 3wt% nano-GF is twice better than the 3wt% OMMT one.

Figure 17 : Structure of the DGEBA epoxy resin

Figure 18 : Electrochemical parameters obtained from potentiodynamic polarization measurementsafter 50 days immersion of samples [NEM-2010]

Figure 19 : Rc versus immersion time in 5% NaCl solution for neat epoxy with different

weight of Clays and glasses used in an epoxy resin coated specimens [NEM-2010]

The corrosion rate is also low for the two systems.The corrosion potential for all samples is more positive than that observed in the case of bare metal. The corrosion current density, Icorr, values for nano-composite coatings decrease gradually as the amounts of OMMT and nano-GF increase up to 3 wt%. Thus, the 3 wt% GF–epoxy coated sample has the lowest value of Icorr(0.188 lA/cm2). On the other hand, the most positive value for Ecorr indicates that 3 wt% GF–epoxy samples have thermodynamically the lowest cor-rosion tendency after 50 days immersion.have thermodynamically the lowest cor-rosion tendency after 50 days immersion.

For a long Immersion time, the 3wt% glass specimen shows a better Rc, so a better corrosion protection than the other systems.

19

The amounts of water uptake obtained from samples weight measurements at certain time intervals up to 100 days are shown in the curves just before. The ini-tial slope of this graph is proportional to the diffusion constant of water in poly-mer and the plateau region as a function of the square root of immersion time, represents the saturation water content of the polymer.

As shown in water uptake curves, the slope of the graphs decreased as the amounts of additives increased to 3 wt%, which indicates a lower diffusion constant for nanocomposite samples in comparison with that of pristine polymer. After 100 days immersion, 3 wt% GF–epoxy gained 1.521 g in weight, resul-ting in 2.8 wt% water uptake. Also, the calculated diffusion coefficient was 3.9 x 10-8 cm2.s-1which shows the best diffu-sion performance compared to all other samples. This finding reaffirms the pre-vious results of electrochemical measu-rements.According to the two systems, a salt spray test was also used to study the corrosion resistance.Indeed, the salt spray test was conduc-ted as an accelerated corrosion tes-ting method to evaluate corrosion per-formance of the prepared samples as described before. After exposure of

the samples for about 500 h (21 days), as shown in the picture below, nume-rous blisters were observed near the scratches and over the whole coated surface in the case of pristine epoxy coa-ted specimen. Also, a brown adherent corrosion product (which is a mixture of iron hydroxides) was observed all over the sample surface. No blister was found in samples coated with OMMT–epoxy or GF–epoxy, but delamination and water penetration were observed around the scratches which decreased in the order of 1 wt% OMMT sample >3 wt% OMMT sample >1 wt% GF sample >3 wt% GF sample. This is consistent with the re-sults of barrier tests. The enhancement of corrosion resistance of all the inves-tigated nanocomposite coatings may be due to the nature, shape and size of the nano-additives. These additives fill the voids, crevices and pinholes of the poly-mer and substrate and improve coating adhesion to the substrate. As mentioned before, the nanolayers of these additives enforce corroding agents to travel a tor-tuous path to reach the substrate. As it is known, the nanoglass flakes have an extended surface area and higher aspect ratio than the layers of nanoclay. So, glass flakes layers create longer bar-rier spots toward corroding agents than montmorillonite clay, thereby improving the corrosion resistance of the coating.

Figure 21 : Surface appearance of the samples after exposing to salt spray for 500 h. (a) Neat epoxy, (b) 1 wt% OMMT–epoxy, (c) 3 wt% OMMT–epoxy, (d) 1 wt% GF–epoxy, and (e) 3 wt% GF–epoxy coated panels. [NEM-2010]

20

II-2-d-Conclusion

This solution has kept the attention of Tata Steel because they hadn’t heard about it. Despite its efficiency, this method hasn’t been retained because of the length and the cost of the process.

21

II-3-Conversion coating with phytic acid [ELS-2012]

Protection of galvanized steel from cor-rosion in NaCl solution by coverage with phytic acid self-assembled monolayers modified with thiols.

II-3-a-Introduction

This solution is based on the recent ar-ticle released in Corrosion Science (n° 55, p.339-350, Feb 2012) and written by Mr. El-Sayed and his team. As mentio-ned in the introduction of the report, the main target is to find a new envi-ronmental-friendly conversion coating to protect galvanized steels from cor-rosion. Indeed, in spite of a significant protective efficiency against galvanized steels’ corrosion, the chromate coa-ting is being banned by the European Union. TataSteel takes an interest in this study because the process seems to be simple, fast and effective, which means: more economical. Currently, our goal is to explain in detail the experimental procedure in order to transpose it in our lab. The reliability of their results could be proved, or not, thanks to our conclu-sion following our operating procedure. The main significant point of this study is the use of a new compound as a cor-rosion inhibitor which is nontoxic, stable, soluble, inert,that has a high affinity and cheap: phytic acid. This molecule is usually used in biology as an inhibitor for some minerals (irons) by chelating. This is a mechanism which is typical of this process. A second point is really interes-ting: in order to lead to a self-assembled monolayer on galvanized steels, strong bonds between thiols and zinc have been formed thanks to two organic molecules, 2,3-dimercapto-1-propanol (DMP) and dithio-oxamide (DTOA). The study shows the efficiency of this kind of coating that

we want to check. Following the intro-duction, some experiments have been achieved to underline the real protective efficiency against corrosion of a coating with phytic acid and a self-assembled monolayer of thiols and to reveal the mechanisms involved. The two most im-portant aims of our work are the certifi-cation of the study and the explanation of the involved mechanisms.

Figure 22 : Molecule of phytic acid:myo-inosi-tol hexakisphosphate

Figure 23 : Molecule of DMP

Figure 24 : Molecule of DTOA

22

II-3-b-Experimental Procedure of The Article

In order to optimize the protection of galvanized steel, A-R. El-Sayed and his team worked on a process including the use of phytic acid modified with some cations and thiols.Indeed, a high grade reagents of phy-tic acid (PA) , diethylenetriaminepenta-methanephosphonic acid (DETPMPS), 2,3-dimercapto-1-propanol(DMP), di-thio-oxamide(DTOA), MgSO4 and Cr(NO3)3 were used for the treatment of the gal-vanized steel. Furthermore, organic sol-vents, ethanol and n-propanol were all high grade chemicals, used in the pre-paration and modification of DMP and DTOA, respectively, on galvanized steel. A pretreatment was also made by using high grade reagents of H2SO4, H2O2 and alkaline solutions to prepare the samples before the coating process.

An aqueous solution of 0.5 M NaCl was prepared by dissolving an analyti-cal reagent of NaCl in distilled water. Concerning the galvanized steel, a series of samples with dimension of 30 X 40 X 1 mm were prepared as electrochemical test. However the apparent exposed area in the electrolytic cell is 1 cm2. Each sample was cleaned sequentially with ethanol and distilled water pretreatment, then soaked. The solutions of phytic acid (PA) and DETPMPS (0.5 mM) were prepared by dissolving the appropriate amount in volume in distilled water. The pH value was adjusted to about 4 by diluted a KOH solution.

The solutions of DMP and DTOA (1 mM) were prepared by dissolving the appro-priate amount by volume in distilled water and 5% ethanol and 5% n-propa-nol, respectively. Solutions (1 mM) of both MnSO4 and Cr(NO3)3 were prepared by dissolving the appropriate amount in

weight in distilled water. The tempera-ture of all investigated baths was 45 °C.

For the coating, different bath were used, composed of 0,5 mM of Phytic Acid or/with 1mM of MnSO4, 1mM of DMP/ DTOA and 0,5 mM of DETPMPS.

II-3-c-Measurements

Many measurements were made in or-der to analyze the samples and observe the efficiency of the process proposed by M. El-Sayed and his team. At first, the corrosion resistance of the coating film was evaluated using poten-tiodynamic polarization and electroche-mical impedance spectroscopy (EIS) measurements.The polarization curves measurements were performed via a model voltalabPo-tentiostat, and conducted in 0.5 M NaCl solution using a conventional three elec-trode cell. The specimen under study with an expo-sure area of 1 cm2, a platinum sheet of 16 cm2 and a saturated calomelelectrode (SCE) were used as the working, counter and reference electrodes, respectively.

All electrochemical measurements were measured after a steady open circuit po-tential (OCP). The polarization curve was measured potentiodynamically by swee-ping the potential in the positive direc-tion at a scan rate of 1 mV/s and a sweep range from an initial potential of -0.150 V to a final potential of +0.150 V (both are relative to OCP).EIS measurements were carried out using AC signals of amplitude 5 mV peak to peak at OCP (Ecorr) in the frequency range from 10 kHz to 5 mHz.

To conclude, all experiments were conducted for each sample under the same conditions in order to ensure re-production of the results at room tempe-rature (20 ± 1 °C).

23

II-3-d-Results and discussion

We are going to talk essentially about the Polarization measurement. Howe-ver, we will also illustrate the EIS mea-surements to corroborate the efficiency of the different processes.

Polarization curves of coating samples in 0,5 M NaCl solution, and retreatment in H2SO4/ H20 were plot in order to discuss about the experimental procedure (dif-ferent plots with respectively phytic acid, DMP, DTOA, Mn used alone or together). The duration of the immersion of the samples took 2 h.

Figure 25 : Polarization curves of coating samples in 0.5 M NaCl solution, and retreat-ment in H2SO4/H2O2 ( Phytic acid, Phytic acid

with Mn, Phytic acid with DMP and Phytic acid with both DMP and Mn) [ELS-2012]

Figure 26 : Polarization curves of coating samples in 0.5 M NaCl solution, and pretreat-

ment in H2SO4/H2O2. ( with DMP and DTOA)

Figure 27 : Polarization curves of coating samples in 0.5 M NaCl solution, and pretreat-ment in H2SO4/H2O2 ( case of DTOA, Phytic acid and Mn used alone or together). [ELS-2012]

The corrosion parameters were calcula-ted on the basis of the cathodic and ano-dic potential vs current density characte-ristics in the Tafel potential region.

First, we are going to discuss about samples with the pretreatments H202/H2S04.The results showed that the inhibitive effect of the coated films on the anodic

24

process is greater than that on the ca-thodic one. The marked suppression of the anodic process was observed with the coating film of the phytic acid modi-fied with DMP on the surface, sugges-ting stabilization of Zn atoms by adsorp-tion of DMP through phytic acid forming a stable bond between sulfur and Zn atoms.The curves also showed inhibition of the cathodic process by coating the surface with this film, being attributed to blocking diffusion of molecular oxygen through the film.

If we analyze the following data in the table below, we can see that the corro-sion current density highly decreased in the case of a coated surface with multi-layer of both PA and PA + Mn2+ modified with DMP compared with the case of PA used alone.

The data also exhibit that the protective efficiency (P%) value decreases in the following sequence:[phytic acid modified with DMP >phytic acid þ Mn2þ modified with DMP >phytic acid þ Mn2þ >phytic acid]

This trend shows that phytic acid (first dipping) modified with DMP (second dipping) has a high P% (97%), and the conversion layer appears thick and com-pact. Accordingly, a surface completely covered by the conversion layer could

prevent the penetration of Cl-ions.

The corrosion current density (icorr) va-lues of the samples treated by DTOA and DMP are very low (0.96 and 0.19 lA/cm2, respectively) compared with that of the uncoated sample (6.08 lA/cm2). On the other hand, corresponding cor-rosion potential (Ecorr) values of DTOA and DMP were identified as – 1034 mV and - 1024 mV, respectively. This indi-cates that the corrosion potential of the coating samples by DTOA and DMP shifts to more positive potential compared wit-hthat of the uncoated sample (- 1113 mV vs. SCE) in 0.5 M NaCl.

Therefore, DMP passivated sample exhibits better corrosion resistance (P%=96.9%) than that of DTOA passiva-ted one (84.2%). This behavior can be at-tributed to the more stable monolayers-formed in the case of DMP than those of DTOA. This stability is correlated with the close packing of the monolayers on the surface.

The optimization of both structures shows that DMP has longer C–S bond length than that of DTOA (C–S = 1.91 Å and 1.70 Å, respectively, as you can see in figure 21 on the next page).

Figure 28 : Corrosion parameters obtained from Tafel extrapolation curves for galvanized steel in 0.5 M NaCl solution coated with different compounds, and the pretreatment in H2SO4/H2O2 [ELS-2012]

25

Figure 29 : Calculated atomic charge for (a) 2,3-dimercapto-1-propanol (DMP) and (b) dithio-oxamide (DTOA). [ELS-2012]

The effectiveness of the monolayers ageing must be connected to the one which relates to the protection against the observed corrosion under the same conditions. The sensitivity to both cor-rosion and ageing should be attributed to the initial presence of holes/defects which can be the starting point of chemi-cal reactions which become increasingly fast.

In order to compare the pretreated samples in both H2SO4/H2O2 mixture and hot alkaline solution followed with dip-ping in H2SO4/H2O2 mixture, the effect of hot alkaline solution as pretreatment of the uncoated and coated samples has been studied.

The following figure demonstrates po-larization curves of galvanized steel samples, uncoated and coated with the films of DMP and phyticacid and Mn2+, modified with DMP. The polarization curves of uncoated sample pretreated in hot alkaline followed with H2SO4/H2O2 solutions, exhibit that the corrosion cur-rent density is higher in the case of the former pretreatment (8.33 lA/cm2) than

that of the latter one (6.08 lA/cm2). This behavior can be attributed to the pre-treatment in hot alkaline solution that dissolves most oxides formed on the sample surface, thus making the surface more active.These protective films are persistent du-ring immersion in aerated 0.5 M NaCl for 2 h. Thus, the persistence of these films is far superior on the galvanized steel. This indicates that the presence of phy-tic acid and Mn2+ layer (first dipping) with DMP conversion coating (second dip-ping), exhibited slightly increase in P% value compared with that of DMP layer.

Figure 30 : Polarization curves of coating samples in 0.5 M NaCl solution, and pretreatment in alkaline and

H2SO4/H2O2 (for DTOA, Phytic Acid and Mn used alone or together). [ELS-2012]

26

The important data are summarized in the following table in order to compare the different solu-tion with a pretreatment in alkaline solution and H2SO4/H2O2.

The data show that the value of P% in the case of phytic acid with Mn2+ modified with DTOA (91.7%) is higher than that of DTOA film (77%). This behavior would support to the combination between phytic acid with Mn2+ SAM and DTOA. Therefore, the thickness of the multilayer seems to be large enough to prevent galvanized steel corrosion sufficiently.

