4 Pretreatment Objective When you have gone through this chapter you should be able to discuss methods of pretreatment used for surface preparation of some metals. Introduction In this chapter, different pretreatment methods used for surface preparation of steel, zinc and aluminium are discussed. This chapter will focus on pretreatment of steel as this is the most commonly used construction material of these three metals. The chapter begins with different kinds of degreasing methods. Degreasing is followed by dry mechanical preparation methods: manual and mechanical wire brushing, grinding and abrasive blasting. Subsequently, flame cleaning, which is a thermal pretreatment method, is discussed. The “dry” methods are followed by the “wet” methods: wet abrasive blasting, high pressure hosing and ultra high pressure water jetting. Pickling in acid solutions is a chemical pretreatment method, which is a part of the pretreatment process in hot galvanizing. After pickling, it is only natural to discuss chemical pretreatment. Under chemical pretreatment two methods are men- tioned: phosphatizing and chromatizing. Finally, rust removers and rust cleaning detergents based on phosphoric acid are discussed. These remove rust and mill scale and at the same time the surface is passivated, obtaining a certain degree of protection. Wash primers will also be discussed in this chapter as the phosphoric acid in the wash primer provides the surface with unique properties especially as a primer on zinc and aluminium. Cleaning and surface preparation Is cleaning and surface preparation the same? Yes, cleaning is a kind of surface preparation, but surface preparation is not always carried out for the purpose of cleaning. When a steel frame is phosphatised prior to powder coating, phosphatizing is a surface preparation method. Cleaning, which is a part of the surface preparation process, should be carried out in advance. In this chapter, mainly surface prepara- tion methods and working procedures are discussed in connection with surface preparation of iron and steel. But also treatment of zinc and aluminium are being discussed. 120 Corrosion prorectionPrior to painting or coating a steel surface, the surfaces should be cleaned for scale (mill scale) and rust. If galvanized materials are exposed outdoor without protection, corrosion prod- ucts (white rust) will develop on the surface over time. Prior to painting or applica- tion of any other coating, white rust must be removed and the zinc surface treated in order to obtain proper adhesion. Aluminium will protect itself by forming an oxide layer on the surface. If the aluminium is to be painted, the oxide layer will provide poor adhesion. Some plastic materials will deteriorate when exposed to sunlight and must be pretreated prior to painting, varnishing or lining. Contaminants such as oil, grease, wax, oil, soot, dust, sand or soil, i.e. every- thing that is usually called dirt, must be removed. The same goes for water-soluble salts (chlorides, sulphates) and condensation in the form of acid or alkaline com- pounds. It is important to remove any of these external contaminants prior to paint- ing and coating irrespective of the underlying substrate, If previously painted surfaces are to be repaired or repainted, any damaged paint must be removed completely or as much as is economically sound or neces- sary. In some cases, it may be necessary to remove all the damaged paint despite it may appear intact. This is especially the case when undercorrosion is suspected. The cleaner the surface, the more powerful are the resulting strength that binds the paint to the surface. The adhesion strength that applies in every tiny little bit of contact points between the surface and the coating will together form adhesion that can be measured over a certain area. (See chapter 13 regarding measuring adhe- sion). Especially in a corrosive environment, the adhesion between the substrate and the coating plays a vital role. It is very difficult if not impossible to clean a surface completely. The cost would be exorbitant. However, numerous practical tests as well as laboratory tests have proven that in the end it may also be very expensive to perform a too poor cleaning job. In many cases therefore you should ask yourself whether the cleaned surface is sufficiently clean or not. Le. sufficiently clean for further treatment, what are the conditions the final system will be exposed to, and what is the expected lifetime. Surface preparation is the most important single factor when a surface is to be protected by a film-forming material, e.g. paint. Good and proper surface prepa- ration will prolong the lifetime. The methods of surface preparation can be divided into three categories: 1. Degreasing and removal of oil, dirt, etc. 2. Removal of rust, mill scale and any cover adhering to the surface 3. Chemical processed layers with properties that passivate and improve the adhe- sion Anumber of factors in the surface preparation process are important for the choice of surface preparation method. These are The size of the subject The number of items The construction material The coating system (paint system) 4 Pretreatment 121Degreasing Phosphatizing Abrasive blasting Mill scale | Cleaning Pretreatment Both cleaning and pretreatment Figure 4.1 Degreasing Everybody knows how water on a greasy surface forms beads. Water on a poorly cleaned windscreen, on a newly polished car or on oily thin plates are all good examples of this. If these surfaces are cleaned sufficiently, i.e. removal of any wax and grease, and then applied with water, the water will again spread out over the surface and form a coherent film. Greasy surface - water drops form beads a Nor-greasy surface - water flows out onto the surface and forms an even film Figure 4.2 On this greasy surface the water