L6-TGN-104 (Rev 1) Corrosion Painting Blasting Inspection Guideline
L6-TGN-104 (Rev 1) Corrosion Painting Blasting Inspection Guideline
L6-TGN-104 (Rev 1) Corrosion Painting Blasting Inspection Guideline
Contents
1) PURPOSE .......................................................................................................... 1
2) APPLICATION ................................................................................................... 2
3) INTRODUCTION ............................................................................................... 2
4) PROTECTION FROM CORROSION ..................................................................... 8
5) CATHODIC PROTECTION .................................................................................. 9
6) METAL AD POLYMER CORROSION/STRESS FAILURE ..................................... 14
7) PAINT ............................................................................................................. 19
8) TYPES OF PAINT COATINGS ............................................................................. 34
9) PAINT TESTING METHODS ............................................................................... 42
10) COATING METHODS ....................................................................................... 44
11) SURFACE BLASTING (Various Applications) ................................................... 50
12) INTERNATIONAL STANDARDS ....................................................................... 61
13) APPLICABLE DOCUMENTS .............................................................................. 62
14) GUIDELINE HISTORY ..................................................................................... 63
1) PURPOSE
The purpose of this guideline is to assist with the Third Party Inspection of Materials or Equipment at manufacturing
locations, in order to determine if the Materials or Equipment meet the Client’s expressed needs, expectations,
Purchase Order, call off, etc. placed on the manufacturer.
This guideline shall be read in conjunction with the specified revisions of applicable national or international Codes and
Standards; the Client’s specifications; the Manufacturers’ procedures; the Quality Plan and/or any other related
documents pertinent to the Order.
This document assists Inspectors in completing the inspection in accordance with the Client’s prescribed scope, it does
not determine the minimum or maximum range or scope of the inspection to be carried out. Hence elements of the
guide may not be applicable in all cases.
It is also intended to ensure that all relevant information is included in the Inspection Report in such a way that all the
issues relating to the Purchase Order, Contract, Manufacturing and Client requirements are correctly addressed and
documented.
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2) APPLICATION
This guideline is applicable to the inspection of new and refurbished equipment. The level of inspection also depends
on the complexity of the equipment involved. Hence, it is the responsibility of the Inspector to check the sections
described herein are relevant to their work.
Inspection during field installation of the fore-going equipment is outside the scope of this Technical Guideline Note.
3) INTRODUCTION
Corrosion
Corrosion is the gradual destruction of material, usually metals, by chemical reaction with its environment. In the most
common use of the word, this means electrochemical oxidation of metals in reaction with an oxidant such as oxygen.
Rusting, the formation of iron oxides is a well-known example of electrochemical corrosion. This type of damage
typically produces oxide(s) or salt(s) of the original metal. Corrosion can also occur in materials other than metals,
such as ceramics or polymers, although in this context, the term degradation is more common. Corrosion degrades the
useful properties of materials and structures including strength, appearance and permeability to liquids and gases.
Many structural alloys corrode merely from exposure to moisture in air, but the process can be strongly affected by
exposure to certain substances. Corrosion can be concentrated locally to form a pit or crack, or it can extend across a
wide area more or less uniformly corroding the surface. Because corrosion is a diffusion-controlled process, it occurs on
exposed surfaces. As a result, methods to reduce the activity of the exposed surface, such as passivation and
chromate conversion, can increase a material's corrosion resistance. However, some corrosion mechanisms are less
visible and less predictable.
Galvanic Corrosion
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Galvanic corrosion occurs when two different metals have physical or electrical contact with each other and are
immersed in a common electrolyte, or when the same metal is exposed to an electrolyte with different concentrations.
In a galvanic couple, the more active metal (the anode) corrodes at an accelerated rate and the more noble metal (the
cathode) corrodes at a retarded rate. When immersed separately, each metal corrodes at its own rate. What type of
metal(s) to use is readily determined by following the galvanic series. For example, zinc is often used as a sacrificial
anode for steel structures. Galvanic corrosion is of major interest to the marine industry and also anywhere water
(containing salts) contacts pipes or metal structures.