Figure 31 : Corrosion parameters obtained from Tafel extrapolation curves for galvanized steel in 0.5 M NaCl solu-tion coated with different compounds and the pretreatment in both alkaline solution and H2SO4/H2O2 [ELS-2012]

By comparing the pretreatment of the galvanized steel in H2SO4/H2O2-mixture before the forma-tion of DTOA film and phyticacid with Mn2+ modified with DTOA film, they exhibited higher pro-tective efficiency values (84.2% and 97.9% for the two investigated films, respectively) than those for the pretreatment in both hot alkaline solution and H2SO4/H2O2-mixture (77% and 91.7%). The higher P% values of the films formed on the surfaces pretreated in H2SO4/H2O2-mixture only can be attributed to the presence of some oxide on the surface which assisted in the protective abili-tyof the investigated films. Finally, we can conclude that the presenceof the oxide within the film plays an important role in theprotection of galvanized steel from corrosion in 0.5 M NaCl.

According to the EIS (Electrochemical Impedance Spectroscope) measurements, M El-Sayed and his team obtained the following data with the same procedures that we have seen before.

Figure 32: Impedance parameters for coating samples in 0.5 M NaCl solution, and pretreatment in H2SO4/H2O2

[ELS-2012]

Figure 33 : Impedance parameters for coating samples in 0.5 M NaCl solution, and pretreatment in alkaline and H2SO4/H2O2 [ELS-2012]

By comparing the impedance parameters of the pretreated samples in both H2SO4/H2O2-mixture only and hot alkaline solution in addition to H2SO4/H2O2-mixture before coating conversion layer, some differences of the estimated values are observed.

That is, most investigated conversion coating of the samples pretreated only in H2SO4/H2O2-mix-

27

ture showed that the protective efficien-cy (P%) values are greater than those of pretreated in both hot alkaline solution and H2SO4/H2O2-mixture. As mentioned before (Tafel-plots), this behavior may be attributed to the presence of traces of oxide on the surface in the case of samples pretreated in H2SO4/H2O2-mix-ture.

Therefore, this oxide facilitates the ad-sorption of self-assembling molecules (SAM) on the substrate, in particular, the compounds containing sulfur atoms (DTOA and DMP). M El-Sayed stated that the presence of traces of oxides on the surface appears to be important, confir-ming that the thiol is probably grafted onto the ZnO.

Finally, the protective efficiency (P%) va-lues obtained from impedance measu-rements of both the two pretreated sur-faces are in agreement with the results obtained by Tafel-plots extrapolation under the same conditions.

II-3-e-Conclusion of their study

In order to prepare thick films of the phy-tic acid and phytic acid with Mn2+ adsor-bed on galvanized steel, multistep modi-fication using DMP and DTOA is carried out. On the other hand, a comparative study of self-assembled monolayers of DMP and DTOA is performed for the first time. The protective efficiency (P%) values of films are examined by Tafel-plots and impedance measurements of the coated galvanized steel in 0.5 M NaCl solution.The values of the protective ef-ficiency for the films of DMP and DTOA arehigher than those for just a galvani-zed steel sample. The protective ability of the film against corrosion seems to be persistent during immersion in the

solution.More interesting: the presence of phytic acid layer (first dipping) with the DMP conversion coating (second dipping) increases in P% value compa-red with a pure DMP conversion coating layer.Finally the pretreatment in a H2O2/SO4 solution is the most efficient accor-ding to the results of the study. Nevertheless, in our opinion, the presentation of the results appears too much optimistic. That’s why we are thin-king we have to check the three most efficient coatings by using the same operating procedure in order to com-pare both results with precision. We can make another objection: there is little information about the involved mecha-nisms, just a few assumptions. The team of Mr. El-Sayed could have made a characterization of several coatings to bring to light their structure with a scanning electron microscope for ins-tance. We need more information to un-derstand and master the mechanism of these coatings so that the process can be reproducible. Unfortunately, a signi-ficant data is missing: the study doesn’t compare the protective efficiency of the coatings with these of a phosphated gal-vanized steel‘s sample. It’s important to know if this solution for a conversion coating is as efficient as the current one.[ELS-2012]

II-3-f-Explanation of the mechanisms

In this part we are going to explain where the phytic acid/DMP conversion coating efficiency comes from. What are basi-cally the mechanisms involved in the adhesive and anti-corrosion properties.We start with a galvanized steel subs-trate which means that its surface is made of zinc. We use a H2SO4/H2O2 pre-treatment solution in order to prepare the surface. This will clean the surface,

28

II-3-g-Our Experimental Protocol

In order to complete the publication and verify that the curves that are given, we propose an experimental protoole to tes-tit. Annex 1 presents this experimental protocle and Annex 2 presents the diffi-culties we met during this experimenta-tions. Results will be presented during the oral presentation of this project.

free from contaminants such as oils, greases, waxes, corrosion products and other soils. Moreover, this treatment will “free” some Zn2+ ions on the surface.Now we are going to talk about the phy-tic acid; it has some P-O- bonds. It is a reaction by chelating: creation of a com-plex with ionic bonds between 2PO2- and Zn2+ so that the phytic acid holds tight to the substrate. The diffusion of Zn2+ can be limited. The shape of the phytic acid molecule allows us to think that a part of the OH linked to the phosphorus will in-deed create bonds with the substrate but that another part of the OH bonds loca-ted on the opposite part of the molecule will be free to adhere with a future poly-mer coating put on the top of the conver-sion coating. This way, the use of phytic acid allows a good adhesion between a future polymer painting and the galvani-zed steel substrate.We also use DMP that will take part of the conversion coating as a corrosion in-hibitor. We assume that the DMP works as a barrier thanks to the steric effects of its sulfur atoms which limit the diffusion of Cl- or O2.To maintain itself properly on the surface of the substrate its R-HS group will bond with the Zn2+ of the sur-face. It will possibly create bonds with a future paint layer (polyurethane) thanks to its OH bonds. Indeed there is a strong interaction between NCO and OH groups. This way, the solution of phytic acid and DMP that is used fulfils the adhesion and anti-corrosion criteria that were imposed.

29

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n pr

oper

ties,

Ec

onom

ical

, eas

y an

d sh

ort

proc

esse

s ++

++

Pre-

trea

tmen

t nee

ded,

2

bath

s ne

eded

( D

MP/

DTO

A an

d ph

ytic

aci

d), l

ess

effi-

cien

t tha

n ch

rom

atat

ion-

--

Org

anic

Very

goo

d w

ith

chel

atio

n ef

fect

an

d O

H b

onds

++

+++

1

Conclusion

30

Conclusion

The propositions of new conversion coa-tings which are more eco-friendly exist in many different publications. But this is often the same mechanisms which are used through the publications : for example Montmorillonite and Vanadium coatings are not new, and it has already been tried by many siderurgist. Pro-blems of industrialisation are often the main issues. Even if those solutions have good properties against corrosion, it can not be used in the industry because of too long, too dangerous, or too expensive processes.

That is why, the challenge is to find total-ly new solutions which are not known by siderurgists. The acid phytic conversion coating was totally new because it was published in February 2012. That’s why this process was very interesting for us and Tata Steel. The process is not com-plicated and does not take very long.Our experiments on this solution will complete this publication, and will help Tata Steel improve this solution in their research department.

31

Quelques mots sur l’organisation du groupe

Ce projet proposé par l’entreprise Tata Steel a mobilisé 6 étudiants pendant 30 semaines, à raison d’environ 2h de tra-vail par semaine pour chaque personne. Comment le travail s’est-il organisé au sein du groupe et comment la commu-nication avec l’entreprise s’est –elle établie? Différents outils ont été mis en place pour une bonne organisation du groupe.

Les outiLs de travaiLTout d’abord, un diagramme de Gant a été élaboré avec les dates importantes du projet. Nous nous y réfèrions régu-lièrement afin de vérifier que nous étions bien dans les temps prévus. Lorsque les dates butoires arrivaient, l’ensemble du groupe travaillait simultanément afin d’être opérationnel le jour J. Nous avons également établi un cahier des charges fonctionnel en collaboration avec nos tuteurs. Ce cahier des charges nous a permis de bien définir les objectifs du projet, les conditions de travail et les grandes dates à respecter. Chacun des membres du groupe pouvait s’y référer à tout moment en cas de questionnement sur certains points. Nous l’avons égale-ment rédigé en anglais afin que l’entre-prise puisse y avoir accès.Le développement sous jacent à ce projet s’appuie sur les connaissances acquises en cours, en bibliographie et par des échanges avec des experts. Ces informa-tions, à caractère général sont à consi-dérer dans le domaine public. Elles ne souffrent pas de restriction de diffusion. Cependant lors de ce projet, le groupe a été amené à avoir accès à des informa-tions industrielles du groupe Tata Steel. Sur ce point nous nous sommes enga-gés donc à ne pas diffuser ces informa-tions. Dans ce même cadre nous avons

utilisé la plate-forme sécurisée LED d’échange de documents. L’échange d’informations confidentielles sur des plateformes publiques comme Google était prohibé. La plateforme d’échange de documents LED a donc été un de nos outils de travail tout au long du projet.

Les réunions de groupeNous n’avons pas toujours utilisé tous les créneaux mis à notre disposition pour nous réunir. Nous préférions tra-vailler chacun de notre coté en échan-geant des mails plutôt que de perdre du temps à discuter en réunion. Les réunions n’avaient donc lieu que si le groupe devait prendre des décisions importantes, rencontrer les tuteurs, ou bien les représentants de Tata Steel. Les réunions se voulaient le plus effi-caces possible. De nombreux mails ont donc été échangés entre nous tous, afin de tenir les autres informés de l’avan-cée de nos travaux respectifs. La com-munication entre tous les membres du groupe s’est donc faite sans problème malgré un nombre total de réunions res-treint sur toute la durée du projet. Il est vrai qu’en comparaison avec certains autres groupes, nous nous sommes très peu rencontrés, mais nous consi-dérions que le travail personnel ou par petits sous-groupes de 2 ou 3 était sou-vent bien plus efficace que des réunions dans lesquelles les discussions sur le projet finissaient souvent par digresser.Pour les réunions que nous avons tout de même organisées avec nos tuteurs INSA ou l’entreprise Tata Steel, nous préparions nos questions ou nos pré-sentations à l’avance afin d’être plus ef-ficaces le jour venu. Lorsqu’un membre devait être absent pour une raison per-sonnelle lors de ces réunions, il pré-

32

venait à l’avance et le chef de projet se chargeait de lui envoyer un mail par la suite afin de le mettre au courant de ce qu’il s’était dit et décidé en son absence.Nous avons également pris des rendez-vous avec d’autres professeurs que nos tuteurs lorsque nos questionnements ne touchaient plus leurs domaines de com-pétences. Nous avons ainsi rencontré des professeurs d’adhésion, de biomolé-cules, ou de polymères afin de leur poser nos questions, que nous avions préala-blement ciblées avant les différents ren-dez-vous.

La répartition du travaiLLe travail a été équitablement réparti dès le début, chacun devait traiter une sous-partie du projet. Puis, à la fin, lorsque la solution la plus intéressante a dû être testée, chacun a participé aux expé-riences afin de bien connaître la solution finale et d’être à l’aise pour l’explication de nos manipulations lors de la soute-nance orale finale. La préparation d’un protocole expéri-mental nous a demandé beaucoup de temps et d’organisation puisqu’elle est intervenue à la fin du projet. Il nous a fallu commander les produits néces-saires, établir un protocole précis et enfin, mettre en place les expériences. Madame Fregonese, qui est plus habi-tuée que nous pour les commandes de produits chimiques, nous a donc beau-coup aidés pour cette étape du projet.

Les difficuLtés rencontréesIl a été difficile d’accorder nos objectifs avec l’emploi du temps de TataSteel. Nous sommes restés sans réponse à nos questions pendant un long mois au début du projet. De plus, nous avons changé de référents par la suite, ce qui a à nouveau modifié le sujet du projet. La principale difficulté a donc été la communication avec l’entreprise : lorsqu’elle attendait

quelque chose de notre part, nous de-vions faire vite, mais lorsque nous avions des questions, ou besoin d’organiser une visioconférence, nous restions souvent sans réponse. Nous avons donc souvent dû avoir recours à l’appui de nos tuteurs pour obtenir des réponses.

La rédaction finaLeLa rédaction du rapport final a été par-tagée entre tous les membres du groupe en fonction de ce sur quoi ils avaient tra-vaillé tout au long du projet. Le chef de projet s’est chargé de centraliser toutes ces différentes parties et a mis en page l’ensemble.Chacun des membres du groupe était également chargé de rédiger ses propres références bibliographiques et de les en-voyer au chef de projet afin qu’elles ap-paraissent dans la liste bibliographique du dossier final. Nous nous sommes fixés de finir le rap-port écrit une semaine avant la date de-mandée afin de se laisser une semaine de plus pour relire et corriger les fautes d’anglais. Nos tuteurs ont également pu apporter leurs corrections pendant cette semaine.

BiLan finaLLe bilan de ce groupe est relativement positif puisque nous n’avons été confron-tés à aucun conflit ou malentendu au cours de ces 30 semaines. Chacun des membres du groupe a travaillé de façon à faire avancer le projet et à ne pas accu-muler de retard. Chacun avançait dans le même sens, et l’ambiance de travail était agréable avec une bonne dynamique. Chaque membre du groupe a su mettre ses propres intérêts de coté et travailler en équipe.