drops will form beads while they flow out and form an even surface on the non-greasy surface This has to do with the surface tension and can be explained as follows: Solid substances, liquids and gasses in contact with each other exhibit attractive forces. Also individual substances exhibit attractive forces between the molecules that hold the substance together. These attractive forces also work between the sparkling drops and the greasy surface. In this case, the attractive forces between the mol- ecules in the water drops are stronger than between the water and grease on the surface. Le. the tension of the surface causes the water drops to contract because the surface tension of the water is higher than the surface tension of the grease. On clean surfaces on the other hand, the attractive forces between the water molecules and the surface molecules in a glass, a coating and steel are stronger than between the water molecules themselves. Therefore, the water drops are drawn over the surfaces and at the same time wetting the surface. I.e. the attractive forces of the clean surfaces are stronger than that of the water. When a surface is cleaned, the surface tension increases. Knowing the physics of surface tension it can be claimed that the higher the surface tension of a substrate, the better the adhesion of a coating to that substrate. Many kinds of degreasing methods exist, but all can be divided into two group: + Degreasing in or by solvents or in solvent vapours that dissolve grease + Degreasing in water-soluble chemicals that decompose or emulsify the grease. 122 Corrosion PROTECTIONWater-based Solvent-based r— T egreasing by steam Hosing ez Dipping Dipping Fe] LEE washing wth oes Use of high eneray Use of low energy Figure 4.3 Degreasing in water-soluble, alkaline chemicals In the case of alkaline degreasing not only oil and grease are removed, but also contaminants in the oil and grease. Combined with high pressure washing or high pressure jetting, also water-soluble salts are removed. Degreasing can be done by dipping in bath by open-air spraying by spraying in more or less closed chambers by scrubbing or brushing Before deciding upon degreasing agent, it should be ensured that the composition of the degreaser, will not harm the substrate to be degreased. Zinc and aluminium will be damaged if the degreaser is too alkaline, Also the types of fats and oils and other contaminants must be known prior to finding the correct degreasing agent. Most alkaline degreasers consist of chemical compounds as phosphates, hy- droxides and silicates. These are water-soluble. In most cases, the degreaser con- tains 0.5-5% surface-active compounds such as wetting agents and emulsifiers. Hydroxides, e.g. sodium hydroxide (caustic soda) are strongly alkaline. Their main purpose is to saponify animal fat and vegetable oil. Animal fat derives from animals whereas vegetable oil derives from plants. Saponification is the process used for producing soap. The animal fat reacts with the alkalis and develops into soluble soap, which is dissolved in hot water. The tensides are important during the degreasing process since the wetting agent reduces the surface tension of the liquid. The access of the liquid to the metal surface is enhanced and the fat is forced away or wound up just as we wind up a string, the so-called winding effect. The purpose of the emulsifier is to disperse the oil drops in the bath or in the case of degreasing by spraying the liquefied film. The result is an emulsion. When non-saponifying mineral oils and fats are present, the emulsifying agent penetrates to the surface and emulsifies the oils and fats. In this way, also mineral oil and fat are removed. 4 Pretreatment 123It is not a question of making the baths or the washing liquid as alkaline as possible. It has been proven that the ability of the degreasing solution to emulsify fat is more important than the ability to saponify animal fat and vegetable oil. Sodium silicate and sodium ortho silicate are alkaline compounds, which have good emul- sifying properties. Care must be taken not to use a too strong alkaline solution when degreasing zinc and aluminium. When degreasing iron and steel on the other hand, solutions with stronger alkalinity can be used, preferably with a pH value from 12 to 14. The baths should be hot. In some facilities, the liquid is even boiling. The baths should be agitated in order to enhance the degreasing action. By agitation is meant that the degreasing liquid is set in motion by stirring. Spraying is also used. The baths should be skimmed off to remove any fats and oils, which float on the surface. Heavily polluted baths must be exchanged. Washing with alkaline solutions is less efficient than dipping in liquid baths and spraying since the temperature will be lower. Only if none of the other methods can be used, washing by hand is done. After alkaline degreasing, it is important to rinse carefully with fresh water to remove any alkaline remnants before continuing pretreatment. Alkalis are etching and especially the hot solutions are dangerous. Skin and eyes must be protected from splashes of the alkaline solution. If by adcident skin or eyes are hit by splashes from the alkaline solution, rinse carefully with plenty of fresh water for a long time. Also acidic degreasing compounds exist, but these will not be discussed in this section. Use of emulsifying solvents Emulsifying solvents (engine degreasers) are concentrated solutions of organic sol- vents, emulsifying agents and water. Before use, the concentrate is often thinned with 4 to 10 parts of paraffin or white spirit. According to the size or the design of the object, the solvent can be applied by dipping, spraying or by brush. After the solvent has reacted for some minutes, the surfaces are washed down with water. The best