Factors such as relative size of anode, types of metal, and operating conditions (temperature, humidity, salinity, etc.)
affect galvanic corrosion. The surface area ratio of the anode and cathode directly affects the corrosion rates of the
materials. Galvanic corrosion is often utilised in sacrificial anodes.
Galvanic Series
In a given environment (one standard medium is aerated, room-temperature seawater), one metal will be either more
noble or more active than others, based on how strongly its ions are bound to the surface. Two metals in electrical
contact share the same electrons, so that the "tug-of-war" at each surface is analogous to competition for free
electrons between the two materials. Using the electrolyte as a host for the flow of ions in the same direction, the
active metal will take electrons from the noble one. The resulting mass flow or electrical current can be measured to
establish a hierarchy of materials in the medium of interest. This hierarchy is called a galvanic series and is useful in
predicting and understanding corrosion.
Corrosion Removal
Often it is possible to chemically remove the products of corrosion. For example, phosphorus acid in the form of navel
jelly is often applied to ferrous tools or surfaces to remove rust. Corrosion removal should not be confused with electro
polishing, which removes some layers of the underlying metal to make the surface smooth. For example, phosphoric
acid may also be used to electro polish copper but it does this by removing copper, not the products of copper
corrosion.
Resistance to Corrosion
Some metals are more intrinsically resistant to corrosion than others (for some examples, see galvanic series). There
are various ways of protecting metals from corrosion including painting, hot dip galvanising, and combinations of these.
Intrinsic Chemistry
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The materials most resistant to corrosion are those for which corrosion is thermodynamically unfavourable. Any
corrosion products of gold or platinum tend to decompose spontaneously into pure metal, which is why these elements
can be found in metallic form on Earth and have long been valued. More common "base" metals can only be protected
by more temporary means.
Some metals have naturally slow reaction kinetics, even though their corrosion is thermodynamically favourable. These
include such metals as zinc, magnesium, and cadmium. While corrosion of these metals is continuous and on-going, it
happens at an acceptably slow rate. An extreme example is graphite, which releases large amounts of energy upon
oxidation, but has such slow kinetics that it is effectively immune to electrochemical corrosion under normal conditions.
Passivation
Passivation refers to the spontaneous formation of an ultrathin film of corrosion products known as passive film, on the
metals surface that act as a barrier to further oxidation. The chemical composition and microstructure of a passive film
are different from the underlying metal. Typical passive film thickness on aluminium, stainless steels and alloys is
within 10 nanometres. The passive film is different from oxide layers that are formed upon heating and are in the
micrometre thickness range – the passive film recovers if removed or damaged whereas the oxide layer does not.
Passivation in natural environments such as air, water and soil at moderate pH is seen in such materials as aluminium,
stainless steel, titanium, and silicon.
Passivation is primarily determined by metallurgical and environmental factors. The effect of pH is summarised using
Pourbaix diagrams, but many other factors are influential. Some conditions that inhibit passivation include high pH for
aluminium and zinc, low pH or the presence of chloride ions for stainless steel, high temperature for titanium (in which
case the oxide dissolves into the metal, rather than the electrolyte) and fluoride ions for silicon. On the other hand,
unusual conditions may result in passivation of materials that are normally unprotected, as the alkaline environment of
concrete does for steel rebar. Exposure to a liquid metal such as mercury or hot solder can often circumvent
passivation mechanisms.
Pitting Corrosion
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Certain conditions, such as low concentrations of oxygen or high concentrations of species such as chloride, which
complete as anions, can interfere with a given alloy's ability to re-form a passivating film. In the worst case, almost all
of the surface will remain protected, but tiny local fluctuations will degrade the oxide film in a few critical points.
Corrosion at these points will be greatly amplified, and can cause corrosion pits of several types, depending upon
conditions. While the corrosion pits only nucleate under fairly extreme circumstances, they can continue to grow even
when conditions return to normal, since the interior of a pit is naturally deprived of oxygen and locally the pH
decreases to very low values and the corrosion rate increases due to an autocatalytic process. In extreme cases, the
sharp tips of extremely long and narrow corrosion pits can cause stress concentration to the point that otherwise tough
alloys can shatter; a thin film pierced by an invisibly small hole can hide a thumb sized pit from view. These problems
are especially dangerous because they are difficult to detect before a part or structure fails. Pitting remains among the
most common and damaging forms of corrosion in passivated alloys, but it can be prevented by control of the alloy's
environment.