33

Remerciements

Marion Frégonèse

Bernard Normand

Magali Wainer and the other from Tata Steel

Fouzia Hannour

Jean-François Gerard

Fréderic Lortie

Sylvie Moebs

Françoise Picard

and

Fethi, for the help he brought to us during our experimentationsAnd all the others who help us during our experiments in the lab

34

References(ARC-2012] ARCHITEXTUR. Texture - Métal Galvanisé N°01, disponible sur : http://www.architextur.eu/OSC/catalog/product_info.php?products_id=451&page=6, 2012-03-30[AUF-2005] M. AUFRAY, Caractérisation physico-chimique des interphases époxyde-amine / oxyde ou hydroxyde métallique, et de leurs constituants, Matériaux polymères et composites, Lieu de soutenance : Institut National des Sciences Appliquées de Lyon, 2005, 186 pages[ELS-2012] A.R. EL-SAYEDA, U. HARMB, KM. MANGOLDB, W. FÜRBETHB, Protection of galvanized steel from corrosion in NaCl solution by coverage with phytic acid SAM modified with some cations and thiols, Corrosion Science, Volume 55, February 2012, Pages 339-350[DUN-2002] D. DUNLAP, J. PAREKHJI, A. JINGJONG YOUR, San José State University, USA,Experimental Methods in Materials Engineering, December 10, 2002[FED-2009] M. FEDEL (2009) Environmentally friendly hybrid coatings for corrosion protection:silane based pre-treatments and nanostructured waterborne coatings. PhDthesis,University of Trento[GIG-2004] M.P. GIGANDET, L. THIERY,Traitements de conversion sans chrome hexavalent, Techniques de l’ingénieur, 10 déc. 2004, Référence M1559 (base documentaire :Traitements de surface des métaux en milieu aqueux / Référence 42359210).[GUA-2004] H. GUAN, R.G. BUCHHEIT, Corrosion Protection of Aluminum Alloy 2024-T3 by Vanadate Conversion Coatings, CORROSION SCIENCE, March 2004, p284-296, ISSN: 0010-938X[GUE-2005] T. GUÉGUEN, Phosphatation, Date de publication : 10 sept. 2005, www.tech-niques-ingenieur.fr Référence M1575[HUN-2011] W.I HUNG, K.C. CHANG, Y.H. CHANG, J.M YEH. Advanced Anticorrosive Coa-tings Prepared from Polymer-Clay Nanocomposite Materials, Advances in Nanocomposites - Synthesis, Characterization and Industrial Applications, Boreddy Reddy (Ed.), 2011, 582p, ISBN: 978-953-307-165-7[MIN-2012] J. MIN, J.H. PARK, H.K. SOHN, J.M. PARK, Synergistic effect of potassium metal siliconate on silicate conversion coating for corrosion protection of galvanized steel, Journal of Industrial and Engineering Chemistry, 18 (2), p.655-660, Mar 2012[NEM-2010] M.NEMATOLLAHI, M.HEIDARIAN, M.PEIKARI, S.M. KASSIRIHA, N.ARIANPOUYA and M.ESMAEILPOUR, Comparison between the effect of nanoglass flake and montmorillo-niteorganoclay on corrosion performance of epoxy coating, Corrosion Science, 2010, vol 52, n°5, page 1809-1817, ISSN 0010-938X[RON-2011] Z. RONG, J. YEHUA, F. YUNYING, New Passivating Method to Galvanized Zn Coa-tings on Steel Substrate, Advanced Materials Research, 2011, Vols. 163-167, p 4555-4558.[SAI- 2012] SAINT GOBAIN, Saint Gobain Canalizacao, available at http://www.saint-gobain-canali¬zacao.com.br/ln_predial/smuconex.asp?lng=eng, date : fevrier 2012[SAN-2005] T.S.N. SANKARA NARAYANAN, surface pretreatment by phosphate conversion coatings - a review, India : National Metallurgical Laboratory, Madras Centre CSIR, April 22, 2005, 48 pages[TOT-2007] H. TO THI XUAN, T.A. TRUC, T.H. NAM, V.K OANH, J.B. JORCIN, N. PÉBÈRE, Corrosion protection of carbon steel by an epoxy resin containing organically modified clay, Surface & Coatings Technology, 2007, No 201, p 7408-7415, ISSN : 7408–7415[VOL-2002] C. Volzone, J. O. Rinaldi, J. Ortiga, N2 and CO2 Adsorption by TMA- and HDP-Montmorillonites,Materials Research, 2002, volume 5, n°4, p 475-479, ISSN 1516-1439[ZHO-2011] Z. Zhongli, L. Ning, L. Deyu, L. Haiping, M. Songlin, A vanadium-based conver-sion coating as chromate replacement for electrogalvanized steel substrates, Journal of Alloys and Compounds, 2011, No 509 ,p 503-507, ISSN: 0925-8388

35

Other references that we consultedActuAl SurfAce treAtmentS

• G. BERANGER, H. MAZILLE, Revêtements et traitements de surface, approche technologique, Techniques de l’ingénieur, 8 fév. 2012, Référence M1426 (base documentaire Traitements de sur-face des métaux : contexte et gestion environnementale/ Référence 7200076539).

• FENGGEGAO, B. HULL, Nanocomposites. Patent No US 6,835,766 B1; Dec.28, 2004• S. HUA, G. XIAOFEI,W. YUE, Comparative Research on Properties of Trivalent and Hexavalent Pas-

sive Film on Galvanized steel, Advanced Materials Research, 2012, Vols. 396-398, p 1760-1763.• W. LIN, L. MIN, L. YUPENG, The electrochemical behavior and microstructure of chromium-free

passivation film on Galvanized steel, Advanced Materials Research, 2011, Vols. 150-151, p 947-950.• S. HUA, G. XIAOFEI,W. YUE, Comparative Research on Properties of Trivalent and Hexavalent Pas-

sive Film on Galvanized steel, Advanced Materials Research, 2012, Vols. 396-398, p 1760-1763.• A. SHANAGHI, A. R. SABOUR, T. SHAHRABI, and M. ALIOFKHAZRAEE, Protection of Metals and

Physical Chemistry of Surfaces, 2009, Vol. 45, No. 3, pp. 305–311, ISSN 2070-2051• F. YANG, H. WU, Synergistic Corrosion Resistance of Cerium Film and Silane Film on Hot-dip Gal-

vanized Steel.Applied Mechanics and Materials, 2010, Vols. 34-35, p 2021-2025.

corroSion inhibitorS

• B. BUSCH, M. OLDSBERG, Galvanized steel corrosion inhibitor”. Patent 5.407.597. April 18, 1995• MC MURRAY, N.W. HAMILTON , D. ANTHONY . Corrosion inhibitors. WO/2002/008345 (A1).

01/31/2002.

VAnAdium conVerSion coAting

• T.W. CAPE, “Process and composition for sealing a conversion coated surface with a solution containing vanadium .” Patent number 4.828.615. May 9, 1989

montmorillonite conVerSion coAting

• E. GIMENEZ TORRES ET AL, Polymeric Matrix Nanocomposite Materials Having Improved Mecha-nical and Barrier Properties and Procedure for Preparing Same, Patent No 20110288224; Septem-ber 24, 2011

• KWONG, Process for producing advanced ceramics. Patent No 5,552,353; Sep.3, 1996• SHMUELKENING, Anti-corrosive paintings and coatings containing nanoparticles. Patent No

20110294918; Jan.12, 2011• UPULNISHANTHARATNAYAKE ET AL, Process for making reinforcing elastomer-clay nanocompo-

sites. Patent No 20120004347; Jan.05,2012• L. YING-MAN ET AL, Anticorrosive Nanocomposite Coating Material, and a preparation process

Thereof. Patent No 20100305235; Dec.02, 2010

36

Annex 1 : Experimental protocole• IntroductionWe tested the three more effcient coatings presented in the article that we studied . The aim of this manipulation is to know if there is a passivation of the samples for high poten-tials.Our three coatings were : 1 - Phytic acid + DMP (P=97,0%)2 - DMP (P=96,9%)3 - Phytic acid + Mn2+ + DTOA (P=97,9%)

The pretreatment of the sample will be done with sulfuric acid, which is shown as the more efficient in the article.

• Equipment- Samples of galvanized and phosphated plates sent by Tata Steel- Three electrodes cell :-Potentiostat - Work sample- Conter electrode in platinum - Reference calomel electrode- Acquisition software - Drying system with warm air- pH paper- Glassware- Exhaust hood- Kab Caot, gloves, protection glasses

• Chemicals- Distilted water- Ethanol- n-propanol- Sulfuric acid (H2SO4) : 0,05M- Hydrogen peroxide (H2O2) : 35 wt. % in H2O - Phytic acid (inositolhexaphosphoricacid) : 50% in H2O - Monohydrated Manganese Sulfate (MnSO4.H2O) - 2,3 dimercapto-1-propanol (DMP) : 5 mL

- Dithio-oxamide (DTAO) : 5 gr- KOH solution (pas de spécification)- NaCl solution : 0,5 M

• SecuritySee annexes 3 to 8

• PreparationWe prepare the following dilutions, the vo-lumes hve to be definied depending on the quantity that we need for our samples, H2SO4 : 0,05M (1) H2O2 : 0,5% (2) Phytic acid : 0,5 mM : pH has to be adjusted at 4 with the KOH solution (thanks to the pH paper) MnSO4 : 1 mM DMP : 0,1 mM : dilution in distilled water with 5% of ethanol DTOA : 0,1 mM : dilution in distilled water with 5% of ethanolMix M= (1) + (2)

• ManipulationAt first, the sample is cleaned with distilled water and ethanol. Then it is dryed with warm air and bathed in the mix M for 10 s, then it is again cleaned and dryed like before. The sample will now follow the steps explai-ned in the precedent table.We will plot the polarisation curves and impe-dance curves for each one of these samples. The electrolyte is a NaCl solution which concentration is 0.5M. We will mesure the corrosion potential, the corrosion curves will be plot between -150mV and +300mV in order to know if there is a passivation plateau.Other samples with scratches will be sub-merged in the NaCl electrolyte for a couple of days in order to observe if the rust develops inside the scratches.

Coating Pretratments First Bath time Second Bath time

A Phytic acid + DMP Pretreatment Phytic acid 30s DMP 60s

B DMP Pretreatment DMP 60s

C Phytic acid + Mn2+ + DTOA Pretreatment Phytic acid +

MnSO4 30s DTOA 60s

37

Annex 2 : Difficulties during experimentations

The dilutions were our first stepand were supposed to be done quickly, but apparently things never turn out the way it is written on the paper.

1-Dilution of DTOA and MnSO4 in n-propanol and distilled water:

We obtained an orange-red solution. The DTOA, which is basically powder didn’t dis-solve totally. We still had DTOA flakes in the solution. In order to help it dissolve, knowing that our efforts shaking it up were useless, we tried to heat it and stir at the same time. At 50°C we didn’t see any improvement.We made a second dilution with ten times less DTOA powder to see if it could help it to dis-solve in the same volume of water and n-propanol. It didn’t work either. So at last, we decided to make a third solution with the same amount of DTOA as in the second one but dissolving it first just in the n-propanol. It did dissolve after half an hour of stirring and heating. Afterwards we added the dis-tilled water and we were pleased to see that the DTOA was still dissolved. We could finally continue the dissolution, adapting naturally the volumes to the difference of weight we had at the beginning of the third and last try of dilution.

2-Dilution of DMP in ethanol and distilled water:

The DMP which appeared to be a very viscous liquid didn’t dissolve in the solution at all. We tried to shake it up as much as we could but it didn’t help. As we didn’t have much of DMP we waited a while before trying another dilu-tion. Once we saw that the DTOA had dissolved in the n-propanol we gave the DMP a try and mixed it only with the ethanol. It worked, the DMP dissolved and so we knew that we could eventually complete the dilution and obtain the right solution in the end.

3-Dilution of the phytic acid in distilled water.

For this one we had no problem dissolving it. The problems began when we tried to buf-fer it with KOH in order to increase its pH till 4. It didn’t work with the volume we had so we decided to split the volume in 2, keeping the proportions, and to add KOH to half of the volume till we reached the wanted pH. It worked.

At this point we were finally ready to start pretreating and bathing our galvanized steel samples.

38

Annex 3 : Technical specifications of Cloisite 30B

Sout

hern

Cla

y Pr

oduc

ts, I

nc.

1212

Chu

rch

Stre

et

Gon

zale

s, T

X 78

629

Ph

one:

800

-324

-289

1

Fax:

830

-672

-190

3

ww

w.s

cpro

d.co

m

Clo

isite

® 3

0B

Typ

ical

Phy

sica

l Pro

pert

ies

Bul

letin

Des

crip

tion:

C

lois

ite®

30B

is a

nat

ural

mon

tmor

illoni

te m

odifi

ed w

ith a

qua

tern

ary

amm

oniu

m s

alt.

Des

igne

d U

sed:

C

lois

ite®

30B

is a

n ad

ditiv

e fo

r pla

stic

s an

d ru

bber

s to

impr

ove

vario

us p

hysi

cal

prop

ertie

s, s

uch

as re

info

rcem

ent,

CLT

E, s

yner

gist

ic fl

ame

reta

rdan

t and

bar

rier.

Typi

cal P

rope

rtie

s:

Trea

tmen

t/Pro

perti

es:

Org

anic

M

odifi

er (1

)M

odifi

er

Con

cent

ratio

n %

M

oist

ure

% W

eigh

t Lo

ss o

n Ig

nitio

n C

lois

ite®

30B

M

T2E

tOH

90

meq

/100

g cl

ay<

2%

30%

CH

2CH

2OH

|

CH

3 ─ N

+ ─ T

|

C

H2C

H2O

H

W

here

T is

Tal

low

(~65

% C

18; ~

30%

C16

; ~5%

C14

)

Ani

on: C

hlor

ide

(1) M

T2E

tOH

: m

ethy

l, ta

llow

, bis

-2-h

ydro

xyet

hyl,

quat

erna

ry a

mm

oniu

m

Typi

cal D

ry P

artic

le S

izes

: (m

icro

ns, b

y vo

lum

e)

10%

less

than

: 50

% le

ss th

an:

90%

less

than

: 2µ

m

6µm

13

µm

Col

or:

Off

Whi

te

Den

sity

:

Loos

e B

ulk,

lbs/

ft3 P

acke

d B

ulk,

lbs/

ft3 D

ensi

ty, g

/cc

14.2

5 22

.71

1.98

X

Ray

Res

ults

: d 0

01 =

18.

5Å

Fo

r add

ition

al in

form

atio

n or

tech

nica

l ass

ista

nce

cont

act S

outh

ern

Cla

y P

rodu

cts,

Inc.

to

ll fre

e at

800

-324

-289

1.