result is obtained with hot water, e.g. high pressure hosing combined with hot steam. Also high pressure hosing with cold water can be used. If high pressure hosing is carried out with hot water, steam or a combination of these two methods, the greasy film left on the surface will be insignificant. Solvent-based degreasing Solvent-based degreasing may take place in liquid form in tubs in vapour form in tubs by washing with rags wetted with a suitable solvent Washing with rags wetted with solvents The method is not suited for cleaning of strongly greasy surfaces or mass-produced 124 Corrosion protectionparts or in the case of high requirements to cleanness. It is neither suitable as a degreasing method for complex constructions or areas where access is difficult. Itis important to notice that any water-soluble salts (sulphates, chlorides) present ‘on the surface are not removed by the solvents. The method may be suited for large constructions with only sporadically oil and grease. In these cases this method is used in order to avoid assembling high pres- sure hosing equipment. Furthermore, most of the solvents evaporate at a rapid rate and the surfaces are ready for further treatment as soon as they are dry. However, attention should be paid to the fact that a thin greasy film is often left on the surface after the solvents have evaporated from the surface. In order to ensure the best result, always use clean rags to avoid spreading the grease to otherwise clean surfaces. Solvents are often used for washing and degreasing purposes before further surface preparation in tanks and confined spaces. Working with solvents is a seri- ous hazard to health if proper ventilation is not provided and if the workforce do not wear proper safety equipment. Working with solvents therefore requires a com- bination of providing proper ventilation and proper safety equipment. Furthermore, when working with solvents the risk of explosion is enhanced. This is dealt with in more detail in chapter 14: safety, health and environment. Table 4.1 is a summary of solvents used for degreasing, including the health hazards they imply. Table 4.1 Solvents for degreasing [ a ] = Agent Description | Flash _—_| Explosion Toxicity | joint — | limit | White spirit - | Petroleum JApprox. 10.85 vol% [May cause | fraction with | 38°C skin eczema *\a boiling point | High flash| | | jof 150-200°¢ | 52°C | Toluene Transparent, [7° [1.36.8 voi |May cause | aromatic | skin eczema | | carbons | Xylene Transparent, | 27°C [1.06.0 vol.% [May cause aromatic skin eczema carbons Trichloroethylene Transparent, | None | Norlammable|Toxic. May strong-smeliing at room cause skin heavy liquid temperature eczema. Carcinogenic. Perchloroethylene | Similar to None |Norfiammabie|Toxic. May | trichloroethylene | cause skin | but has a higher eczema. boiling point | Carcinogenic. | 4 Prernearwent 125Dipping in solvents If a greasy object is dipped in solvents, a thin film of solvents will remain on the surface when the object is removed from the solvents. After a while the solvents will evaporate, but not all of the grease. Instead, some of it will remain on the surface as a thin greasy layer. Heavily polluted surfaces should also be agitated mechanically by brushing or scrubbing. Degreasing in trichloro ethylene vapours Within some areas of the surface preparation industry, degreasing in vapours from e.g. trichloro ethylene, tetrachloro ethylene and trichloro ethane is still a preferred degreasing method. It is most commonly used on plants that require cleaning of components in caskets, series or mass-produced goods and other small compo- nents, At the same time, these plants have high requirements to the cleanness after degreasing. Paint contractors sometimes have these facilities. Depending on the type of the material and production method, the choice is most often made between two types. of facilities: ‘ Facilities in which the components are lowered into a tub (the vapour area) by means of a crane or a hoist Facilities with a conveyor traverse The principles and operation of these two types of facilities are in short: In both types of facilities, heating elements in the bottom of the tubs causes the solvents to boil. The vapour generated fills the tub up to the cooling pipe. The tub remains clean all the time despite the solvents become polluted after each treat- ment. When lowering cold objects into the vapour, the vapour will condense on the surface of the material. The solvent together with dissolved oil and grease run off the material down to the bottom of the tub (liquid phase). The temperature of the object will soon be the same as that of the vapour and the surface will dry rapidly. Some facilities contain a reservoir for cold degreasing liquids. Any grease the vapour has not removed can be washed down in order to loosen the grease. Thereby, mechanical treatment is obtained. By spraying any dirt will also be removed and furthermore degreasing time can be prolonged. As previously stated, there are facilities in which the material is lowered into the tub by a crane or a hoist. A drawing of this type of facility is shown in Figure 4.4, which shows how a facility with a conveyor may look like. In principle, vapours from the chlorinated solvents should not rise any higher than to the cooling pipes. In case this occurs, exhausts have been mounted at the top of the tub. The purpose of these exhausts is to absorb any vapour on the way out of, the tub. When removing objects from the tub there will anyway be some amount of overflow of the vapour. Facilities, which are not in use, must be covered to prevent any spillage of 126 Corrosion PROTECTIONsolvent vapours. In Table 4.2 some types of solvents used for vapour degreasing can be found. Note that the higher the boiling point, the longer the degreasing time. Exhaust duct J— Flash-off zone Cooling pipes. Vapour zone T— Condensate Solvent — Heating zone Figure 4.4 Due to environment and health reasons use of chlorinated solvents is being phased out. Table 4.2 7 7 Chlorinated solvents | Type : | Boiling point °C Relative time of treatment | Methylene chloride | 40 - Trichloroethane | 74 — | Trichloroethylene 87 — | Perchloroethylene 124 a Mechanical and thermal surface preparation Almost everybody has tried to remove rust and old paint by wire brushes, scrapers, hammers or rotating and chipping equipment. Everybody experiences the same: It is a heavy and tiresome job. Ithas been attempted to quantify how much rust can be removed by wire brush- ing or scraping: By wire brushing, 5-10% of the total amount of rust can be removed By hard-metal scraper almost 1/3 of the rust is removed by scraping back and forth 30 times, or approx. 