ADVANCED CHEMISTRY FINAL REPORT

Fhassi Maulavi Anfiqi Adhika Ardhana Falian Lubis Fikri Dwisatrio Fajar Surya Muhammad

1306437050 1306388912 1306437132 1306437170

CIVIL ENGINEERING DEPARTMENT ENGINEERING FACULTY UNIVERSITAS INDONESIA DEPOK 2014

Table of Content

Preface Chapter 1 Introduction 1.1 Problem Analysi 1.2 Objectives 1.3 Solution Chapter 2 Content 2.1 Material Structure 2.2 Material 2.3 Structure Corrosion 2.4 Corrosion Effect 2.5 Protection Method Chapter 3 Conclusion References

Chapter 1 Preliminary 1.1 Problem Analysis

In general, reinforced concrete has proved to be successful in terms of both structural performance and durability. However, there are instance of premature failure of reinforced concrete components due to corrosion of the reinforcement. The two factors provoking corrosion are the ingress of chloride ions from deicing salts or sea water or the reaction of the alkaline pore solution with carbon dioxide from the atmosphere, a process known as carbonation. Despite of the huge demand, a simple, cheap and reliable technique which either protects the steel from corrosion or at least lower sits corrosion rate is still lacking. Over the past decade, however, concrete repair industry has developed some major techniques that are claimed to prevent or at least reduce corrosion of steel in concrete. The use of these corrosion inhibitors is of increasing interest as they can be used in reinforced concrete either as preventive measure for new structure or as surface applied inhibitors for preventive and restorative purpose. In addition, to the mixing water does not require any additional working steps and allows a simple handling of the inhibitor, unless if affects the properties of the cement paste adversely. Application from the concrete surface could be a promising technique to protect already existing structures from corrosion or increase the lifetime of structures that already show corrosion attack. The application of inhibitors on the concrete surface requires the transport of the substance to the rebar where it has to reach a sufficiently high concentration to protect steel against corrosion or reduce the rate of the ongoing corrosion. Very often the long experience with chemicals operating as corrosion inhibitors e.g. in the oil field, gas or petroleum industry is taken as an example for the successful use of corrosion inhibitors, transferring this success also to applications on reinforced concrete. This is completely not correct because the mechanism of inhibitors action is completely different. There are some behaviors happened: In the application of oil and gas industry (and most others) the steel to be protected is uniformly corroding in slightly acidic or neutral media. Thus the inhibitors have to protect the bare metal surface e.g. as adsorption inhibitors acting specifically on the anodic or on the cathode partial reaction of the corrosion process or as film forming

inhibitors blocking the surface more or less completely. Usually a reduction in corrosion rate of 95 to 99% is achieved with a very small inhibitor concentration in the order of 10-3 10-2 mol/l. Steel in concrete instead is in a highly alkaline environment, the high concentration of hydroxyl ions acts as passive media promoting inhibitor and indeed, steel in concrete is passive, thus protected by a thin oxy-hydroxide layer. This is the starting point for any mechanistic action of inhibitors in concrete. Inhibitors for chloride induced pitting corrosion are by far less studied. Inhibitors for pitting corrosion can act by film forming prior to the ingress of chlorides, by buffering the pH in the local pit environment, by competitive surface adsorption processes between inhibitor and chloride ions or by competitive migration of inhibitor and chloride ions into the pit. Another point in the life terminology of inhibitors has to be clarified: a corrosion inhibitor can extend the service life due to chemical/electrochemical interaction with the reinforcement. Any other substances that may prevent the onset of corrosion or reduce ongoing corrosion by surface treatment or by admixtures that reduce porosity of the concrete are not considered to be corrosion inhibitors. The most frequently used technique is adding of the inhibitors to the mixing water of concrete as admixtures for new structures in order to prevent or at least delay the onset of corrosion. Calcium nitrite is the most extensively tested admixed corrosion inhibitor and when applied according the specifications together with high quality concrete and sufficient cover a long and proven track record in USA, Japan and in Middle East. Another inorganic inhibitor, sodium mono-fluoro phosphate Na2PO3F (MFP), can be used only as surface applied inhibitor due to adverse chemical reaction with fresh concrete. Laboratory studies of preventive inhibitor action against chloride included corrosion showed that by applying several intense flushing before the ingress of chlorides, it could prevent the onset of the corrosion during the test duration of 90 days even at chloride concentrations as high as 2% by weight of cement. A critical concentration MFP/chlorides greater than 1 had to be achieved, otherwise the reduction in corrosion rate will not be significant. In solutions containing Ca(OH)2