Dis

clai

mer

of W

arra

nty:

The

info

rmat

ion

pres

ente

d he

rein

is b

elie

ved

to b

e ac

cura

te b

ut is

not

to b

e ta

ken

as a

war

rant

y, g

uara

ntee

, or

repr

esen

tatio

n fo

r whi

ch w

e as

sum

e le

gal r

espo

nsib

ility

. Thi

s in

form

atio

n do

es n

ot g

rant

per

mis

sion

, lic

ense

, or a

ny ri

ghts

or

reco

mm

enda

tions

to p

ract

ice

any

form

of p

ropr

ieta

ry in

telle

ctua

l pro

perty

with

out o

btai

ning

the

appr

opria

te li

cens

e or

gra

nt fr

om th

e pr

oper

ty o

wne

r. Th

e in

form

atio

n is

offe

red

sole

ly fo

r you

r con

side

ratio

n, in

vest

igat

ion

and

verif

icat

ion,

but

you

mus

t det

erm

ine

the

suita

bilit

y of

the

prod

uct f

or y

our s

peci

fic a

pplic

atio

n. T

he p

urch

aser

ass

umes

all

risk

of u

se o

f han

dlin

g th

e m

ater

ial,

incl

udin

g bu

t not

lim

ited

to tr

ansf

errin

g th

e m

ater

ial w

ithin

pur

chas

er's

faci

litie

s, u

sing

the

mat

eria

l in

appl

icat

ions

spe

cifie

d by

the

purc

hase

r and

ha

ndlin

g an

y pr

oduc

t whi

ch in

clud

es th

e m

ater

ial,

whe

ther

or n

ot in

acc

orda

nce

with

any

sta

tem

ents

mad

e he

rein

.

39

Annex 2 : Technical specifications of Cloisite Na+S

ou

the

rn C

lay

Pro

du

cts

, Inc

.1

21

2 C

hu

rch

Stre

et

Go

nza

les

, TX

78

62

9P

ho

ne

: 80

0-3

24

-28

91

Fa

x: 8

30

-67

2-1

90

3

ww

w.s

cp

rod

.co

m

Clo

isite

® N

a+

Ty

pic

al P

hy

sic

al P

rop

ertie

s B

ulle

tin

Descrip

tion

:C

loisite

® N

a+ is a

natu

ral m

ontm

orillo

nite

.

Desig

ned

Used

:C

loisite

® N

a+ is a

n a

dditive

for p

lastics to

impro

ve va

rious p

lastic p

hysica

l pro

pertie

s,su

ch a

s rein

force

ment, H

DT

, CLT

E a

nd b

arrie

r.

Typ

ical P

rop

ertie

s:

Tre

atm

ent/P

ropertie

s:O

rganic

Modifie

rM

odifie

rC

once

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40

Annex 3 : MSDS of Hydrogen Peroxyde

Sigma-Aldrich - 349887 Page 2 of 7

contact lenses, if present and easy to do. Continue rinsing. Supplemental Hazard Statements

none

According to European Directive 67/548/EEC as amended. Hazard symbol(s)

R-phrase(s) R22 Harmful if swallowed. R37/38 Irritating to respiratory system and skin. R41 Risk of serious damage to eyes. S-phrase(s) S26 In case of contact with eyes, rinse immediately with plenty of water and

seek medical advice. S39 Wear eye/face protection.

2.3 Other hazards - none 3. COMPOSITION/INFORMATION ON INGREDIENTS

3.2 Mixtures Molecular Weight : 34,01 g/mol Component Classification Concentration

Hydrogen peroxide CAS-No.

EC-No. Index-No.

7722-84-1 231-765-0 008-003-00-9

Ox. Liq. 1; Acute Tox. 4; Skin Corr. 1A; H271, H302, H314, H332 O, C, R 5 - R 8 - R20/22 - R35

35 - 50 %

For the full text of the H-Statements and R-Phrases mentioned in this Section, see Section 16 4. FIRST AID MEASURES

4.1 Description of first aid measures

General advice Consult a physician. Show this safety data sheet to the doctor in attendance.

If inhaled If breathed in, move person into fresh air. If not breathing, give artificial respiration. Consult a physician.

In case of skin contact Take off contaminated clothing and shoes immediately. Wash off with soap and plenty of water. Consult a physician.

In case of eye contact Rinse thoroughly with plenty of water for at least 15 minutes and consult a physician.

If swallowed Do NOT induce vomiting. Never give anything by mouth to an unconscious person. Rinse mouth with water. Consult a physician.

4.2 Most important symptoms and effects, both acute and delayed To the best of our knowledge, the chemical, physical, and toxicological properties have not been thoroughly investigated.

4.3 Indication of any immediate medical attention and special treatment needed no data available

Sigma-Aldrich - 349887 Page 1 of 7

SIGMA-ALDRICH sigma-aldrich.com SAFETY DATA SHEET

according to Regulation (EC) No. 1907/2006 Version 3.3 Revision Date 11.01.2012

Print Date 14.03.2012 GENERIC EU MSDS - NO COUNTRY SPECIFIC DATA - NO OEL DATA

1. IDENTIFICATION OF THE SUBSTANCE/MIXTURE AND OF THE COMPANY/UNDERTAKING

1.1 Product identifiers Product name : Hydrogen peroxide solution, 35 wt.%

Product Number : 349887 Brand : Sigma-Aldrich

1.2 Relevant identified uses of the substance or mixture and uses advised against

Identified uses : Laboratory chemicals, Manufacture of substances

1.3 Details of the supplier of the safety data sheet

Company : Sigma-Aldrich Chimie S.a.r.l L'Isle D'Abeau Chesnes F-38297 ST. QUENTIN FALLAVIER

Telephone : +33 (0)4 74 82 28 40 Fax : +33 (0)4 74 95 68 08 E-mail address : eurtechserv@sial.com

1.4 Emergency telephone number

Emergency Phone # : I.N.R.S.:+33 (0)1 45 42 59 59 2. HAZARDS IDENTIFICATION

2.1 Classification of the substance or mixture

Classification according to Regulation (EC) No 1272/2008 [EU-GHS/CLP] Oxidizing liquids (Category 2) Acute toxicity, Oral (Category 4) Skin irritation (Category 2) Serious eye damage (Category 1) Specific target organ toxicity - single exposure (Category 3)

Classification according to EU Directives 67/548/EEC or 1999/45/EC Harmful if swallowed. Risk of serious damage to eyes. Irritating to respiratory system and skin.

2.2 Label elements

Labelling according Regulation (EC) No 1272/2008 [CLP] Pictogram

Signal word Danger Hazard statement(s) H272 May intensify fire; oxidiser. H302 Harmful if swallowed. H315 Causes skin irritation. H318 Causes serious eye damage. H335 May cause respiratory irritation. Precautionary statement(s) P220 Keep/Store away from clothing/ combustible materials. P261 Avoid breathing dust/ fume/ gas/ mist/ vapours/ spray. P280 Wear protective gloves/ eye protection/ face protection. P305 + P351 + P338 IF IN EYES: Rinse cautiously with water for several minutes. Remove

Sigma-Aldrich - 349887 Page 3 of 7

5. FIREFIGHTING MEASURES

5.1 Extinguishing media

Suitable extinguishing media Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide.

5.2 Special hazards arising from the substance or mixture Oxygen Nature of decomposition products not known.

5.3 Advice for firefighters Wear self contained breathing apparatus for fire fighting if necessary.

5.4 Further information Use water spray to cool unopened containers.

6. ACCIDENTAL RELEASE MEASURES

6.1 Personal precautions, protective equipment and emergency procedures Use personal protective equipment. Avoid breathing vapors, mist or gas. Ensure adequate ventilation. Evacuate personnel to safe areas.

6.2 Environmental precautions Prevent further leakage or spillage if safe to do so. Do not let product enter drains. Discharge into the environment must be avoided.

6.3 Methods and materials for containment and cleaning up Contain spillage, and then collect with an electrically protected vacuum cleaner or by wet-brushing and place in container for disposal according to local regulations (see section 13).

6.4 Reference to other sections For disposal see section 13.

7. HANDLING AND STORAGE

7.1 Precautions for safe handling Avoid contact with skin and eyes. Avoid inhalation of vapour or mist. Keep away from sources of ignition - No smoking.Keep away from heat and sources of ignition.

7.2 Conditions for safe storage, including any incompatibilities Store in cool place. Keep container tightly closed in a dry and well-ventilated place. Containers which are opened must be carefully resealed and kept upright to prevent leakage.

Recommended storage temperature: 2 - 8 °C

7.3 Specific end uses no data available

8. EXPOSURE CONTROLS/PERSONAL PROTECTION

8.1 Control parameters

Components with workplace control parameters

8.2 Exposure controls

Appropriate engineering controls Handle in accordance with good industrial hygiene and safety practice. Wash hands before breaks and at the end of workday.

Personal protective equipment

Eye/face protection Tightly fitting safety goggles. Faceshield (8-inch minimum). Use equipment for eye protection tested and approved under appropriate government standards such as NIOSH (US) or EN 166(EU).

Sigma-Aldrich - 349887 Page 4 of 7

Skin protection Handle with gloves. Gloves must be inspected prior to use. Use proper glove removal technique (without touching glove's outer surface) to avoid skin contact with this product. Dispose of contaminated gloves after use in accordance with applicable laws and good laboratory practices. Wash and dry hands. The selected protective gloves have to satisfy the specifications of EU Directive 89/686/EEC and the standard EN 374 derived from it. Body Protection Complete suit protecting against chemicals, The type of protective equipment must be selected according to the concentration and amount of the dangerous substance at the specific workplace.

Respiratory protection Where risk assessment shows air-purifying respirators are appropriate use a full-face respirator with multi-purpose combination (US) or type ABEK (EN 14387) respirator cartridges as a backup to engineering controls. If the respirator is the sole means of protection, use a full-face supplied air respirator. Use respirators and components tested and approved under appropriate government standards such as NIOSH (US) or CEN (EU).

9. PHYSICAL AND CHEMICAL PROPERTIES

9.1 Information on basic physical and chemical properties a) Appearance Form: liquid, clear

Colour: colourless

b) Odour no data available

c) Odour Threshold no data available

d) pH no data available

e) Melting point/freezing point

-40 °C

f) Initial boiling point and boiling range

126 °C at 1.013 hPa

g) Flash point no data available

h) Evaporation rate no data available

i) Flammability (solid, gas) no data available

j) Upper/lower flammability or explosive limits

no data available

k) Vapour pressure 31,1 hPa at 30 °C

l) Vapour density 1,17 - (Air = 1.0)

m) Relative density 1,130 g/cm3

n) Water solubility no data available

o) Partition coefficient: n-octanol/water

no data available

p) Autoignition temperature

no data available

q) Decomposition temperature

no data available

r) Viscosity no data available

s) Explosive properties no data available

t) Oxidizing properties The substance or mixture is classified as oxidizing with the category 2.

9.2 Other safety information no data available

41

Sigma-Aldrich - 349887 Page 6 of 7

12. ECOLOGICAL INFORMATION

12.1 Toxicity no data available

12.2 Persistence and degradability no data available

12.3 Bioaccumulative potential no data available

12.4 Mobility in soil no data available

12.5 Results of PBT and vPvB assessment no data available

12.6 Other adverse effects Harmful to aquatic life.

13. DISPOSAL CONSIDERATIONS

13.1 Waste treatment methods

Product Burn in a chemical incinerator equipped with an afterburner and scrubber but exert extra care in igniting as this material is highly flammable. Offer surplus and non-recyclable solutions to a licensed disposal company.

Contaminated packaging Dispose of as unused product.

14. TRANSPORT INFORMATION

14.1 UN number ADR/RID: 2014 IMDG: 2014 IATA: 2014

14.2 UN proper shipping name ADR/RID: HYDROGEN PEROXIDE, AQUEOUS SOLUTION IMDG: HYDROGEN PEROXIDE, AQUEOUS SOLUTION IATA: Hydrogen peroxide, aqueous solution

14.3 Transport hazard class(es) ADR/RID: 5.1 (8) IMDG: 5.1 (8) IATA: 5.1 (8)

14.4 Packaging group ADR/RID: II IMDG: II IATA: II

14.5 Environmental hazards ADR/RID: no IMDG Marine pollutant: no IATA: no

14.6 Special precautions for user no data available

15. REGULATORY INFORMATION

This safety datasheet complies with the requirements of Regulation (EC) No. 1907/2006.

15.1 Safety, health and environmental regulations/legislation specific for the substance or mixture no data available

15.2 Chemical Safety Assessment no data available

16. OTHER INFORMATION

Text of H-code(s) and R-phrase(s) mentioned in Section 3

Acute Tox. Acute toxicity

Sigma-Aldrich - 349887 Page 5 of 7

10. STABILITY AND REACTIVITY

10.1 Reactivity no data available

10.2 Chemical stability no data available

10.3 Possibility of hazardous reactions no data available

10.4 Conditions to avoid no data available

10.5 Incompatible materials Brass, Copper, Powdered metals, Iron, Iron and iron salts.

10.6 Hazardous decomposition products Other decomposition products - no data available

11. TOXICOLOGICAL INFORMATION

11.1 Information on toxicological effects

Acute toxicity no data available

Skin corrosion/irritation no data available

Serious eye damage/eye irritation no data available

Respiratory or skin sensitization no data available

Germ cell mutagenicity no data available

Carcinogenicity

IARC: 3 - Group 3: Not classifiable as to its carcinogenicity to humans (Hydrogen peroxide)

Reproductive toxicity no data available

Specific target organ toxicity - single exposure no data available

Specific target organ toxicity - repeated exposure no data available

Aspiration hazard no data available

Potential health effects

Inhalation May be harmful if inhaled. Material is extremely destructive to the tissue of the mucous membranes and upper respiratory tract.

Ingestion Harmful if swallowed. Causes burns. Skin May be harmful if absorbed through skin. Causes skin burns. Eyes Causes eye burns.

Signs and Symptoms of Exposure To the best of our knowledge, the chemical, physical, and toxicological properties have not been thoroughly investigated.

Additional Information RTECS: Not available

Sigma-Aldrich - 349887 Page 7 of 7

H271 May cause fire or explosion; strong oxidiser. H302 Harmful if swallowed. H314 Causes severe skin burns and eye damage. H332 Harmful if inhaled. Ox. Liq. Oxidizing liquids Skin Corr. Skin corrosion C Corrosive R 5 Heating may cause an explosion. R 8 Contact with combustible material may cause fire. R20/22 Harmful by inhalation and if swallowed. O Oxidising R35 Causes severe burns.

Further information Copyright 2012 Sigma-Aldrich Co. LLC. License granted to make unlimited paper copies for internal use only. The above information is believed to be correct but does not purport to be all inclusive and shall be used only as a guide. The information in this document is based on the present state of our knowledge and is applicable to the product with regard to appropriate safety precautions. It does not represent any guarantee of the properties of the product. Sigma-Aldrich Co., shall not be held liable for any damage resulting from handling or from contact with the above product. See reverse side of invoice or packing slip for additional terms and conditions of sale.