30-35% by scraping 45 times one way. In practice it is completely unrealistic to carry out scraping 45 times on the same spot. But the figures give a good indication of the efficiency. 4 Pretreatment 127When scraping or wire brushing manually, much force is put on the tool to remove as much rust as possible. The static strain of the body in combination with the dynamic strain when scraping and wire brushing back and forth is exhausting. Therefore, it is easy to end the job before the surface is sufficiently clean. Mechanical equipment will remove rust and old paint faster and more efficient than manual equipment. The equipment will execute the dynamic work, the rotating orchipping movement, whereas we perform the static work when we hold the equip- ment. Therefore, mechanical equipment with rotating wire brushes is used to re- move rust from large areas. The most high-powered equipment is efficient, but a high weight makes it heavy to handle. In confined spaces, dust from the rust developed during mechanical cleaning will remain in the air for a long time. Dust filter and safety glasses should always be used during work. Furthermore, adequate ventilation should be provided in con- fined spaces. Today, the major part of construction steel is delivered wheel-abrasive blast cleaned and shopprimed. Consequently, there is less need for wire brushing and scraping rust on new constructions. What should be treated is welding seams and any damage of the shopprimer. Usually it is small areas. If feasible, these areas are cleaned by abrasive blasting instead of wire brushing and scraping. Scraping, wire brushing and chipping are used as methods for removing rust and old paint on constructions, which are to be maintained by painting. These methods are only used on the condition that no underrust is hidden beneath the old paint film. In the case of underrust, the extent and amount should be established. Should large areas with underrust or corrosion be the case, a solution may be to abrasive blast clean the entire construction or part of it to the desired preparation grade. Abrasive blast cleaning Abrasive blast cleaning is a collective name for methods of which grains of differ- ent size are projected against the surface of a workpiece. The method is widely used within the craft and manufacturing industries and is an efficient way of cleaning or preparing surfaces prior to coating or lining. Abra- sive blast cleaning is also used for cleaning moulds for rubber and plastic materials and for cleaning and deburring of cast iron. Different kinds of methods for abrasive blast cleaning have long been used for decorating stones and glass. Ceramic can be decorated by blasting before it is finally fired. Concrete can be both cleaned and decorated. High tensile (or probably hardened) steel is shot-peened to reduce or adjust surface tensions. Springs and machine elements, which for example are exposed to torsion or bending movements are treated the same way. The treatment will prolong the lifetime of the elements. The method may also be used for shaping constructions into e.g. laminated springs and aircraft wings [1]. Now relevant methods and materials in connection with surface preparation of steel, zinc-coated steel, aluminium and concrete will be discussed. By equipment and facilities for abrasive blasting is meant machines, which are able to transport, accelerate and control the flow of an abrasive. 128 Corrosion PROTECTIONFigure 4.5 Stationary centrifugal blasting machine for profiles (beams, bar steel) and single pieces “To fil in fo filter bag ust and other contaminants Container for abrasive Recycled abrasive Centrifugal whee! Figure 4.6 Mobile self-propelled centrifugal blasting machine for cleaning of levelled surfaces (ship decks, tank tops, and similar) In principle, three methods exist: Pneumatic (driven by compressed air) methods in which the abrasive is mixed with compressed air in a mixing valve and a tube or hosing system. Subse- quently, the abrasive is blasted against the material in a fan-shaped jet. 4 Pretreatment 129Hydraulic methods where water from a high pressure aggregate with high ve- locity is blasted against the object (water jetting). To increase the efficiency of this method, an abrasive may be added to the water. Mechanical methods where the centrifugal force will actuate the abrasive di- rectly when it is fed from the centre and out to the periphery of the paddle wheel. The wheel subsequently projects the abrasive against the object (wheel blast cleaning). The abrasive is a grained or fluid substance, which is projected against an object to clean or prepare the surface. Abrasives can often be divided into the following main groups: Mineral abrasives Metallic abrasives Organic abrasives Mineral abrasives comprise the following subgroups: Natural mineral abrasives Sand quartz (prohibited in many countries) Garnet Olivine Synthetic mineral abrasives Coal slag (aluminium silicate) Iron furnace slag Nickel slag