MFP is reported to react with the calcium ion to form insoluble products as calcium phosphate and calcium fluoride, thus the active substance, the PO3F- ion disappears from the pore solution. The main problem using MFP as surface applied liquid is the penetration to the reinforcement in order to act as inhibitor. Organic inhibitor, especially alkanolamines and amines and their salts with organic and inorganic acids are used as components in corrosion inhibitor blends of usually complex formulations. These blends often are not sufficiently well described so most of the published work has been undertaken with commercially available systems. A comparative test of different organic amines in alkaline solutions showed very good corrosion inhibition of the commercial inhibitor blend at high concentration, pure dimethyl-ethanolamine instead being practically ineffective. Recent research work at ETH Zurich investigating a commercial migrating inhibitor blend has shown that the blend can be fractionated into a volatile (dimethyl-ethanolamine) and a non-volatile (benzoate) component. For a complete prevention of corrosion initiation in sat. Ca(OH)2 solution with 1 M NaCl added the presence of both components at the steel surface in a concentration ratio of inhibitor/chloride ca. 1 was necessary (figure 1). Modern surface analytical techniques such as XPS have shown that for the formation of a significantly thicker organic film on iron in alkaline solutions both components of the commercial inhibitor blend have to be present. This might be significant for the mechanism of the inhibitor action. The inhibitor in recommended dosage could delay the average time to corrosion initiation of passive steel in mortar by a factor of 3 (figure 2).

1.2

Objectives

This writing is to define whether the alkanolamines is the right option to be the inhibitor to prevent the reinforced concrete structure from corrosion or not. The corrosion of embedded reinforcement has long been recognized as one of the most prevalent durability factors affecting whole life costs of concrete structures such as bridges, parking ramps, building worldwide. Similarly, the life of steel structures is shortened by corrosion. Nowadays, there are some discoveries that shows the alkanolamines can be used against corrosion. It originally found in 1986 as a mixed type of inhibitor and has been applied in the admixture materials such as concrete and embedded steel reinforcement. Migratory Corrosion Inhibitors (MCI) is a chemical method for controlling corrosion and lowering it whole life costs. Incorporating MCI into coatings provide them with the ability to protect the coated areas but also areas adjacent to the coating and also using MCI that can migrate to embedded reinforcement to provide corrosion protection, as well as a physical barrier to eliminate further ingress of corrosive materials such as water chloride into the concrete itself. Some major tests that have been done to determine what materials is the most effective and efficient against the corrosion of reinforced concrete structure (admixture materials). The first generation MCIs based on amino alcohols were found to extend the time to corrosion initiation and cut corrosion rates in halt compared to controls. The next and third generation migrating corrosion inhibitors are based on amine carboxylate technology and can generally double the time to the onset of corrosion. Once corrosion starts, they can slow the corrosion rate to four times or more less than that of a control. Some results has been discovered from many laboratories and filed studies which used the concrete as the trial. MCIs have the following characteristics when used in concrete for corrosion protection; a) MCIs can be incorporated as admixtures to concrete in small dosages. b) MCIs have little to no effect on air content, setting time, slump and slump loss, compressive strength, freeze-thaw resistance and etc.

c) MCIs are effective in corrosion protection of steel in concrete when used as an admixture or by surface impregnation. Under some conditions, MCIs provided better protection of rebar than calcium nitrite. From those facts that have been proven the alkanolamines family such as MCI is the most suitable inhibitor for preventing the reinforced concrete structure from corrosion, evaluated the results that show this kind of inhibitor is effective on slowing the initiation of corrosion in concrete. 1.3 Problem Solution

Corrosion is one of many problems that can be happened to a material that will damaged it and make the material or even a structure collapse. Each engineer especially the civil engineers want the design they build becoming a great project but these kind of problem would not be a distracter when project is built but the problem will occurred after the project already built. Corrosion usually coming from the surrounding areas of the structure or the building itself, it will continuously damaged the material especially concrete and reducing the strength of it structure, to prevent this kind of issue as we mentioned from the last chapter, the alkanolamines is the right choice to avoid the structure from being damaged or collapsed. The matter is the management within the engineers that build certain structure itself whether they think about the maintenance or not, usually the maintenance plan is included in the grand design. The technique we offered is using the alkanolamines as the inhibitor by blend it together or even used it as a coating after the structure has been built. From many alkanolamines that exist let evaluate the MCI first, from the study MCI can be used as a non destructive measure for corrosion protection both as admixtures and surface treatments to concrete structures.