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Intergranular Corrosion
Stainless steel can pose special corrosion challenges, since its passivating behaviour relies on the presence of a major
alloying component (chromium, at least 11.5%). Because of the elevated temperatures of welding and heat treatment,
chromium carbides can form in the grain boundaries of stainless alloys. This chemical reaction robs the material of
chromium in the zone near the grain boundary, making those areas much less resistant to corrosion. This creates a
galvanic couple with the well-protected alloy nearby, which leads to weld decay (corrosion of the grain boundaries in
the heat-affected zones) in highly corrosive environments.
Stainless steel is said to be sensitised if chromium carbides are formed in the microstructure. A typical microstructure
of a normalised type 304 stainless steel shows no signs of sensitisation while heavily sensitised steel shows the
presence of grain boundary precipitates. The dark lines in the sensitised microstructure are networks of chromium
carbides formed along the grain boundaries.
Special alloys, either with low carbon content or with added carbon "getters" such as titanium and niobium (in types
321 and 347, respectively), can prevent this effect, but the latter require special heat treatment after welding to
prevent the similar phenomenon of knifeline attack. As its name implies, corrosion is limited to a very narrow zone
adjacent to the weld, often only a few micrometres across, making it even less noticeable.
Crevice Corrosion
Corrosion in the crevice between the tube and tube sheet (both made of type-316 stainless steel) of a heat exchanger in a
seawater desalination plant.
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Crevice corrosion is influenced by the crevice type (metal-metal, metal-non-metal), crevice geometry (size, surface
finish), and metallurgical and environmental factors. The susceptibility to crevice corrosion can be evaluated with
ASTM standard procedures. A critical crevice corrosion temperature is commonly used to rank a material's resistance
to crevice corrosion.
Microbial Corrosion
Microbial corrosion, commonly known as Microbiologically Influenced Corrosion (MIC), is a corrosion caused or
promoted by microorganisms, usually chemoautotroph. It can apply to both metallic and non-metallic materials, in the
presence or absence of oxygen. Sulphate-reducing bacteria are active in the absence of oxygen (anaerobic); they
produce hydrogen sulphide, causing sulphide stress cracking. In the presence of oxygen (aerobic), some bacteria may
directly oxidise iron-to-iron oxides and hydroxides, other bacteria oxidise sulphur and produce sulphuric acid causing
biogenic sulphide corrosion. Concentration cells can form in the deposits of corrosion products, leading to localised
corrosion.
Accelerated Low-Water Corrosion (ALWC) is a particularly aggressive form of MIC that affects steel piles in seawater
near the low water tidemark. It is characterised by an orange sludge, which smells of hydrogen sulphide when treated
with acid. Corrosion rates can be very high and design corrosion allowances can soon be exceeded leading to
premature failure of the steel pile. Piles that have been coated and have cathodic protection installed at the time of
construction are not susceptible to ALWC. For unprotected piles, sacrificial anodes can be installed local to the affected
areas to inhibit the corrosion or a complete retrofitted sacrificial anode system can be installed. Affected areas can also
be treated electrochemically by using an electrode to first produce chlorine to kill the bacteria, and then to produce a
calcareous deposit, which will help shield the metal from further attack.
High-Temperature Corrosion
High-temperature corrosion is chemical deterioration of a material (typically a metal) as a result of heating. This non-
galvanic form of corrosion can occur when a metal is subjected to a hot atmosphere containing oxygen, sulphur or
other compounds capable of oxidising (or assisting the oxidation of) the material concerned. For example, materials
used in aerospace, power generation and even in car engines have to resist sustained periods at high temperature in
which they may be exposed to an atmosphere containing potentially highly corrosive products of combustion.