Aluminium oxide Ceramic glass Other types © Metallic abrasives comprise Cast-iron grit and shot Steel grit and shot Aluminium Other types Organic abrasives comprise - Plastics Nutt shells Water Ice crystals Carbon dioxide pellets Zinc-coated grain Some abrasives are unsuitable for recycling. Therefore, these abrasives are called disposable abrasives whereas abrasives which can be used several times are called recycled abrasives. ‘The factors mentioned below are important for the surface preparation process in connection with efficiency, quality, environment and economy: 130 Corrosion PROTECTIONParameters for abrasives Type Shape of grain Hardness, strength and tendency to generate dust Chemical composition Grain size and distribution Whether it is harmful to the organism (health hazard) Parameters for abrasive blast-cleaning equipment Air pressure and air volume Nozzle, type and size Equipment, type and size Nozzle handling, distance and angle to the object Abrasive and abrasive/air mixture Size of compressor and energy consumption Visibility and amount of dust Parameters for construction Steel quality Rust degree Contamination Design Cleanness and roughness Physical cleanness Chemical cleanness Roughness _ Miscellaneous , Facilities Accessibility to the surfaces. Climatic conditions Flame cleaning Flame cleaning has previously been a very common surface preparation method. Now wheel blast cleaned and primed steel has taken over resulting in construction stee] free of rust and mill scale, In most cases itis therefore only necessary to repair welding zones and any damage in the shopprimer and clean the surfaces prior to painting. The decline in the shipbuilding industry is one of the reasons that the use of flame cleaning is less widespread together with the fact that many ships are built of centrifugally blast cleaned and shopprimed steel. Flame cleaning is a suitable surface preparation method for large, exterior sur- faces of a ship's hull built of untreated steel. The capacity, however, is very low compared with abrasive blasting. Furthermore, abrasive blasting provides a cleaner surface. 4 Pretreatment 134Flame cleaning is a so-called thermal cleaning method. It is the flame and the heating of the surface that perform the job. The purpose of the method is To loosen as much mill scale as possible To loosen and transform the rust into less hazardous oxides as seen from a corrosion point of view To burn organic compounds such as oil, grease and similar To dry the steel surface To paint on a heated surface Flame cleaning is performed by moving a burner across the steel surface at a cer- tain rate. When heated, the expansion rate of the mill scale and rust is higher than that of steel. The tension from this expansion causes the mill scale to crack and loosen provided it does not adhere too well to the surface. Provided moisture is present in the crevices and beneath the mill scale, the water evaporation may also cause the mill scale to loosen. The surface temperature may reach approx. 150°C. This temperature does not cause any structural changes of the steel. The thickness of the material should be more than 5-6 mm. Flame cleaning does not remove all well adhering or loose rust or mill scale. Therefore, the process must always be followed by mechanical wire brushing. Thick layers of rust should be chipped off prior to flame cleaning. Abrasive blast cleaning and wire brushing have long been standardized surface preparation methods. Now also flame cleaning has been included in this standard. The standard is an international standard with the designation ISO 8501-1. The abbreviation used for flame cleaning in this standard is FL. By following up on jobs with flame cleaning, it has been possible to estimate how much mill scale and rust are removed from the steel surface. New steel of which the surface is almost covered by mill scale, A-steel, it should be possible to remove approx. 20% of the rust or millscale. If much or most of the mill scale has been loosened and the surface has rusted (B and C -steel) between 70-100% of the contaminants carr be loosened and removed. Flame cleaning facilitates painting on a heated substrate. If this possibility is to be utilized, final clean up must not take too long. It has been common practice to paint while the surface temperature has been between 30-50°C. In the case of repeated flame cleaning, allow the surface to cool. If not, heating takes place at a too slow rate and the tensions in the surface necessary to remove Tust and mill scale are not obtained. The operators should use personal safety equipment such as safety glass, gloves, etc. and necessary respiratory protection. Furthermore, fire and explosion hazard when using the equipment should be observed and general regulations followed. Water-based cleaning methods Wet abrasive blasting (slurry blasting) is a method, utilizing a mix of water and abrasives and is primarily used for cleaning surfaces or for removal or reducing the amount of dust from the abrasives or the substrate. Slurry blasting may also soften 132 CorROsION PROTECTIONthe surface. The water softens the surface or contaminants, enhancing the cleaning performance of the abrasives, e.g. removal of some types of antifouling on ship’s hulls. ‘The two main principles of slurry blasting are Blast cleaning using high pressure and water: The water accelerates the abrasives Slurry blasting using air and abrasives: The air pressure accelerates the abrasives, In the first principle, relatively much water is used compared to the abrasives. The water pressure is relatively high, in industrial contexts usually between 70-170 Mpa. The abrasives are drawn into the water stream through a hose or a pipe from the abrasive container (the ejector effect). In the other principle in which air pressure is utilized to convey and