Previously we mentioned about the very old inhibitor that invented many years ago which is alkanolamines and amines and their salts with organic and inorganic acids are used as components in corrosion inhibitor. It is the same situation happening with the MCI that react with salt, there are less salt penetrated was seen on an MCI treated on the bridge section after 7 years of heavy road salt exposure. This effect is achieved due to the amine carboxylate chemistry of cortec MCIs. When the selected cortec MCI molecules migrate through the concrete, they react with calcium in the substrate. As a result of this reaction, insoluble salts of carboxylic acids are formed, and the amine portion of the molecules is released. This creates two obvious advantages: 1. The formation of insoluble salts blocks pores making the concrete less permeable. 2. Amine is fast migrating and moves quickly towards embedded reinforcement.

3. The migrating portions of MCI released by the amine carboxylate also have a stronger attraction to the steel reinforcement that amino alcohol based products. The reaction an amine carboxylate based MCI has with the substrate creates true positively and negatively charged molecules that in turn migrate toward embedded reinforcement to form a film. These turn charges have a greater affinity for the the steel than the + and charges an amino alcohol based product would have, allowing for even longer corrosion protection. There is another way to prevent the corrosion which is transport of the inhibitor into mortar or concrete, it is claimed for several inorganic and organic inhibitor blends that these inhibitors can be applied to existing reinforced concrete structures and the corrosion inhibitor will be carried by water or by vapor phase migration into proximity of the reinforcing steel. Several diffusion experiments showed that especially in the measured diffusion rates exist. This might partially be due to the different experimental setup (humidity) and measuring techniques used. In addition, it is difficult to determine the diffusion rate of an inhibitor blend of unknown composition. A detailed study on the transport of a proprietary amino alcohol based inhibitor into cement paste and mortar is reported by Tritthartd. The results showed that both, the amount and the rate of inhibitor ingress into alkaline cement paste is higher for the pure amino alcohol compared to the inhibitor blend containing also phosphates. This discrepancy could be explained by reaction of the inorganic phosphate component with the calcium ions in the fresh cement paste blocking the further ingress of the inhibitor. To avoid a reaction with calcium ions, the transport of the inhibitor was studied on cores taken from a 100 years old, fully carbonated concrete structure, varying the dosage and the way of inhibitor application. The recommended dosage (500 g/m 2) and way of application (several brushings) showed only a moderate concentration of the amino alcohol in the first 15 mm. an increase in the dosage to 1500 g/m2 increased the amino alcohol concentration, but the penetration depth remained low. Only a pounding for 28 or 50 days resulted in a significant inhibitor concentration (both amino alcohol and phosphate) at depths higher than 30 mm.

More often only one the most volatile component of the inhibitor blend can be studied as in the case of a proprietary migrating through a mortar disk could be measured. No information of the diffusion of the non-volatile part could be obtained so it can be assumed reasonably that only the volatile compound is diffusing. The fact that both components of a inhibitor blend are needed at the steel surface to get an inhibiting effect but only one component easily diffuses through the porous concrete may explain the discrepancy between solution experiments and mortar or filed tests. A high diffusion rate logically does not depend on the diffusion direction; so it has been found that the volatile component of organic inhibitor blends evaporates. Those are the solution for the corrosion happening in the reinforced concrete structure using the amino alcohol or alkanolamines.

Chapter 2 Contents

2.1 Raw Materials Concrete The raw materials which are needed to produce concrete are: 1. Limestone: CaCO3 CaO + O2 (lime oxide). 2. Clay, which contains Silica : SiO2 (silica oxide);

Alumina : Al2O3 (alumina oxide); and Iron : Fe2O3 (ferro oxide).