The products of high-temperature corrosion can potentially be turned to the advantage of the engineer. The formation
of oxides on stainless steels, for example, can provide a protective layer preventing further atmospheric attack,
allowing a material to be used for sustained periods at both room and high temperatures in hostile conditions. Such
high-temperature corrosion products, in the form of compacted oxide layer glazes, prevent or reduce wear during high-
temperature sliding contact of metallic (or metallic and ceramic) surfaces.
Metal Dusting
Metal dusting is a catastrophic form of corrosion that occurs when susceptible materials are exposed to environments
with high carbon activities, such as synthesis gas and other high CO environments. The corrosion manifests itself as a
break-up of bulk metal-to-metal powder. The suspected mechanism is firstly the deposition of a graphite layer on the
surface of the metal, usually from Carbon Monoxide (CO) in the vapour phase. This graphite layer is then thought to
form metastable M3C species (where M is the metal), which migrate away from the metal surface. However, in some
regimes no M3C species is observed indicating a direct transfer of metal atoms into the graphite layer.
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Surface Treatments
Applied Coatings
Galvanised Surface
Plating, painting, and the application of enamel are the most common anti-corrosion treatments. They work by
providing a barrier of corrosion-resistant material between the damaging environment and the structural material.
Aside from cosmetic and manufacturing issues, there are trade-offs in mechanical flexibility versus resistance to
abrasion and high temperature. Plating’s usually fail only in small sections, and if the plating is more noble than the
substrate (for example, chromium on steel), a galvanic couple will cause any exposed area to corrode much more
rapidly than an unplated surface would. For this reason, it is often wise to plate with active metal such as zinc or
cadmium. Painting by either roller or brush is more desirable for tight spaces; spray would be better for larger coating
areas such as steel decks and waterfront applications. Flexible polyurethane coatings, like Durabak-M26 for example,
can provide an anti-corrosive seal with a highly durable slip resistant membrane. Painted coatings are relatively easy to
apply and have fast drying times although temperature and humidity may cause drying times to vary.
Reactive coatings
If the environment is controlled (especially in recirculating systems), corrosion inhibitors can often be added to it.
These form an electrically insulating or chemically impermeable coating on exposed metal surfaces, to suppress
electrochemical reactions. Such methods obviously make the system less sensitive to scratches or defects in the
coating, since extra inhibitors can be made available wherever metal becomes exposed. Chemicals that inhibit corrosion
include some of the salts in hard water (Roman water systems are famous for their mineral deposits), chromates,
phosphates, polyaniline, other conducting polymers and a wide range of specially designed chemicals that resemble
surfactants (i.e. long-chain organic molecules with ionic end groups).
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Anodisation
Aluminium alloys often undergo a surface treatment. Electrochemical conditions in the bath are carefully adjusted so
that uniform pores several nanometres wide appear in the metal's oxide film. These pores allow the oxide to grow
much thicker than passivating conditions would allow. At the end of the treatment, the pores are allowed to seal,
forming a harder-than-usual surface layer. If this coating is scratched, normal passivation processes take over to
protect the damaged area.
Anodising is very resilient to weathering and corrosion, so it is commonly used for building facades and other areas
where the surface comes into regular contact with the elements. Whilst being resilient, it must be cleaned frequently. If
left without cleaning, panel edge staining will naturally occur.
Biofilm Coatings
A new form of protection has been developed by applying certain species of bacterial films to the surface of metals in
highly corrosive environments. This process increases the corrosion resistance substantially. Alternatively,
antimicrobial-producing bio films can be used to inhibit mild steel corrosion from sulphate-reducing bacteria.
5) CATHODIC PROTECTION
Cathodic protection (CP) is a technique to control the corrosion of a metal surface by making that surface the cathode
of an electrochemical cell. Cathodic protection systems are most commonly used to protect steel, water, and fuel
pipelines and tanks; steel pier piles, ships, and offshore oil platforms.
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Typical Sacrificial anode details and installation (hull of a ship and offshore jacket)
For effective CP, the potential of the steel surface is polarised (pushed) more negative until the metal surface has a
uniform potential. With a uniform potential, the driving force for the corrosion reaction is halted. For galvanic CP
systems, the anode material corrodes under the influence of the steel, and eventually it must be replaced. The
polarisation is caused by the current flow from the anode to the cathode, driven by the difference in electrochemical
potential between the anode and the cathode.