accelerate the abrasives and water, the supplied water, which usually derives from the water supply piping systems, is usually less than that of the first principle. The mixed air/ abrasive stream is fed from a blasting pot. The water is mixed inside the nozzle or just outside the nozzle orifice of the blasting nozzle. The velocity of the particle flow is reduced when the supplied water is accelerated and conveyed with the mix- ture. In addition to these principles there are systems in which abrasives and water are mixed in a container. The mixture is often dosed into a compressed air stream and through hoses conveyed to the nozzle. The recoil power can be substantial provided large quantities of water are used. The appearance of a wet abrasive blasted steel surface is during blasting and immediately after similar to the one observed in the case of dry abrasive blasting as the abrasives clean, cut and deform the surface the same way as dry abrasives. When the surface has dried off, the surface changes colour and gloss, i.e. flash rusting. Flash rust is a more or less adhering rust screen on the surface. After wet abrasive blasting, it may be necessary to wash down the surface to remove any slurry that may settle on the surface. This will prolong the time the surface is exposed to moisture and consequently formation of rust. Wet abrasive blasting will remove a large part of water-soluble contaminants. The American standard, SSPC-SP 12, describes the condition of untreated steel surfaces before and immediately after wet abrasive blasting. Making and selecting photos for the standard are in progress. Some paint manufacturers have their own standards, which have already been incorporated in the working procedures in many places. The standards also include photos of different rust degrees. High pressure water cleaning and water jetting When water without adding any kind of abrading material is used for cleaning surfaces, the ability of the water to clean a surface depends on the energy of the water when it hits the surface. This energy may vary a great deal. The hydro blast- ing methods therefore can be used for cleaning very different surfaces and materi- als with different coatings and types of contamination. In Norwegian there is no precise term for the methods only using water under pressure for cleaning. The usual term is most probably high pressure hosing, which 4 Pretreatment 133,comprises the methods from simple low pressure cleaning to ultra high pressure water jetting. In English, the term “hydro blasting”, “hydro jetting” and “water jetting” are found. It is important to distinguish between Jow pressure cleaning and high pressure water jetting. The standard from SSPC-SP 12 suggests several definitions on water pressure: Table 4.3 Definition of high pressure cleaning and high pressure water jetting according to the American standard (NACE/SSPC): [metre | Water pressure MPa Area of use | | Low pressure water cleaning | Lower than 34 For industrial and | | - LPWC | domestic use | | High pressure water cleaning | From 34 to 70 Heavy cleaning | | - HPWwC. | ] | High pressure water jetting | From 70-210 | Removal of paint, | | - HPWS | partly rust | | Ultra-high pressure water Higher than 210 Removal of coatings jetting - UHPWS and linings and rust | LPWC_ = Low Pressure Water Cleaning HPWC_ = High Pressure Water Cleaning HPWJ = High pressure Water Jetting UHPWJ = Ultra High Pressure Water Jetting ‘The following terms may also be used: LPWW_ = Low Pressure Water Washing HPWW. = High Pressure Water Washing HPH High Pressure Hydroblasting UHPH = Ultra High Pressure Hydroblasting Water jetting is used for cleaning different surfaces. In the case of concrete con- structions, any weak concrete can in addition to cleaning the surface be removed by water chiselling, and laying bare plus clean the reinforcement bars. A water jetted steel surface looks different than an abrasive blasted (dry blasting) surface or wet blasted steel surface. This is because abrasives have not been added to the water. When the abrasives hit the surface, the surface is chipped or deformed by the abrasives causing deformations in the surface, which reflect light. Such a surface will therefore appear bright and glossy. Even water under ultra high pressure does not cut or deform the steel as do abrasives. The lack of glossy surface deformations makes the surface look dull even before flash rusting. Steel of rust grade D with active pit corrosion will appear with a marbled or fissured look. If the corrosion products are washed away, the steel will get a light a whereas the surrounding areas will appear mat grey, brownish or almost lack. 134 Corrosion protectionThis appearance is different from what is seen after blasting with abrasives. With abrasive blasting the anodic pits are usually dark due to corrosion products left on the surface whereas the surrounding areas appear light and clean. Hydroblasted steel changes appearance at a rapid rate as the surface dries up and flash rust starts to develop. This means that some oxidizing of the steel has taken place. If the amount of flash rust is of a magnitude that the surface cannot meet the requirements to cleanness prior to repainting, the rust must be removed or reduced, e.g. by stiff brushes (piassave), synthetic sanding pads, wire brushes or with high pressure fresh water cleaning. High pressure cleaning is most suited for surfaces where the water can run off the cleaned surfaces. After cleaning some flash rust will occur, however, it is possible to obtain a cleaning degree down to light flash rusting. Of the dry methods only the mechanical methods will effectively remove heavy flash rusting from large areas. After cleaning by mean of the dry methods, the surfaces should be cleaned to remove the loosened flash rust. Light abrasive sweep blasting is