3. Gypsum (added during the manufacturing of concrete to reduce its setting time).

Amino alcohol The raw materials which are needed manufacture amino alcohol are:

1. Hydroxy (-OH). 2. Amino (-NH2, -NHR, and -NR2) functional group on an alkane backbone.

2.2 Building Materials To manufacture concrete, first we have to grind the raw materials into a very fine powder. After that, we mix them intimately in predetermined proportion and burn them in a large rotary kiln at a temperature of about 1400 C or 2550 F after the material sinters and partially

fuses into clinker. Cool and ground the clinker to a fine powder with some gypsum added to reduce the setting time.

2.3 Weathering Here are some causes of damage on concrete. 1. Chemical Damage on concrete can be caused chemically by: - Alkali aggregate reaction; - Chemical exposure; and - Bacteria.

Chemical attack (and subsequent reinforement corrosion) on a factory roof 2. Physical In physical damage, concrete can be damaged by: - Thermal movement; - Freeze or thaw action; - Efflorescence or leaching; - Salt crystal expansion; and - Erosion.

Freeze or thaw effect on a parking structure. 3. Mechanical Concrete is mechanically damaged, as a result of: - Impact of vibration and explosion; - Abrasion and wear; - Overloading; and - Earthquake.

Cracking caused by incorrect handling or fixing of precast panels.

2.4 Weathering Impact Here are some example of the impact of damage. Chemical damage Structure Monchaltorf sewage treatment plant, preliminary sedimentation, aeration, and final sedimentation tanks.

Problem The concrete surfaces of the sedimentation tanks are damaged, as a result of the attack the sewage (acids, sulphates, fats, etc.) and the rouine high-pressure water cleaning. The surface of the concrete is eroded badly. A few reinforcement bars near the surface are also exposed following this erosion and also now corroding from the chemical attack.

The existing joint sealants had embrittled and has been disbonded from the sides of the joints. Structure Factory roof over production facilities.

Problem Aggresive chemical attack on the concrete, followed by corrosion of the steel reinforcement in a high temperature, high humidity environment. Physical damage Structure Multi-storey concrete parking structure.

Problem Freeze or thaw damage on concrete columns and soffits from conedensation and deicing salts exposure.

Mechanical damage Structure 24 storey housing block. Reinforced concrete frame with architectural precast concrete cladding panels.

Problem Loading and impact damaged architectural precast cladding panels (from time of original construction). Cracks and inadequate cover over steel reinforcement.

2.5 Protection Method Salts and Amides The amino alcohols form salts at room temperature with mineral acids or organic acids. The mineral acid salts are hygroscopic and difficult to be obtained in anhydrous form. The mineral acid salts have been widely used as catalysts for urea and melamine resins. The fatty acid salts can be useful as emulsifiers.

Amides can be prepared from alcohols by a reaction with a methyl ester of an organic acid. These reactions must be happening at a low temperature (60 - 70 C) to prevent the formation of oxazoline. The use of a reduced pressure is desirable to support fast removal of the methanol. An alkaline catalyst, for example sodium methoxide at a level of 0.75%, is needed.

Two equivalent of fatty acid and one of AMP react in the existence of an acid catalyst to form the amide ester. A dibasic acid, such as adipic will give a poly(amide ester). These amide esters are heat stable because there is no free hydroxyl existed to form the oxazoline. Formation of the complete amide ester of AEPD or Tris Amino is very difficult because the temperatures or catalysts which are needed for the esterification tends to support the formation of oxazoline ring.

Oxazoline Formation The oxazoline from AEPD can be formed by dehydration of the amide at elevated temperatures or directly by the reaction of AEPD with the organic acid at 175 185 C with the

removal of the water of reaction. Only one of the hydroxyl groups is involved in the formation of oxazoline. The other is free the next reaction.

The free hydroxyl group is easily esterified through the reaction with an additional mole

of fatty acid at higher temperatures than the required to give the oxazoline. Three moles of water are obtained, and the AEPD has an effective functionality of 2 when reacted in this way.

Since three hydroxyl groups are existed with Tris Amino, the oxazoline diester is obtained when the amino alcohol reacts with three moles of an organic acid. This shows the normal functionality of 3 for Tris amino in a resin preparation. Four moles of water are obtained in this reaction.

Dibasic acids which will not form imides can be utilized to prepare bis(oxazolines), then an oxazoline can be formed from both carboxyls of adipic acid as shown. In addition, a divinyl compound can be prepared by the reaction of the bis(oxazoline) with two moles of formaldehyde.