Anodic Protection
Anodic protection impresses anodic current on the structure to be protected (opposite to the cathodic protection). It is
appropriate for metals that exhibit passivity (e.g., stainless steel) and suitably small passive current over a wide range
of potentials. It is used in aggressive environments e.g. solutions of sulphuric acid.
Rate of Corrosion
A simple test for measuring corrosion is the weight loss method. The method involves exposing a clean weighed piece
of the metal or alloy to the corrosive environment for a specified time followed by cleaning to remove corrosion
products and weighing the piece to determine the loss of weight. The rate of corrosion (R) is calculated as
R = KW/(ρAt)
Where:
k is a constant
W is the weight loss of the metal in time t
A is the surface area of the metal exposed
ρ is the density of the metal (in g/cm³).
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Economic Impact
In 2002, the US Federal Highway Administration released a study titled Corrosion Costs and Preventive Strategies in
the United States on the direct costs associated with metallic corrosion in the US industry. In 1998, the total annual
direct cost of corrosion in the US was circa $276 billion (3.2% of the US gross domestic product, GDP).
Rust is one of the most common causes of bridge accidents. As rust has a much higher volume than the originating
mass of iron, its build-up can also cause failure by forcing apart adjacent parts. It was the cause of the collapse of the
Mianus river bridge in 1983, when the bearings rusted internally and pushed one corner of the road slab off its support.
Three drivers on the roadway at the time died as the slab fell into the river below. The following NTSB investigation
showed that a drain in the road had been blocked for road re-surfacing, and had not been unblocked; as a result,
runoff water penetrated the support hangers. Rust was also an important factor in the Silver Bridge disaster of 1967 in
West Virginia, when a steel suspension bridge collapsed within a minute, killing 46 drivers and passengers on the
bridge at the time.
Similarly, corrosion of concrete-covered steel and iron can cause the concrete to spall, creating severe structural
problems. It is one of the most common failure modes of reinforced concrete bridges. Measuring instruments based on
the half-cell potential can detect the potential corrosion spots before total failure of the concrete structure is reached.
Corrosion in Non-Metals
Most ceramic materials are immune to corrosion. The strong chemical bonds that hold them together leave very little
free chemical energy in the structure; they can be thought of as already corroded. When corrosion does occur, it is
almost always a simple dissolution of the material or chemical reaction, rather than an electrochemical process. A
common example of corrosion protection in ceramics is the lime added to soda-lime glass to reduce its solubility in
water; though it is not nearly as soluble as pure sodium silicate, normal glass does form sub-microscopic flaws when
exposed to moisture. Due to its brittleness, such flaws cause a dramatic reduction in the strength of a glass object
during its first few hours at room temperature.
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Corrosion of Polymers
Polymer degradation involves several complex and often poorly understood physiochemical processes. These are
strikingly different from the other processes discussed here, and so the term "corrosion" is only applied to them in a
loose sense of the word. Because of their large molecular weight, very little entropy can be gained by mixing a given
mass of polymer with another substance, making them generally quite difficult to dissolve. While dissolution is a
problem in some polymer applications, it is relatively simple to design against. A more common and related problem is
swelling, where small molecules infiltrate the structure, reducing strength and stiffness and causing a volume change.
Conversely, many polymers (notably flexible vinyl) are intentionally swelled with plasticisers, which can be leached out
of the structure, causing brittleness or other undesirable changes. The most common form of degradation, however, is
a decrease in polymer chain length. Mechanisms, which break polymer chains, are familiar to biologists because of
their effect on DNA: ionising radiation (most commonly ultraviolet light), free radicals, and oxidisers such as oxygen,
ozone, and chlorine. Ozone cracking is a well-known problem affecting natural rubber for example. Additives can slow
this process very effectively, and can be as simple as a UV-absorbing pigment (i.e., titanium dioxide or carbon black).
Plastic shopping bags often do not include these additives so that they break down more easily as litter.