often used to remove flash rust. Water jetting is an efficient method to remove water-soluble salts from corroded surfaces. Furthermore, oil and grease removed during water jetting become emulsi- fied. This effect does not exclude that requirements to degreasing prior to water jetting are specified. If the surface temperature of a steel surface is measured before and after water jetting, it is observed that the temperature has increased during water jetting. Two conditions have caused the temperature to rise: On its way through the high pres- sure unit (the pump), the water is supplied with the amount of energy necessary to obtain the water jetting pressure. Some of the energy is transformed into heat caus- ing the water temperature to rise. Some of the heat is then transferred to the steel. The main reason for the increase in temperature is also that the kinetic energy in the water will be transformed to heat when it hits the steel surface. The increase of the temperature can be high. The water evaporates at a more rapid rate and the sur- faces dries off more rapidly. Pickling Dipping of steel (iron) in diluted acids in order to remove rust has been known for a long time. The method is called pickling and today mostly known as a part of the pretreatment process of hot-dipped galvanizing of steel. Pickling is also a part of other galvanizing processes and when coating steel with other metals or conversion coatings. The method was previously used for removing rust and mill scale from steel plates and profiles prior to painting. In the USA, large facilities for pickling and shoppriming of steel could be found especially within the shipbuilding industry. In Norway, those types of facilities were very rarely found. However, one plant, which could handle small parts (profiles, etc.) up to a length of 16 metres and wide parts up to a length of 8 m, was put in operation at the beginning of the 70’ies. The process was divided into 5 stages: 4 Pretreatment 135Degreasing (hot alkaline solutions) Rinsing (fresh water) Pickling (diluted hydrochloric acid) Rinsing (fresh water) Passivation (hot, diluted phosphoric acid solution) WRU Degreasing, pickling and rinsing resulted in a very clean, but active surface, which flash rusted at a rapid rate. The workpiece was therefore dipped in a hot phosphoric acid solution immediately after final rinsing down. This process provided a thin, passivating phosphate layer on the surface even though this process is called non- film forming phosphatizing. The layer only provided temporary protection against corrosion, but the adhesion to the following coating was improved. While the workpiece was still hot, a shopprimer was applied and in some cases also anticorrosive oils were applied. The plant was only in operation for approximately one year. The result of the pre-treatment was very good, however, too expensive compared to the prices the wheel abrasive blast cleaning and priming facilities could offer. Furthermore, per- haps the largest group of customers, i.e. the oil industry, demanded the objects to be applied a zinc-rich primer or zinc-rich paint. This type of priming or painting requires a certain roughness of the substrate in order to obtain proper adhesion — i.e. a mechanical anchorage to the substrate is required. The surface of pickled steel is too smooth and will consequently result in a poor mechanical anchor pattern for most zinc-rich products. By contrast, most other paint types adhere well to pickled, possibly passivated steel. The pickling- process The various stages in the pickling process have now been covered in brief. We will subsequently take a closer look at various operations and baths. First the objects must be degreased. The choice of method depends on the type of object, the size, design and contamination present on the surface. Most of the methods mentioned in the section on degreasing can be used. Degreasing with rags is too demanding if the result should be satisfactory. In most cases old paint, mark- ing colours, etc. must be removed prior to degreasing. Some paints can also be loosened in a hot lye bath provided it is sufficiently alkaline, but abrasive blast cleaning is recommended. Before lowering the steel into the pickling bath, it must be free from grease and any paint that may hinder the pickling solution in getting into contact with the oxides (rust and mill scale). If degreasing is done by alkalis, any residues of these substances must be rinsed off carefully. The pickling solution consists of diluted acid. Any alkaline substance left on the steel will neutralize the acid. The result is that the acid will become more and more inefficient. Hydrochloric acid (HCI) and sulphuric acid H,SO, are the two acids that are generally used. In some cases, phosphoric acid H,PO, is used. The hydrochloric acid pickling solution is concentrated hydrochloric acid, app 33%, which is diluted with equal parts of water. The result is a solution of app 16%. Note: the acid must be added to the water, not the other way round. The 136 Corrosion PROTECTIONpickling solution is used at room temperature. Sulphuric acid is often used as 5% (by volume) in water. The temperatures of the baths are between 75-80°C. Phosphoric acid is used for pickling of steel in solutions of 10% either directly as the pickling solution or as passivation after hydrochloric acid pickling. The pickling bath is hot; the temperature is between 70- 80°. Ready-mixed, pickling solutions (10%) based on inhibited phosphoric acid are used for pickling (cleaning) of piping systems. The phosphoric acid pickling does not provide the steel surface with a proven phosphate layer, having a crystalline structure. The surface is merely passivated. The passivation will protect the surface against oxidizing (corrosion) for a short eriod. . The pickling time varies from some