42

Annex 4 : MSDS of Manganese (II) Sulfate Monohydrate

Sigma-Aldrich - M7634 Page 3 of 7

5.2 Special hazards arising from the substance or mixture Sulphur oxides, Manganese/manganese oxides

5.3 Advice for firefighters Wear self contained breathing apparatus for fire fighting if necessary.

5.4 Further information no data available

6. ACCIDENTAL RELEASE MEASURES

6.1 Personal precautions, protective equipment and emergency procedures Use personal protective equipment. Avoid dust formation. Avoid breathing vapors, mist or gas. Ensure adequate ventilation. Evacuate personnel to safe areas. Avoid breathing dust.

6.2 Environmental precautions Prevent further leakage or spillage if safe to do so. Do not let product enter drains. Discharge into the environment must be avoided.

6.3 Methods and materials for containment and cleaning up Pick up and arrange disposal without creating dust. Sweep up and shovel. Keep in suitable, closed containers for disposal.

6.4 Reference to other sections For disposal see section 13.

7. HANDLING AND STORAGE

7.1 Precautions for safe handling Avoid contact with skin and eyes. Avoid formation of dust and aerosols. Provide appropriate exhaust ventilation at places where dust is formed.

7.2 Conditions for safe storage, including any incompatibilities Store in cool place. Keep container tightly closed in a dry and well-ventilated place.

Keep in a dry place.

7.3 Specific end uses no data available

8. EXPOSURE CONTROLS/PERSONAL PROTECTION

8.1 Control parameters

Components with workplace control parameters

8.2 Exposure controls

Appropriate engineering controls Handle in accordance with good industrial hygiene and safety practice. Wash hands before breaks and at the end of workday.

Personal protective equipment

Eye/face protection Safety glasses with side-shields conforming to EN166 Use equipment for eye protection tested and approved under appropriate government standards such as NIOSH (US) or EN 166(EU).

Skin protection Handle with gloves. Gloves must be inspected prior to use. Use proper glove removal technique (without touching glove's outer surface) to avoid skin contact with this product. Dispose of contaminated gloves after use in accordance with applicable laws and good laboratory practices. Wash and dry hands. The selected protective gloves have to satisfy the specifications of EU Directive 89/686/EEC and the standard EN 374 derived from it. Body Protection Complete suit protecting against chemicals, The type of protective equipment must be selected according to the concentration and amount of the dangerous substance at the specific workplace.

Sigma-Aldrich - M7634 Page 4 of 7

Respiratory protection For nuisance exposures use type P95 (US) or type P1 (EU EN 143) particle respirator.For higher level protection use type OV/AG/P99 (US) or type ABEK-P2 (EU EN 143) respirator cartridges. Use respirators and components tested and approved under appropriate government standards such as NIOSH (US) or CEN (EU).

9. PHYSICAL AND CHEMICAL PROPERTIES

9.1 Information on basic physical and chemical properties a) Appearance Form: powder

Colour: light red

b) Odour no data available

c) Odour Threshold no data available

d) pH 3,0 - 3,5 at 50 g/l at 20 °C

e) Melting point/freezing point

700 °C

f) Initial boiling point and boiling range

no data available

g) Flash point no data available

h) Evaporation rate no data available

i) Flammability (solid, gas) no data available

j) Upper/lower flammability or explosive limits

no data available

k) Vapour pressure no data available

l) Vapour density no data available

m) Relative density 2,95 g/cm3

n) Water solubility no data available

o) Partition coefficient: n-octanol/water

no data available

p) Autoignition temperature

no data available

q) Decomposition temperature

no data available

r) Viscosity no data available

s) Explosive properties no data available

t) Oxidizing properties no data available

9.2 Other safety information Bulk density 1 - 1,2 kg/m3

10. STABILITY AND REACTIVITY

10.1 Reactivity no data available

10.2 Chemical stability no data available

10.3 Possibility of hazardous reactions no data available

10.4 Conditions to avoid Avoid moisture.

Sigma-Aldrich - M7634 Page 1 of 7

SIGMA-ALDRICH sigma-aldrich.com SAFETY DATA SHEET

according to Regulation (EC) No. 1907/2006 Version 4.1 Revision Date 09.01.2012

Print Date 14.03.2012 GENERIC EU MSDS - NO COUNTRY SPECIFIC DATA - NO OEL DATA

1. IDENTIFICATION OF THE SUBSTANCE/MIXTURE AND OF THE COMPANY/UNDERTAKING

1.1 Product identifiers Product name : Manganese(II) sulfate monohydrate

Product Number : M7634 Brand : Sigma-Aldrich Index-No. : 025-003-00-4 CAS-No. : 10034-96-5

1.2 Relevant identified uses of the substance or mixture and uses advised against

Identified uses : Laboratory chemicals, Manufacture of substances

1.3 Details of the supplier of the safety data sheet

Company : Sigma-Aldrich Chimie S.a.r.l L'Isle D'Abeau Chesnes F-38297 ST. QUENTIN FALLAVIER

Telephone : +33 (0)4 74 82 28 40 Fax : +33 (0)4 74 95 68 08 E-mail address : eurtechserv@sial.com

1.4 Emergency telephone number

Emergency Phone # : I.N.R.S.:+33 (0)1 45 42 59 59 2. HAZARDS IDENTIFICATION

2.1 Classification of the substance or mixture

Classification according to Regulation (EC) No 1272/2008 [EU-GHS/CLP] Specific target organ toxicity - repeated exposure (Category 2) Chronic aquatic toxicity (Category 2)

Classification according to EU Directives 67/548/EEC or 1999/45/EC Toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment. Harmful: danger of serious damage to health by prolonged exposure through inhalation and if swallowed.

2.2 Label elements

Labelling according Regulation (EC) No 1272/2008 [CLP] Pictogram

Signal word Warning Hazard statement(s) H373 May cause damage to organs through prolonged or repeated exposure. H411 Toxic to aquatic life with long lasting effects. Precautionary statement(s) P273 Avoid release to the environment. Supplemental Hazard Statements

none

According to European Directive 67/548/EEC as amended. Hazard symbol(s)

Sigma-Aldrich - M7634 Page 2 of 7

R-phrase(s) R48/20/22 Harmful: danger of serious damage to health by prolonged exposure

through inhalation and if swallowed. R51/53 Toxic to aquatic organisms, may cause long-term adverse effects in the

aquatic environment. S-phrase(s) S22 Do not breathe dust. S61 Avoid release to the environment. Refer to special instructions/ Safety

data sheets.

2.3 Other hazards - none 3. COMPOSITION/INFORMATION ON INGREDIENTS

3.1 Substances Formula : MnO4S · H2O Molecular Weight : 169,02 g/mol Component Concentration

Manganese Sulfate Monohydrate CAS-No.

EC-No. Index-No.

10034-96-5 232-089-9 025-003-00-4

-

4. FIRST AID MEASURES

4.1 Description of first aid measures

General advice Consult a physician. Show this safety data sheet to the doctor in attendance.

If inhaled If breathed in, move person into fresh air. If not breathing, give artificial respiration. Consult a physician.

In case of skin contact Wash off with soap and plenty of water. Consult a physician.

In case of eye contact Flush eyes with water as a precaution.

If swallowed Never give anything by mouth to an unconscious person. Rinse mouth with water. Consult a physician.

4.2 Most important symptoms and effects, both acute and delayed Men exposed to manganese dusts showed a decrease in fertility. Chronic manganese poisoning primarily involves the central nervous system. Early symptoms include languor, sleepiness and weakness in the legs. A stolid mask-like appearance of the face, emotional disturbances such as uncontrollable laughter and a spastic gait with tendency to fall in walking are findings in more advanced cases. High incidence of pneumonia has been found in workers exposed to the dust or fume of some manganese compounds., Prolonged or repeated inhalation may cause:, Pneumonia

4.3 Indication of any immediate medical attention and special treatment needed no data available

5. FIREFIGHTING MEASURES

5.1 Extinguishing media

Suitable extinguishing media Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide.

43

Sigma-Aldrich - M7634 Page 6 of 7

and a spastic gait with tendency to fall in walking are findings in more advanced cases. High incidence of pneumonia has been found in workers exposed to the dust or fume of some manganese compounds., Prolonged or repeated inhalation may cause:, Pneumonia

Additional Information RTECS: OP0893500

12. ECOLOGICAL INFORMATION

12.1 Toxicity no data available

12.2 Persistence and degradability no data available

12.3 Bioaccumulative potential no data available

12.4 Mobility in soil no data available

12.5 Results of PBT and vPvB assessment no data available

12.6 Other adverse effects Toxic to aquatic life. Toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment. Toxic to aquatic life.

13. DISPOSAL CONSIDERATIONS

13.1 Waste treatment methods

Product Offer surplus and non-recyclable solutions to a licensed disposal company. Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber.

Contaminated packaging Dispose of as unused product.

14. TRANSPORT INFORMATION

14.1 UN number ADR/RID: 3077 IMDG: 3077 IATA: 3077

14.2 UN proper shipping name ADR/RID: ENVIRONMENTALLY HAZARDOUS SUBSTANCE, SOLID, N.O.S. (Manganese Sulfate

Monohydrate) IMDG: ENVIRONMENTALLY HAZARDOUS SUBSTANCE, SOLID, N.O.S. (Manganese Sulfate

Monohydrate) IATA: Environmentally hazardous substance, solid, n.o.s. (Manganese Sulfate Monohydrate)

14.3 Transport hazard class(es) ADR/RID: 9 IMDG: 9 IATA: 9

14.4 Packaging group ADR/RID: III IMDG: III IATA: III

14.5 Environmental hazards ADR/RID: yes IMDG Marine pollutant: yes IATA: yes

14.6 Special precautions for user

Further information EHS-Mark required (ADR 2.2.9.1.10, IMDG code 2.10.3) for single packagings and combination packagings containing inner packagings with Dangerous Goods > 5L for liquids or > 5kg for solids.

Sigma-Aldrich - M7634 Page 7 of 7

15. REGULATORY INFORMATION

This safety datasheet complies with the requirements of Regulation (EC) No. 1907/2006.

15.1 Safety, health and environmental regulations/legislation specific for the substance or mixture no data available

15.2 Chemical Safety Assessment no data available

16. OTHER INFORMATION

Further information Copyright 2012 Sigma-Aldrich Co. License granted to make unlimited paper copies for internal use only. The above information is believed to be correct but does not purport to be all inclusive and shall be used only as a guide. The information in this document is based on the present state of our knowledge and is applicable to the product with regard to appropriate safety precautions. It does not represent any guarantee of the properties of the product. Sigma-Aldrich Co., shall not be held liable for any damage resulting from handling or from contact with the above product. See reverse side of invoice or packing slip for additional terms and conditions of sale.

Sigma-Aldrich - M7634 Page 5 of 7

10.5 Incompatible materials no data available

10.6 Hazardous decomposition products Other decomposition products - no data available

11. TOXICOLOGICAL INFORMATION

11.1 Information on toxicological effects

Acute toxicity Harmful: danger of serious damage to health by prolonged exposure if swallowed.

Skin corrosion/irritation no data available

Serious eye damage/eye irritation no data available

Respiratory or skin sensitization no data available

Germ cell mutagenicity

Genotoxicity in vitro - Hamster - ovary Cytogenetic analysis

Genotoxicity in vitro - Hamster - ovary Sister chromatid exchange

Genotoxicity in vivo - mouse - Oral Micronucleus test

Genotoxicity in vivo - mouse - Oral Cytogenetic analysis

Genotoxicity in vivo - mouse - Oral sperm

Carcinogenicity

Carcinogenicity - mouse - Oral Tumorigenic:Equivocal tumorigenic agent by RTECS criteria. Endocrine:Thyroid tumors.

IARC: No component of this product present at levels greater than or equal to 0.1% is identified as probable, possible or confirmed human carcinogen by IARC.

Reproductive toxicity

Reproductive toxicity - mouse - male - Oral Paternal Effects: Spermatogenesis (including genetic material, sperm morphology,motility, and count).

Specific target organ toxicity - single exposure no data available

Specific target organ toxicity - repeated exposure May cause damage to organs through prolonged or repeated exposure.

Aspiration hazard no data available

Potential health effects

Inhalation Harmful if inhaled. May cause respiratory tract irritation. Ingestion Harmful if swallowed. Skin Harmful if absorbed through skin. May cause skin irritation. Eyes May cause eye irritation.

Signs and Symptoms of Exposure Men exposed to manganese dusts showed a decrease in fertility. Chronic manganese poisoning primarily involves the central nervous system. Early symptoms include languor, sleepiness and weakness in the legs. A stolid mask-like appearance of the face, emotional disturbances such as uncontrollable laughter

44

Annex 5 : MSDS of Sulfuric acid

Aldrich - 339741 Page 1 of 7

SIGMA-ALDRICH sigma-aldrich.com SAFETY DATA SHEET

according to Regulation (EC) No. 1907/2006 Version 4.1 Revision Date 13.01.2012

Print Date 14.03.2012 GENERIC EU MSDS - NO COUNTRY SPECIFIC DATA - NO OEL DATA

1. IDENTIFICATION OF THE SUBSTANCE/MIXTURE AND OF THE COMPANY/UNDERTAKING

1.1 Product identifiers Product name : Sulfuric acid

Product Number : 339741 Brand : Aldrich Index-No. : 016-020-00-8 CAS-No. : 7664-93-9

1.2 Relevant identified uses of the substance or mixture and uses advised against

Identified uses : Laboratory chemicals, Manufacture of substances

1.3 Details of the supplier of the safety data sheet

Company : Sigma-Aldrich Chimie S.a.r.l L'Isle D'Abeau Chesnes F-38297 ST. QUENTIN FALLAVIER

Telephone : +33 (0)4 74 82 28 40 Fax : +33 (0)4 74 95 68 08 E-mail address : eurtechserv@sial.com

1.4 Emergency telephone number

Emergency Phone # : I.N.R.S.:+33 (0)1 45 42 59 59 2. HAZARDS IDENTIFICATION

2.1 Classification of the substance or mixture

Classification according to Regulation (EC) No 1272/2008 [EU-GHS/CLP] Skin corrosion (Category 1A)

Classification according to EU Directives 67/548/EEC or 1999/45/EC Causes severe burns.