Glass corrosion
Corrosion of Glasses
Glass disease is the corrosion of silicate glasses in aqueous solutions. It is governed by two mechanisms: diffusion-
controlled leaching (ion exchange) and hydrolytic dissolution of the glass network. Both mechanisms strongly depend
on the pH of contacting solution: the rate of ion exchange decreases with pH as 10−0.5pH whereas the rate of
hydrolytic dissolution increases with pH as 100.5pH.
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The overall corrosion rate is a sum of contributions from both mechanisms (leaching + dissolution) NR i=Nrxi+NRh.
Diffusion-controlled leaching (ion exchange) is characteristic of the initial phase of corrosion and involves replacement
of alkali ions in the glass by a hydronium (H3O+) ion from the solution. It causes an ion-selective depletion of near
surface layers of glasses and gives an inverse square root dependent of corrosion rate with exposure time. The
diffusion-controlled normalised leaching rate of cations from glasses (g/cm2d) is given by:
Where t is time, Di is the ith cation effective diffusion coefficient (cm 2/d), which depends on pH of contacting water as
Di = Di0x10–pH and ρ is the density of the glass (g/cm3).
Glass network dissolution is characteristic of the later phases of corrosion and causes a congruent release of ions into
the water solution at a time-independent rate in dilute solutions (g/cm 2d):
where rh is the stationary hydrolysis (dissolution) rate of the glass (cm/d). In closed systems the consumption of
protons from the aqueous phase increases the pH and causes a fast transition to hydrolysis. However, a further
saturation of solution with silica impedes hydrolysis and causes the glass to return to an ion-exchange, e.g. diffusion-
controlled regime of corrosion.
In typical natural conditions normalized corrosion rates of silicate glasses are very low and are of the order of 10−7–
10−5 g/(cm2d). The very high durability of silicate glasses in water makes them suitable for hazardous and nuclear
waste immobilisation.
Effect of addition of a certain glass component on the chemical durability against water corrosion of a specific base glass
(corrosion test ISO 719)
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There exist numerous standardised procedures for measuring the corrosion (also called chemical durability) of glasses
in neutral, basic, and acidic environments, under simulated environmental conditions, in simulated body fluid, at high
temperature and pressure, and under other conditions.
The standard procedure ISO 719 describes a test of the extraction of water-soluble basic compounds under neutral
conditions: 2g of glass, particle size 300–500μm, is kept for 60 minutes in 50ml de-ionised water of grade 2 at 98°C;
25ml of the obtained solution is titrated against 0.01 mol/l HCI solution. The volume of HCI required for neutralisation
is classified according to the table below.
Extracted Na2O Hydrolytic
Amount of 0.01M HCI needed to neutralize extracted basic oxides, ml
equivalent, μg class
< 0.1 < 31 1
0.1-0.2 31-62 2
0.2-0.85 62-264 3
0.85-2.0 264-620 4
2.0-3.5 620-1085 5
> 3.5 > 1085 >5
Hydrogen Embrittlement
Hydrogen embrittlement is the process by which various metals, most importantly high-strength steel, become brittle
and fracture following exposure to hydrogen. Hydrogen embrittlement is often the result of unintentional introduction
of hydrogen into susceptible metals during forming or finishing operations and increases cracking in the material. This
phenomenon was first described in 1875.
Hydrogen embrittlement is also used to describe the formation of zircaloy hydride. Use of the term in this context is
common in the nuclear industry.
Process
The mechanism starts with lone hydrogen atoms diffusing through the metal. At high temperatures, the elevated
solubility of hydrogen allows hydrogen to diffuse into the metal (or the hydrogen can diffuse in at a low temperature,
assisted by a concentration gradient). When these hydrogen atoms recombine in minuscule voids of the metal matrix
to form hydrogen molecules, they create pressure from inside the cavity they are in. This pressure can increase to
levels where the metal has reduced ductility and tensile strength up to the point where it cracks open (hydrogen
induced cracking, or HIC). High-strength and low-alloy steels, nickel and titanium alloys are most susceptible.