The addition of carbon disulfide into AMP is readily accomplished at 100 C to give the mercapto-oxazoline, withe the liberatiom of heat and hydrogen sulfide.

Chapter 0 Preface First of all we need to praise the Lord Allah that given us the strength to finish this advanced chemistry report, moreover thanks to all the writers that already wrote some articles that has benefits to us which gave us both knowledge and perception to determine which is right and wrong. In similarly, we were originally given task by the lecturer to observing the corrosion inhibitor which the material we are using is the reinforced concrete structure. The main point of this writing is to determine which is our option is right or wrong according to the chemical reaction that happening between the material we used and the chemical material that will tried to damaged or even break up the structure. Moreover, we should find some accurate data that will provide our writing such as the results from research and study by some researcher. On the other hand, we did the report by doing the literature study which is the need to gather all the pieces of information based on articles that has evident from the reliable sources. Those article given us lot of knowledge and help us to finish the report. However, we decided to use the amino alcohol as our main inhibitor to prevent our material which is concrete from corrodes. In the first place, we got so much trouble in order to define the amino alcohol itself because it has so many sub-class which confusing us when do the research in internet and the articles. Furthermore, we determined which, what, where, when this amino alcohol use and quickly understand our main inhibitor and gain the lot of information about it. There are some problems as well about the chemical reaction because we had similar problem to determine which reaction that we should use in order to get the right reaction. After some researches we found that the right chemical reaction to use and immediately put it in our report. Finally our report is done and ready to read for all the readers, we hope our report can give all the readers knowledge and positive effects on them in respect of chemistry.

Chapter 3 Conclusion Corrosion inhibitors could be one of promising technique that used to restore the reinforced concrete structure to almost normal condition and of course it will reduce cost of maintenance and inconveniece of repairing it. Corrosion inhibitors are less need repairment, and if it does the cost could not more the normal repairment. However the used of corrosion inhibitors in repair systems is far less well-established then their application as admixture in new structures. Overall performance of surface applied organic and inorganic corrosion inhibitors intended to stop or at least reduce ongoing chloride induced corrosion cannot be considered as positive, this method also has at least some doubts on case of corrosion due to carbonation. But that doubts cannot really affect to the performance of this corrosion inhibitors. The main thing that should do by concrete repair industry is specify what kind of inhibitors that needed to the concrete repairment. Specify the required inhibitors concentration at the reinforcement and define method to measure how much the concentration needed to the concrete repairment. However the engineers or contractors or even the concrete repair industry should be aware of the fact that the performance of proprietary corrosion inhibitors in repair system didnt recorded yet under marketed systems under different trade names is not yet decumented by independant research work. Migratory Corrosion Inhibitors (MCI) and Vapor Phase Corrosion Inhibitors (VpCI) technologies provide dependable corrosion protection to reinforcing steel embedded in concrete, as shown in the multitude of case histories available. This method also has the advantages of preventing corrosion and providing surrounding protection area that untreated areas which they are directly in contact with. Chloride environment can be used mitigate corrosion by them. They also can be used to carbonation, as well as in other corrosive environments, unlike nitrite based inhibitors, which are generally only effective against chloride include corrosion. Another positive affect migrating corrosion inhibitors and vapor phase corrosion inhibitors are

economical to use, are environmentally friendly, and can be formatted into a variety of product types, ensuring the most suitable product for the application can be used. One of corrosion protection system will often include Migratory Corrosion Inhibitors and Vapor Phase Corrosion Inhibitors, galvanic protection and life time monitoring of the corrosion process. The competing mechanism of corrosion protection are supported by case histories of successful worldwide application.

References Corrosion Inhibitors for Steel in Concrete, B. Elsener, Faculty of Engineering, University of Cagliari (Italy) and Institute of Materials Chemistry and Corrosion, Swiss Federal Institute of Technology, Zrich.\ Angus Technical Data Sheet, Angus Chemical Company NEW TRENDS IN MIGRATING CORROSION INHIBITOR TECHNOLOGY FOR CORROSION PROTECTION OF EMBEDDED STEEL REINFORCEMENT,Boris Miksic, Jessica, Jackson Meyer, Alla Furman, Marlin Hanson. Sika Ferrogard 903, Corrosion Inhibitor Impregnating, Sika Ferrogard Co., November 2005. Acidic attack of cement based materials a review :research and test methods, Vladimr Zivica, 17 June 2004.