2.2 Label elements

Labelling according Regulation (EC) No 1272/2008 [CLP] Pictogram

Signal word Danger Hazard statement(s) H314 Causes severe skin burns and eye damage. Precautionary statement(s) P280 Wear protective gloves/ protective clothing/ eye protection/ face

protection. P305 + P351 + P338 IF IN EYES: Rinse cautiously with water for several minutes. Remove

contact lenses, if present and easy to do. Continue rinsing. P310 Immediately call a POISON CENTER or doctor/ physician. Supplemental Hazard Statements

none

Aldrich - 339741 Page 2 of 7

According to European Directive 67/548/EEC as amended. Hazard symbol(s)

R-phrase(s) R35 Causes severe burns. S-phrase(s) S26 In case of contact with eyes, rinse immediately with plenty of water and

seek medical advice. S30 Never add water to this product. S45 In case of accident or if you feel unwell, seek medical advice immediately

(show the label where possible).

2.3 Other hazards - none 3. COMPOSITION/INFORMATION ON INGREDIENTS

3.1 Substances Formula : H2O4S Molecular Weight : 98,08 g/mol Component Concentration

Sulfuric acid CAS-No.

EC-No. Index-No.

7664-93-9 231-639-5 016-020-00-8

-

4. FIRST AID MEASURES

4.1 Description of first aid measures

General advice Consult a physician. Show this safety data sheet to the doctor in attendance.

If inhaled If breathed in, move person into fresh air. If not breathing, give artificial respiration. Consult a physician.

In case of skin contact Take off contaminated clothing and shoes immediately. Wash off with soap and plenty of water. Consult a physician.

In case of eye contact Rinse thoroughly with plenty of water for at least 15 minutes and consult a physician.

If swallowed Do NOT induce vomiting. Never give anything by mouth to an unconscious person. Rinse mouth with water. Consult a physician.

4.2 Most important symptoms and effects, both acute and delayed Material is extremely destructive to tissue of the mucous membranes and upper respiratory tract, eyes, and skin., spasm, inflammation and edema of the larynx, spasm, inflammation and edema of the bronchi, pneumonitis, pulmonary edema, burning sensation, Cough, wheezing, laryngitis, Shortness of breath, Headache, Nausea, Vomiting, Pulmonary edema. Effects may be delayed., To the best of our knowledge, the chemical, physical, and toxicological properties have not been thoroughly investigated.

4.3 Indication of any immediate medical attention and special treatment needed no data available

5. FIREFIGHTING MEASURES

5.1 Extinguishing media

Suitable extinguishing media Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide.

Aldrich - 339741 Page 3 of 7

5.2 Special hazards arising from the substance or mixture Sulphur oxides

5.3 Advice for firefighters Wear self contained breathing apparatus for fire fighting if necessary.

5.4 Further information no data available

6. ACCIDENTAL RELEASE MEASURES

6.1 Personal precautions, protective equipment and emergency procedures Use personal protective equipment. Avoid breathing vapors, mist or gas. Ensure adequate ventilation. Evacuate personnel to safe areas.

6.2 Environmental precautions Prevent further leakage or spillage if safe to do so. Do not let product enter drains. Discharge into the environment must be avoided.

6.3 Methods and materials for containment and cleaning up Soak up with inert absorbent material and dispose of as hazardous waste. Keep in suitable, closed containers for disposal.

6.4 Reference to other sections For disposal see section 13.

7. HANDLING AND STORAGE

7.1 Precautions for safe handling Avoid inhalation of vapour or mist.

7.2 Conditions for safe storage, including any incompatibilities Store in cool place. Keep container tightly closed in a dry and well-ventilated place. Containers which are opened must be carefully resealed and kept upright to prevent leakage.

7.3 Specific end uses no data available

8. EXPOSURE CONTROLS/PERSONAL PROTECTION

8.1 Control parameters

Components with workplace control parameters

8.2 Exposure controls

Appropriate engineering controls Handle in accordance with good industrial hygiene and safety practice. Wash hands before breaks and at the end of workday.

Personal protective equipment

Eye/face protection Tightly fitting safety goggles. Faceshield (8-inch minimum). Use equipment for eye protection tested and approved under appropriate government standards such as NIOSH (US) or EN 166(EU).

Skin protection Handle with gloves. Gloves must be inspected prior to use. Use proper glove removal technique (without touching glove's outer surface) to avoid skin contact with this product. Dispose of contaminated gloves after use in accordance with applicable laws and good laboratory practices. Wash and dry hands. The selected protective gloves have to satisfy the specifications of EU Directive 89/686/EEC and the standard EN 374 derived from it. Body Protection Complete suit protecting against chemicals, The type of protective equipment must be selected according to the concentration and amount of the dangerous substance at the specific workplace.

Aldrich - 339741 Page 4 of 7

Respiratory protection Where risk assessment shows air-purifying respirators are appropriate use a full-face respirator with multi-purpose combination (US) or type ABEK (EN 14387) respirator cartridges as a backup to engineering controls. If the respirator is the sole means of protection, use a full-face supplied air respirator. Use respirators and components tested and approved under appropriate government standards such as NIOSH (US) or CEN (EU).

9. PHYSICAL AND CHEMICAL PROPERTIES

9.1 Information on basic physical and chemical properties a) Appearance Form: liquid

b) Odour no data available

c) Odour Threshold no data available

d) pH 1,2 at 5 g/l

e) Melting point/freezing point

3 °C

f) Initial boiling point and boiling range

290 °C - lit.

g) Flash point not applicable

h) Evaporation rate no data available

i) Flammability (solid, gas) no data available

j) Upper/lower flammability or explosive limits

no data available

k) Vapour pressure 1,33 hPa at 145,8 °C

l) Vapour density 3,39 - (Air = 1.0)

m) Relative density 1,84 g/cm3 at 25 °C

n) Water solubility soluble

o) Partition coefficient: n-octanol/water

no data available

p) Autoignition temperature

no data available

q) Decomposition temperature

no data available

r) Viscosity no data available

s) Explosive properties no data available

t) Oxidizing properties no data available

9.2 Other safety information Surface tension 55,1 mN/m at 20 °C

10. STABILITY AND REACTIVITY

10.1 Reactivity no data available

10.2 Chemical stability no data available

10.3 Possibility of hazardous reactions no data available

10.4 Conditions to avoid no data available

45

Aldrich - 339741 Page 7 of 7

The above information is believed to be correct but does not purport to be all inclusive and shall be used only as a guide. The information in this document is based on the present state of our knowledge and is applicable to the product with regard to appropriate safety precautions. It does not represent any guarantee of the properties of the product. Sigma-Aldrich Corporation and its Affiliates shall not be held liable for any damage resulting from handling or from contact with the above product. See www.sigma-aldrich.com and/or the reverse side of invoice or packing slip for additional terms and conditions of sale.

Aldrich - 339741 Page 6 of 7

12. ECOLOGICAL INFORMATION

12.1 Toxicity Toxicity to fish LC50 - Gambusia affinis (Mosquito fish) - 42 mg/l - 96 h

12.2 Persistence and degradability no data available

12.3 Bioaccumulative potential no data available

12.4 Mobility in soil no data available

12.5 Results of PBT and vPvB assessment no data available

12.6 Other adverse effects Harmful to aquatic life.

13. DISPOSAL CONSIDERATIONS

13.1 Waste treatment methods

Product Offer surplus and non-recyclable solutions to a licensed disposal company.

Contaminated packaging Dispose of as unused product.

14. TRANSPORT INFORMATION

14.1 UN number ADR/RID: 1830 IMDG: 1830 IATA: 1830

14.2 UN proper shipping name ADR/RID: SULPHURIC ACID IMDG: SULPHURIC ACID IATA: Sulphuric acid

14.3 Transport hazard class(es) ADR/RID: 8 IMDG: 8 IATA: 8

14.4 Packaging group ADR/RID: II IMDG: II IATA: II

14.5 Environmental hazards ADR/RID: no IMDG Marine pollutant: no IATA: no

14.6 Special precautions for user no data available

15. REGULATORY INFORMATION

This safety datasheet complies with the requirements of Regulation (EC) No. 1907/2006.

15.1 Safety, health and environmental regulations/legislation specific for the substance or mixture no data available

15.2 Chemical Safety Assessment no data available

16. OTHER INFORMATION

Further information Copyright 2012 Sigma-Aldrich Co. LLC. License granted to make unlimited paper copies for internal use only.

Aldrich - 339741 Page 5 of 7

10.5 Incompatible materials Bases, Halides, Organic materials, Carbides, fulminates, Nitrates, picrates, Cyanides, Chlorates, alkali halides, Zinc salts, permanganates, e.g. potassium permanganate, Hydrogen peroxide, Azides, Perchlorates., Nitromethane, phosphorous, Reacts violently with:, cyclopentadiene, cyclopentanone oxime, nitroaryl amines, hexalithium disilicide, phosphorous(III) oxide, Powdered metals

10.6 Hazardous decomposition products Other decomposition products - no data available

11. TOXICOLOGICAL INFORMATION

11.1 Information on toxicological effects

Acute toxicity LD50 Oral - rat - 2.140 mg/kg

LC50 Inhalation - rat - 2 h - 510 mg/m3

Skin corrosion/irritation Skin - rabbit - Extremely corrosive and destructive to tissue.

Serious eye damage/eye irritation Eyes - rabbit - Severe eye irritation

Respiratory or skin sensitization no data available

Germ cell mutagenicity no data available

Carcinogenicity

The International Agency for Research on Cancer (IARC) has determined that occupational exposure to strong-inorganic-acid mists containing sulfuric acid is carcinogenic to humans (group 1).

IARC: No component of this product present at levels greater than or equal to 0.1% is identified as probable, possible or confirmed human carcinogen by IARC.

Reproductive toxicity

no data available

Specific target organ toxicity - single exposure no data available

Specific target organ toxicity - repeated exposure no data available

Aspiration hazard no data available

Potential health effects

Inhalation May be harmful if inhaled. Material is extremely destructive to the tissue of the mucous membranes and upper respiratory tract.

Ingestion May be harmful if swallowed. Causes burns. Skin May be harmful if absorbed through skin. Causes skin burns. Eyes Causes eye burns.

Signs and Symptoms of Exposure Material is extremely destructive to tissue of the mucous membranes and upper respiratory tract, eyes, and skin., spasm, inflammation and edema of the larynx, spasm, inflammation and edema of the bronchi, pneumonitis, pulmonary edema, burning sensation, Cough, wheezing, laryngitis, Shortness of breath, Headache, Nausea, Vomiting, Pulmonary edema. Effects may be delayed., To the best of our knowledge, the chemical, physical, and toxicological properties have not been thoroughly investigated.

Additional Information RTECS: WS5600000

46

Annex 6 : MSDS of Phytic acid

Aldrich - 593648 Page 1 of 7

SIGMA-ALDRICH sigma-aldrich.com SAFETY DATA SHEET

according to Regulation (EC) No. 1907/2006 Version 3.1 Revision Date 03.06.2011

Print Date 14.03.2012 GENERIC EU MSDS - NO COUNTRY SPECIFIC DATA - NO OEL DATA

1. IDENTIFICATION OF THE SUBSTANCE/MIXTURE AND OF THE COMPANY/UNDERTAKING

1.1 Product identifiers Product name : Phytic acid solution

Product Number : 593648 Brand : Aldrich

1.2 Relevant identified uses of the substance or mixture and uses advised against

Identified uses : Laboratory chemicals, Manufacture of substances

1.3 Details of the supplier of the safety data sheet

Company : Sigma-Aldrich Chimie S.a.r.l L'Isle D'Abeau Chesnes F-38297 ST. QUENTIN FALLAVIER

Telephone : +33 (0)4 74 82 28 40 Fax : +33 (0)4 74 95 68 08 E-mail address : eurtechserv@sial.com

1.4 Emergency telephone number

Emergency Phone # : I.N.R.S.:+33 (0)1 45 42 59 59 2. HAZARDS IDENTIFICATION

2.1 Classification of the substance or mixture

Classification according to Regulation (EC) No 1272/2008 [EU-GHS/CLP] Skin irritation (Category 2) Eye irritation (Category 2) Specific target organ toxicity - single exposure (Category 3)

Classification according to EU Directives 67/548/EEC or 1999/45/EC Irritating to eyes, respiratory system and skin.

2.2 Label elements

Labelling according Regulation (EC) No 1272/2008 [CLP]

Pictogram

Signal word Warning Hazard statement(s) H315 Causes skin irritation. H319 Causes serious eye irritation. H335 May cause respiratory irritation. Precautionary statement(s) P261 Avoid breathing dust/ fume/ gas/ mist/ vapours/ spray. P305 + P351 + P338 IF IN EYES: Rinse cautiously with water for several minutes. Remove

contact lenses, if present and easy to do. Continue rinsing. Supplemental Hazard Statements

none

Aldrich - 593648 Page 2 of 7

According to European Directive 67/548/EEC as amended.

Hazard symbol(s)

R-phrase(s) R36/37/38 Irritating to eyes, respiratory system and skin. S-phrase(s) S26 In case of contact with eyes, rinse immediately with plenty of water and

seek medical advice.

2.3 Other hazards - none 3. COMPOSITION/INFORMATION ON INGREDIENTS

3.2 Mixtures Synonyms : myo-Inositol hexakis(dihydrogen phosphate)

Formula : C6H18O24P6 Component Classification Concentration

Fytic acid CAS-No.

EC-No.

83-86-3 201-506-6

Skin Irrit. 2; Eye Irrit. 2; STOT SE 3; H315, H319, H335 Xi, R36/37/38

>= 40 - <= 50 %

Water CAS-No.

EC-No.

7732-18-5 231-791-2

- >= 50 - <= 60 %

For the full text of the H-Statements and R-Phrases mentioned in this Section, see Section 16 4. FIRST AID MEASURES

4.1 Description of first aid measures

General advice Consult a physician. Show this safety data sheet to the doctor in attendance.

If inhaled If breathed in, move person into fresh air. If not breathing, give artificial respiration. Consult a physician.

In case of skin contact Wash off with soap and plenty of water. Consult a physician.

In case of eye contact Rinse thoroughly with plenty of water for at least 15 minutes and consult a physician.

If swallowed Never give anything by mouth to an unconscious person. Rinse mouth with water. Consult a physician.

4.2 Most important symptoms and effects, both acute and delayed To the best of our knowledge, the chemical, physical, and toxicological properties have not been thoroughly investigated.

4.3 Indication of any immediate medical attention and special treatment needed no data available

5. FIRE-FIGHTING MEASURES

5.1 Extinguishing media

Suitable extinguishing media Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide.