minutes to several hours depending on the mill scale and rust. Moving the workpieces around in the pickle bath will enhance the pickling process. The acid must remove rust and mill scale without attacking the steel to a considerable extent. Mill scale is composed of different types of iron oxides. At the core, the ferric oxide wustitt (FeO) is found. Outside a layer of magnetite (Fe,O,) is found, and farthest out, the ferric oxide haematite (Fe,O,) is found. Both magnetite and haematite are not very soluble in acids whereas the wustitt layer is easy to dissolve. Penetra- tion takes place through crevices in the brittle mill scale. At the same time the acids dissolves the wustitt they will get in contact with the steel and react with the steel. During this reaction, hydrogen gasses are developed. While gasses develop these can be observed as effervescence on the surface, caus- ing the mill scale to break. What is seen as rust on a surface, which has been exposed to humid air or water, especially in the presence of carbon dioxide (CO,) is the end-product in a process (corrosion) in which iron has dissolved. On the whole, this rust consists of ferric oxides plus more or less volumes of water (water of hydration). Chemists generally write this as Fe,O, - n H,O. Fe,O, is the ferric oxide and - n H,O indicates how much water of hydration is bound to the oxide. If it is only a thin, porous rust layer on the steel, which is to be pickled, the pickling solution will remove this layer. If on the other hand the layer is thick and dense, pickling will take longer. And even longer time if there are several layers of rust. Old rust often appears in layers and these layers are rather thick and dense. It is common that it takes longer for the pickling solution to “eat” through a thick and dense layer than through a thin and porous layer. In addition, it has turned out that the pickling only removes one layer at a time. Therefore it must start all over again for every new rust layer: Many rust layers give a longer pickling time. ‘As mentioned above development of hydrogen gasses is an indication that the steel is being attacked or dissolves. This is not desirable due to several reasons: First more acid is used. Secondly, the steel corrodes, often locally. The gas ascend- ing from the tub contains acid drops and may cause an unpleasant fog. Hydrogen gasses may penetrate the steel, making it brittle. This is called hydrogen embrittlement. To stop the attack on the steel from acids and to prevent unneces- sary use of acid, inhibitors are added. An average inhibitor is an organic compound called hexamine. Approximately 2 g of hexamine per litre is added to the pickling 4 Pretreatment 137solution. The additive does not prolong the pickling time significantly. Pickling is a process used in connection with application of metallic coatings. The main purpose of the process is to remove the very thin, often invisible film, which is left on the surface after pickling and washing. The bath consists of well diluted acids, alkalis (bases) or salts, often of the same type as in rinsing the subse- quent metal coating bath Chemical conversion coatings Phosphatizing Chemical conversion, i.e. to deposit a rather thin layer of metallic salts on the surface, is not a new process. During excavations from the time of the Roman Empire, objects made from iron with a coating of phosphate have been found, vivianite. This is far from a proven evidence that the Romans knew of the phosphatizing process since the discoveries was made in well slurry together with bones. ‘The discoveries made have lead to the theory that the water in the well slurry and which contains hydrogen sulphide has reacted with iron. In addition, calcium phosphate especially from the bones, have through several chemical reactions re- acted with ferrous sulphate (iron vitriol), developing ferrous phosphates (vivianite) and gipsym. Vivianite is a main constituent in an iron phosphate layer. If the Romans did not know of phosphatizing then at least Ch. de Bussy took out an English patent for phosphatizing of iron as protection against corrosion in the year 1864. In the same period, several others experimented with dipping iron in phosphoric acid or phosphate solutions. T.W. Coslett from Birmingham is never- theless recognised as the real founder of the phosphatizing technique. In 1906 he took out a patent for dipping cleaned iron and steel parts into diluted phosphoric acid, having a temperature close to the boiling point [1]. The insoluble metallic salts which are separated on the metal surface work as a passive layer, enhancing the adhesion for paint and varnishes. The various layers have different anticorrosive properties. A coat of zinc phosphate on the steel may hinder underrusting or rust from spreading if damage of the coating occurs. Iron, zinc and manganese phosphatizing are used as chemically converted lay- ers for steel. Iron and zinc phosphatizing will be discussed in more detail. Iron phosphatizing is used for products under low corrosion stresses. The treat- ment provides poor protection in case of outdoor exposure. For this reason, iron phosphate is rarely used as a coating on exterior constructions or facade steel even if overcoated or varnished. The phosphatizing process is usually carried out in four steps. The phosphatizing takes place in a solution of sodium phosphate, alkalipoly phosphate, surface-active compounds and accelerators. The weak acidic alkali phosphate solution has a pH value between ’3.5-6.0. The chemical compound is dissolved in water in a concen- tration of 1-2 per cent. The treatment can be done by dipping or spraying. For degreasing purposes the same acidic chemicals are used as for the phosphatizing. The degreasing properties of the acidic chemicals are not as good as those of the 138 Corrosion PROTECTION