Aldrich - 593648 Page 3 of 7

5.2 Special hazards arising from the substance or mixture Carbon oxides, Oxides of phosphorus

5.3 Advice for firefighters Wear self contained breathing apparatus for fire fighting if necessary.

5.4 Further information no data available

6. ACCIDENTAL RELEASE MEASURES

6.1 Personal precautions, protective equipment and emergency procedures Use personal protective equipment. Avoid breathing vapors, mist or gas. Ensure adequate ventilation. Evacuate personnel to safe areas.

6.2 Environmental precautions Do not let product enter drains.

6.3 Methods and materials for containment and cleaning up Soak up with inert absorbent material and dispose of as hazardous waste. Keep in suitable, closed containers for disposal.

6.4 Reference to other sections For disposal see section 13.

7. HANDLING AND STORAGE

7.1 Precautions for safe handling Avoid contact with skin and eyes. Avoid inhalation of vapour or mist.

7.2 Conditions for safe storage, including any incompatibilities Store in cool place. Keep container tightly closed in a dry and well-ventilated place. Containers which are opened must be carefully resealed and kept upright to prevent leakage.

7.3 Specific end uses no data available

8. EXPOSURE CONTROLS/PERSONAL PROTECTION

8.1 Control parameters

Components with workplace control parameters

8.2 Exposure controls

Appropriate engineering controls Handle in accordance with good industrial hygiene and safety practice. Wash hands before breaks and at the end of workday.

Personal protective equipment

Eye/face protection Safety glasses with side-shields conforming to EN166 Use equipment for eye protection tested and approved under appropriate government standards such as NIOSH (US) or EN 166(EU).

Skin protection Handle with gloves. Gloves must be inspected prior to use. Use proper glove removal technique (without touching glove's outer surface) to avoid skin contact with this product. Dispose of contaminated gloves after use in accordance with applicable laws and good laboratory practices. Wash and dry hands. The selected protective gloves have to satisfy the specifications of EU Directive 89/686/EEC and the standard EN 374 derived from it. Body Protection impervious clothing, The type of protective equipment must be selected according to the concentration and amount of the dangerous substance at the specific workplace.

Aldrich - 593648 Page 4 of 7

Respiratory protection Where risk assessment shows air-purifying respirators are appropriate use a full-face respirator with multi-purpose combination (US) or type ABEK (EN 14387) respirator cartridges as a backup to engineering controls. If the respirator is the sole means of protection, use a full-face supplied air respirator. Use respirators and components tested and approved under appropriate government standards such as NIOSH (US) or CEN (EU).

9. PHYSICAL AND CHEMICAL PROPERTIES

9.1 Information on basic physical and chemical properties a) Appearance Form: liquid

b) Odour no data available

c) Odour Threshold no data available

d) pH no data available

e) Melting point/freezing point

no data available

f) Initial boiling point and boiling range

105 °C

g) Flash point no data available

h) Evaporation rate no data available

i) Flammability (solid, gas) no data available

j) Upper/lower flammability or explosive limits

no data available

k) Vapour pressure no data available

l) Vapour density no data available

m) Relative density no data available

n) Water solubility no data available

o) Partition coefficient: n-octanol/water

no data available

p) Autoignition temperature

no data available

q) Decomposition temperature

no data available

r) Viscosity no data available

s) Explosive properties no data available

t) Oxidizing properties no data available

9.2 Other safety information no data available

10. STABILITY AND REACTIVITY

10.1 Reactivity no data available

10.2 Chemical stability no data available

10.3 Possibility of hazardous reactions no data available

47

Aldrich - 593648 Page 7 of 7

The above information is believed to be correct but does not purport to be all inclusive and shall be used only as a guide. The information in this document is based on the present state of our knowledge and is applicable to the product with regard to appropriate safety precautions. It does not represent any guarantee of the properties of the product. Sigma-Aldrich Co., shall not be held liable for any damage resulting from handling or from contact with the above product. See reverse side of invoice or packing slip for additional terms and conditions of sale.

Aldrich - 593648 Page 6 of 7

12.4 Mobility in soil no data available

12.5 Results of PBT and vPvB assessment no data available

12.6 Other adverse effects no data available

13. DISPOSAL CONSIDERATIONS

13.1 Waste treatment methods

Product Offer surplus and non-recyclable solutions to a licensed disposal company.

Contaminated packaging Dispose of as unused product.

14. TRANSPORT INFORMATION

14.1 UN number ADR/RID: - IMDG: - IATA: -

14.2 UN proper shipping name ADR/RID: Not dangerous goods IMDG: Not dangerous goods IATA: Not dangerous goods

14.3 Transport hazard class(es) ADR/RID: - IMDG: - IATA: -

14.4 Packaging group ADR/RID: - IMDG: - IATA: -

14.5 Environmental hazards ADR/RID: no IMDG Marine pollutant: no IATA: no

14.6 Special precautions for user no data available

15. REGULATORY INFORMATION

This safety datasheet complies with the requirements of Regulation (EC) No. 1907/2006.

15.1 Safety, health and environmental regulations/legislation specific for the substance or mixture no data available

15.2 Chemical Safety Assessment no data available

16. OTHER INFORMATION

Text of H-code(s) and R-phrase(s) mentioned in Section 3

Eye Irrit. Eye irritation H315 Causes skin irritation. H319 Causes serious eye irritation. H335 May cause respiratory irritation. Skin Irrit. Skin irritation STOT SE Specific target organ toxicity - single exposure Xi Irritant R36/37/38 Irritating to eyes, respiratory system and skin.

Further information Copyright 2011 Sigma-Aldrich Co. License granted to make unlimited paper copies for internal use only.

Aldrich - 593648 Page 5 of 7

10.4 Conditions to avoid no data available

10.5 Incompatible materials Strong oxidizing agents

10.6 Hazardous decomposition products Other decomposition products - no data available

11. TOXICOLOGICAL INFORMATION

11.1 Information on toxicological effects

Acute toxicity no data available

Skin corrosion/irritation no data available

Serious eye damage/eye irritation no data available

Respiratory or skin sensitization no data available

Germ cell mutagenicity no data available

Carcinogenicity

IARC: No component of this product present at levels greater than or equal to 0.1% is identified as probable, possible or confirmed human carcinogen by IARC.

Reproductive toxicity no data available

Specific target organ toxicity - single exposure no data available

Specific target organ toxicity - repeated exposure no data available

Aspiration hazard no data available

Potential health effects

Inhalation May be harmful if inhaled. Causes respiratory tract irritation. Ingestion May be harmful if swallowed. Skin May be harmful if absorbed through skin. Causes skin irritation. Eyes Causes serious eye irritation.

Signs and Symptoms of Exposure To the best of our knowledge, the chemical, physical, and toxicological properties have not been thoroughly investigated.

Additional Information RTECS: Not available

12. ECOLOGICAL INFORMATION

12.1 Toxicity no data available

12.2 Persistence and degradability no data available

12.3 Bioaccumulative potential no data available

48

Annex 7 : MSDS of DTOA

Aldrich - 379387 Page 1 of 6

SIGMA-ALDRICH sigma-aldrich.com SAFETY DATA SHEET

according to Regulation (EC) No. 1907/2006 Version 4.1 Revision Date 19.05.2011

Print Date 14.03.2012 GENERIC EU MSDS - NO COUNTRY SPECIFIC DATA - NO OEL DATA

1. IDENTIFICATION OF THE SUBSTANCE/MIXTURE AND OF THE COMPANY/UNDERTAKING

1.1 Product identifiers Product name : Dithiooxamide

Product Number : 379387 Brand : Aldrich CAS-No. : 79-40-3

1.2 Relevant identified uses of the substance or mixture and uses advised against

Identified uses : Laboratory chemicals, Manufacture of substances

1.3 Details of the supplier of the safety data sheet

Company : Sigma-Aldrich Chimie S.a.r.l L'Isle D'Abeau Chesnes F-38297 ST. QUENTIN FALLAVIER

Telephone : +33 (0)4 74 82 28 40 Fax : +33 (0)4 74 95 68 08 E-mail address : eurtechserv@sial.com

1.4 Emergency telephone number

Emergency Phone # : I.N.R.S.:+33 (0)1 45 42 59 59 2. HAZARDS IDENTIFICATION

2.1 Classification of the substance or mixture

Classification according to Regulation (EC) No 1272/2008 [EU-GHS/CLP] Acute toxicity, Oral (Category 4) Skin irritation (Category 2) Eye irritation (Category 2) Specific target organ toxicity - single exposure (Category 3)

Classification according to EU Directives 67/548/EEC or 1999/45/EC Harmful if swallowed. Irritating to eyes, respiratory system and skin.

2.2 Label elements

Labelling according Regulation (EC) No 1272/2008 [CLP]

Pictogram

Signal word Warning Hazard statement(s) H302 Harmful if swallowed. H315 Causes skin irritation. H319 Causes serious eye irritation. H335 May cause respiratory irritation. Precautionary statement(s) P261 Avoid breathing dust/ fume/ gas/ mist/ vapours/ spray. P305 + P351 + P338 IF IN EYES: Rinse cautiously with water for several minutes. Remove

contact lenses, if present and easy to do. Continue rinsing.

Aldrich - 379387 Page 2 of 6

Supplemental Hazard Statements

none

According to European Directive 67/548/EEC as amended.

Hazard symbol(s)

R-phrase(s) R22 Harmful if swallowed. R36/37/38 Irritating to eyes, respiratory system and skin. S-phrase(s) S36/37 Wear suitable protective clothing and gloves.

2.3 Other hazards - none 3. COMPOSITION/INFORMATION ON INGREDIENTS

3.1 Substances Synonyms : Dithiooxalic diamide

Rubeanic acid

Formula : C2H4N2S2 Molecular Weight : 120,2 g/mol Component Concentration

Dithiooxamide CAS-No.

EC-No.

79-40-3 201-203-9

-

4. FIRST AID MEASURES

4.1 Description of first aid measures

General advice Consult a physician. Show this safety data sheet to the doctor in attendance.

If inhaled If breathed in, move person into fresh air. If not breathing, give artificial respiration. Consult a physician.

In case of skin contact Wash off with soap and plenty of water. Consult a physician.

In case of eye contact Rinse thoroughly with plenty of water for at least 15 minutes and consult a physician.

If swallowed Never give anything by mouth to an unconscious person. Rinse mouth with water. Consult a physician.

4.2 Most important symptoms and effects, both acute and delayed To the best of our knowledge, the chemical, physical, and toxicological properties have not been thoroughly investigated.

4.3 Indication of any immediate medical attention and special treatment needed no data available

5. FIRE-FIGHTING MEASURES

5.1 Extinguishing media

Suitable extinguishing media Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide.

Aldrich - 379387 Page 3 of 6

5.2 Special hazards arising from the substance or mixture Carbon oxides, nitrogen oxides (NOx), Sulphur oxides

5.3 Advice for firefighters Wear self contained breathing apparatus for fire fighting if necessary.

5.4 Further information no data available

6. ACCIDENTAL RELEASE MEASURES

6.1 Personal precautions, protective equipment and emergency procedures Use personal protective equipment. Avoid dust formation. Avoid breathing vapors, mist or gas. Ensure adequate ventilation. Evacuate personnel to safe areas. Avoid breathing dust.

6.2 Environmental precautions Do not let product enter drains.

6.3 Methods and materials for containment and cleaning up Pick up and arrange disposal without creating dust. Sweep up and shovel. Keep in suitable, closed containers for disposal.

6.4 Reference to other sections For disposal see section 13.

7. HANDLING AND STORAGE

7.1 Precautions for safe handling Avoid contact with skin and eyes. Avoid formation of dust and aerosols. Provide appropriate exhaust ventilation at places where dust is formed.Normal measures for preventive fire protection.

7.2 Conditions for safe storage, including any incompatibilities Store in cool place. Keep container tightly closed in a dry and well-ventilated place.

7.3 Specific end uses no data available

8. EXPOSURE CONTROLS/PERSONAL PROTECTION

8.1 Control parameters

Components with workplace control parameters

8.2 Exposure controls

Appropriate engineering controls Handle in accordance with good industrial hygiene and safety practice. Wash hands before breaks and at the end of workday.

Personal protective equipment

Eye/face protection Safety glasses with side-shields conforming to EN166 Use equipment for eye protection tested and approved under appropriate government standards such as NIOSH (US) or EN 166(EU).

Skin protection Handle with gloves. Gloves must be inspected prior to use. Use proper glove removal technique (without touching glove's outer surface) to avoid skin contact with this product. Dispose of contaminated gloves after use in accordance with applicable laws and good laboratory practices. Wash and dry hands. The selected protective gloves have to satisfy the specifications of EU Directive 89/686/EEC and the standard EN 374 derived from it. Body Protection Complete suit protecting against chemicals, The type of protective equipment must be selected according to the concentration and amount of the dangerous substance at the specific workplace.

Aldrich - 379387 Page 4 of 6

Respiratory protection For nuisance exposures use type P95 (US) or type P1 (EU EN 143) particle respirator.For higher level protection use type OV/AG/P99 (US) or type ABEK-P2 (EU EN 143) respirator cartridges. Use respirators and components tested and approved under appropriate government standards such as NIOSH (US) or CEN (EU).

9. PHYSICAL AND CHEMICAL PROPERTIES

9.1 Information on basic physical and chemical properties a) Appearance Form: powder

Colour: dark red

b) Odour no data available

c) Odour Threshold no data available

d) pH no data available

e) Melting point/freezing point

Melting point/range: >= 300 °C - lit.

f) Initial boiling point and boiling range

no data available

g) Flash point no data available

h) Evaporation rate no data available

i) Flammability (solid, gas) no data available

j) Upper/lower flammability or explosive limits

no data available

k) Vapour pressure no data available

l) Vapour density no data available

m) Relative density no data available

n) Water solubility no data available

o) Partition coefficient: n-octanol/water

no data available

p) Autoignition temperature

no data available

q) Decomposition temperature

no data available

r) Viscosity no data available

s) Explosive properties no data available

t) Oxidizing properties no data available

9.2 Other safety information no data available

10. STABILITY AND REACTIVITY

10.1 Reactivity no data available

10.2 Chemical stability no data available

10.3 Possibility of hazardous reactions no data available

49

Aldrich - 379387 Page 5 of 6

10.4 Conditions to avoid no data available

10.5 Incompatible materials Oxidizing agents

10.6 Hazardous decomposition products Other decomposition products - no data available

11. TOXICOLOGICAL INFORMATION

11.1 Information on toxicological effects

Acute toxicity LD50 Oral - mouse - 350 mg/kg Remarks: Behavioral:Somnolence (general depressed activity). Behavioral:Convulsions or effect on seizure threshold. Behavioral:Change in motor activity (specific assay).

Skin corrosion/irritation no data available

Serious eye damage/eye irritation no data available

Respiratory or skin sensitization no data available

Germ cell mutagenicity no data available

Carcinogenicity

IARC: No component of this product present at levels greater than or equal to 0.1% is identified as probable, possible or confirmed human carcinogen by IARC.

Reproductive toxicity no data available

Specific target organ toxicity - single exposure Inhalation - May cause respiratory irritation.

Specific target organ toxicity - repeated exposure no data available

Aspiration hazard no data available

Potential health effects

Inhalation May be harmful if inhaled. Causes respiratory tract irritation. Ingestion Harmful if swallowed. Skin May be harmful if absorbed through skin. Causes skin irritation. Eyes Causes serious eye irritation.

Signs and Symptoms of Exposure To the best of our knowledge, the chemical, physical, and toxicological properties have not been thoroughly investigated.

Additional Information RTECS: RP1575000

12. ECOLOGICAL INFORMATION

12.1 Toxicity no data available

12.2 Persistence and degradability no data available

Aldrich - 379387 Page 6 of 6

12.3 Bioaccumulative potential no data available

12.4 Mobility in soil no data available

12.5 Results of PBT and vPvB assessment no data available

12.6 Other adverse effects no data available

13. DISPOSAL CONSIDERATIONS

13.1 Waste treatment methods

Product Offer surplus and non-recyclable solutions to a licensed disposal company. Contact a licensed professional waste disposal service to dispose of this material. Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber.

Contaminated packaging Dispose of as unused product.

14. TRANSPORT INFORMATION

14.1 UN number ADR/RID: - IMDG: - IATA: -

14.2 UN proper shipping name ADR/RID: Not dangerous goods IMDG: Not dangerous goods IATA: Not dangerous goods

14.3 Transport hazard class(es) ADR/RID: - IMDG: - IATA: -

14.4 Packaging group ADR/RID: - IMDG: - IATA: -

14.5 Environmental hazards ADR/RID: no IMDG Marine pollutant: no IATA: no

14.6 Special precautions for user no data available

15. REGULATORY INFORMATION

This safety datasheet complies with the requirements of Regulation (EC) No. 1907/2006.

15.1 Safety, health and environmental regulations/legislation specific for the substance or mixture no data available

15.2 Chemical Safety Assessment no data available

16. OTHER INFORMATION

Further information Copyright 2011 Sigma-Aldrich Co. License granted to make unlimited paper copies for internal use only. The above information is believed to be correct but does not purport to be all inclusive and shall be used only as a guide. The information in this document is based on the present state of our knowledge and is applicable to the product with regard to appropriate safety precautions. It does not represent any guarantee of the properties of the product. Sigma-Aldrich Co., shall not be held liable for any damage resulting from handling or from contact with the above product. See reverse side of invoice or packing slip for additional terms and conditions of sale.

50

Annex 8 : MSDS of DMP

Aldrich - 64046 Page 2 of 7

contact lenses, if present and easy to do. Continue rinsing. Supplemental Hazard Statements

none

According to European Directive 67/548/EEC as amended.

Hazard symbol(s)

R-phrase(s) R22 Harmful if swallowed. R36/37/38 Irritating to eyes, respiratory system and skin. S-phrase(s) S26 In case of contact with eyes, rinse immediately with plenty of water and

seek medical advice. S36 Wear suitable protective clothing.

2.3 Other hazards - none 3. COMPOSITION/INFORMATION ON INGREDIENTS

3.1 Substances Synonyms : Dithioglycerol

British anti-Lewisite BAL Dimercaprol

Formula : C3H8OS2 Molecular Weight : 124,23 g/mol Component Concentration

Dimercaprol CAS-No.

EC-No.

59-52-9 200-433-7

-

4. FIRST AID MEASURES

4.1 Description of first aid measures

General advice Consult a physician. Show this safety data sheet to the doctor in attendance.

If inhaled If breathed in, move person into fresh air. If not breathing, give artificial respiration. Consult a physician.

In case of skin contact Wash off with soap and plenty of water. Take victim immediately to hospital. Consult a physician.

In case of eye contact Rinse thoroughly with plenty of water for at least 15 minutes and consult a physician.

If swallowed Never give anything by mouth to an unconscious person. Rinse mouth with water. Consult a physician.

4.2 Most important symptoms and effects, both acute and delayed Nausea, Headache, Vomiting

4.3 Indication of any immediate medical attention and special treatment needed no data available

Aldrich - 64046 Page 3 of 7

5. FIRE-FIGHTING MEASURES

5.1 Extinguishing media

Suitable extinguishing media Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide.

5.2 Special hazards arising from the substance or mixture Carbon oxides, Sulphur oxides

5.3 Advice for firefighters Wear self contained breathing apparatus for fire fighting if necessary.

5.4 Further information no data available

6. ACCIDENTAL RELEASE MEASURES

6.1 Personal precautions, protective equipment and emergency procedures Wear respiratory protection. Avoid breathing vapors, mist or gas. Ensure adequate ventilation. Evacuate personnel to safe areas.

6.2 Environmental precautions Prevent further leakage or spillage if safe to do so. Do not let product enter drains.

6.3 Methods and materials for containment and cleaning up Soak up with inert absorbent material and dispose of as hazardous waste. Keep in suitable, closed containers for disposal.

6.4 Reference to other sections For disposal see section 13.

7. HANDLING AND STORAGE

7.1 Precautions for safe handling Avoid contact with skin and eyes. Avoid inhalation of vapour or mist. Normal measures for preventive fire protection.

7.2 Conditions for safe storage, including any incompatibilities Store in cool place. Keep container tightly closed in a dry and well-ventilated place. Containers which are opened must be carefully resealed and kept upright to prevent leakage.

Recommended storage temperature: 2 - 8 °C

7.3 Specific end uses no data available

8. EXPOSURE CONTROLS/PERSONAL PROTECTION

8.1 Control parameters

Components with workplace control parameters

8.2 Exposure controls

Appropriate engineering controls Avoid contact with skin, eyes and clothing. Wash hands before breaks and immediately after handling the product.

Personal protective equipment

Eye/face protection Face shield and safety glasses Use equipment for eye protection tested and approved under appropriate government standards such as NIOSH (US) or EN 166(EU).

Skin protection Handle with gloves. Gloves must be inspected prior to use. Use proper glove removal technique (without touching glove's outer surface) to avoid skin contact with this product. Dispose of

Aldrich - 64046 Page 1 of 7

SIGMA-ALDRICH sigma-aldrich.com SAFETY DATA SHEET

according to Regulation (EC) No. 1907/2006 Version 4.1 Revision Date 08.07.2011

Print Date 14.03.2012 GENERIC EU MSDS - NO COUNTRY SPECIFIC DATA - NO OEL DATA

1. IDENTIFICATION OF THE SUBSTANCE/MIXTURE AND OF THE COMPANY/UNDERTAKING

1.1 Product identifiers Product name : 2,3-Dimercapto-1-propanol

Product Number : 64046 Brand : Aldrich CAS-No. : 59-52-9

1.2 Relevant identified uses of the substance or mixture and uses advised against

Identified uses : Laboratory chemicals, Manufacture of substances

1.3 Details of the supplier of the safety data sheet

Company : Sigma-Aldrich Chimie S.a.r.l L'Isle D'Abeau Chesnes F-38297 ST. QUENTIN FALLAVIER

Telephone : +33 (0)4 74 82 28 40 Fax : +33 (0)4 74 95 68 08 E-mail address : eurtechserv@sial.com

1.4 Emergency telephone number

Emergency Phone # : I.N.R.S.:+33 (0)1 45 42 59 59 2. HAZARDS IDENTIFICATION

2.1 Classification of the substance or mixture

Classification according to Regulation (EC) No 1272/2008 [EU-GHS/CLP] Acute toxicity, Oral (Category 3) Skin irritation (Category 2) Eye irritation (Category 2) Specific target organ toxicity - single exposure (Category 3)

Classification according to EU Directives 67/548/EEC or 1999/45/EC Harmful if swallowed. Irritating to eyes, respiratory system and skin.

2.2 Label elements

Labelling according Regulation (EC) No 1272/2008 [CLP]

Pictogram

Signal word Danger Hazard statement(s) H301 Toxic if swallowed. H315 Causes skin irritation. H319 Causes serious eye irritation. H335 May cause respiratory irritation. Precautionary statement(s) P261 Avoid breathing dust/ fume/ gas/ mist/ vapours/ spray. P301 + P310 IF SWALLOWED: Immediately call a POISON CENTER or doctor/

physician. P305 + P351 + P338 IF IN EYES: Rinse cautiously with water for several minutes. Remove

Aldrich - 64046 Page 4 of 7

contaminated gloves after use in accordance with applicable laws and good laboratory practices. Wash and dry hands. The selected protective gloves have to satisfy the specifications of EU Directive 89/686/EEC and the standard EN 374 derived from it. Body Protection Complete suit protecting against chemicals, The type of protective equipment must be selected according to the concentration and amount of the dangerous substance at the specific workplace.

Respiratory protection Where risk assessment shows air-purifying respirators are appropriate use a full-face respirator with multi-purpose combination (US) or type ABEK (EN 14387) respirator cartridges as a backup to engineering controls. If the respirator is the sole means of protection, use a full-face supplied air respirator. Use respirators and components tested and approved under appropriate government standards such as NIOSH (US) or CEN (EU).

9. PHYSICAL AND CHEMICAL PROPERTIES

9.1 Information on basic physical and chemical properties a) Appearance Form: liquid

Colour: light yellow

b) Odour no data available

c) Odour Threshold no data available

d) pH no data available

e) Melting point/freezing point

no data available

f) Initial boiling point and boiling range

120 °C at 20 hPa - lit.

g) Flash point 112 °C - closed cup

h) Evaporation rate no data available

i) Flammability (solid, gas) no data available

j) Upper/lower flammability or explosive limits

no data available

k) Vapour pressure no data available

l) Vapour density no data available

m) Relative density 1,239 g/cm3 at 25 °C

n) Water solubility no data available

o) Partition coefficient: n-octanol/water

no data available

p) Autoignition temperature

no data available

q) Decomposition temperature

no data available

r) Viscosity no data available

s) Explosive properties no data available

t) Oxidizing properties no data available

9.2 Other safety information no data available

51

Aldrich - 64046 Page 7 of 7

15.2 Chemical Safety Assessment no data available

16. OTHER INFORMATION

Further information Copyright 2011 Sigma-Aldrich Co. License granted to make unlimited paper copies for internal use only. The above information is believed to be correct but does not purport to be all inclusive and shall be used only as a guide. The information in this document is based on the present state of our knowledge and is applicable to the product with regard to appropriate safety precautions. It does not represent any guarantee of the properties of the product. Sigma-Aldrich Co., shall not be held liable for any damage resulting from handling or from contact with the above product. See reverse side of invoice or packing slip for additional terms and conditions of sale.

Aldrich - 64046 Page 6 of 7

Eyes Causes serious eye irritation.

Signs and Symptoms of Exposure Nausea, Headache, Vomiting

Additional Information RTECS: UB2625000

12. ECOLOGICAL INFORMATION

12.1 Toxicity no data available

12.2 Persistence and degradability no data available

12.3 Bioaccumulative potential no data available

12.4 Mobility in soil no data available

12.5 Results of PBT and vPvB assessment no data available

12.6 Other adverse effects no data available

13. DISPOSAL CONSIDERATIONS

13.1 Waste treatment methods

Product Offer surplus and non-recyclable solutions to a licensed disposal company. Contact a licensed professional waste disposal service to dispose of this material.

Contaminated packaging Dispose of as unused product.

14. TRANSPORT INFORMATION

14.1 UN number ADR/RID: 2810 IMDG: 2810 IATA: 2810

14.2 UN proper shipping name ADR/RID: TOXIC LIQUID, ORGANIC, N.O.S. (Dimercaprol) IMDG: TOXIC LIQUID, ORGANIC, N.O.S. (Dimercaprol) IATA: Toxic liquid, organic, n.o.s. (Dimercaprol)

14.3 Transport hazard class(es) ADR/RID: 6.1 IMDG: 6.1 IATA: 6.1

14.4 Packaging group ADR/RID: III IMDG: III IATA: III

14.5 Environmental hazards ADR/RID: no IMDG Marine pollutant: no IATA: no

14.6 Special precautions for user no data available

15. REGULATORY INFORMATION

This safety datasheet complies with the requirements of Regulation (EC) No. 1907/2006.

15.1 Safety, health and environmental regulations/legislation specific for the substance or mixture no data available

Aldrich - 64046 Page 5 of 7

10. STABILITY AND REACTIVITY

10.1 Reactivity no data available

10.2 Chemical stability no data available

10.3 Possibility of hazardous reactions no data available

10.4 Conditions to avoid no data available

10.5 Incompatible materials Bases, Oxidizing agents, Reducing agents, Alkali metals

10.6 Hazardous decomposition products Other decomposition products - no data available

11. TOXICOLOGICAL INFORMATION

11.1 Information on toxicological effects

Acute toxicity LD50 Oral - mouse - 217 mg/kg

Skin corrosion/irritation no data available

Serious eye damage/eye irritation no data available

Respiratory or skin sensitization no data available

Germ cell mutagenicity no data available

Carcinogenicity

IARC: No component of this product present at levels greater than or equal to 0.1% is identified as probable, possible or confirmed human carcinogen by IARC.

Reproductive toxicity

Developmental Toxicity - mouse - Subcutaneous Effects on Embryo or Fetus: Fetal death.

Developmental Toxicity - mouse - Subcutaneous Specific Developmental Abnormalities: Craniofacial (including nose and tongue).

Developmental Toxicity - mouse - Subcutaneous Specific Developmental Abnormalities: Musculoskeletal system.

Specific target organ toxicity - single exposure Inhalation - May cause respiratory irritation.

Specific target organ toxicity - repeated exposure no data available

Aspiration hazard no data available

Potential health effects

Inhalation May be harmful if inhaled. Causes respiratory tract irritation. Ingestion Toxic if swallowed. Skin May be harmful if absorbed through skin. Causes skin irritation.