Austempered iron is also susceptible. Steel with an ultimate tensile strength of less than 1000MPa or hardness of less
than 30 HRC are not generally considered susceptible to hydrogen embrittlement. Jewett et al. reports the results of
tensile tests carried out on several structural metals under high-pressure molecular hydrogen environment. These tests
have shown that austenitic stainless steels, aluminium (including alloys), copper (including alloys, e.g. beryllium
copper) are not susceptible to hydrogen embrittlement along with few other metals. For example of a severe
embrittlement measured by Jewett, the elongation at failure of 17-4PH precipitation hardened stainless steel was
measured to drop from 17% to only 1.7% when smooth specimens were exposed to high-pressure hydrogen.
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Counteractions
If the metal has not yet started to crack, the condition can be reversed by removing the hydrogen source and causing
the hydrogen within the metal to diffuse out, possibly at elevated temperatures. Susceptible alloys, after chemical or
electrochemical treatments where hydrogen is produced, are often subjected to heat treatment to remove absorbed
hydrogen. There is a 4-hour time limit for baking out entrapped hydrogen after acid treating the parts. This is the time
between the end of acid exposure and the beginning of the heating cycle in the baking furnace. This per SAE AMS
2759/9 Section 3.3.3.1 which calls out the correct procedure for eliminating entrapped hydrogen.
In the case of welding, often pre- and post-heating the metal is applied to allow the hydrogen to diffuse out before it
can cause any damage. This is specifically done with high-strength steels and low alloy steel such as the
chrome/molybdenum/vanadium alloys. Due to the time needed to re-combine hydrogen atoms into the harmful
hydrogen molecules, hydrogen cracking due to welding can occur over 24 hours after the welding operation is
completed.
Products such as ferrosilicates can be used to treat surfaces normally subject to hydrogen embrittlement in order to
prevent it from taking place.
Related Phenomena
If steel is exposed to hydrogen at high temperatures, hydrogen will diffuse into the alloy and combine with carbon to
form tiny pockets of methane at internal surfaces like grain boundaries and voids. This methane does not diffuse out of
the metal, and collects in the voids at high pressure and initiates cracks in the steel. This selective leaching process is
known as hydrogen attack or high temperature hydrogen attack and leads to decarburisation of the steel and loss of
strength and ductility.
Copper alloys, which contain oxygen, can be embrittled if exposed to hot hydrogen. The hydrogen diffuses through the
copper and reacts with inclusions of Cu2O, forming H2O (water), which then forms pressurised bubbles at the grain
boundaries. This process can cause the grains to literally be forced away from each other, and is known as steam
embrittlement (because steam is produced, not because exposure to steam causes the problem).
Testing
There are two ASTM standards for testing embrittlement due to hydrogen gas. The standard ASTM F1459-06 Standard
Test Method for Determination of the Susceptibility of Metallic materials to Hydrogen Gas Embrittlement (HGE) Test.
uses a diaphragm loaded with a differential pressure. The test ASTM G142-98 (2004) Standard Test Method for
Determination of Susceptibility of Metals to Embrittlement in Hydrogen Containing Environments at high Pressure, High
temperature, or both, uses a cylindrical tensile specimen tested into an enclosure pressurised with hydrogen or helium.
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The stresses can be the result of the crevice loads due to stress concentration, or can be caused by the type of
assembly or residual stresses from fabrication (e.g. cold working); the residual stresses can be relieved by annealing.
Prevention
SCC is the result of a combination of three factors – a susceptible material, exposure to a corrosive environment, and
tensile stresses above a threshold. If you eliminate any one of these factors, SCC initiation becomes impossible. The
conventional approach to controlling the problem has been to develop new alloys that are more resistant to SCC. This
is a costly proposition and can require a massive time investment to achieve only marginal success.
Crack Growth
The subcritical nature of propagation may be attributed to the chemical energy released as the crack propagates. That
is:
Elastic energy released + chemical energy = surface energy + deformation energy
The crack initiates at KIscc and thereafter propagates at a rate governed by the slowest process, which most of the
time is the rate at which corrosive ions can diffuse to the crack tip. As the crack advances so, K rises (because crack
length appears in the calculation of stress intensity). Finally, it reaches KIc, whereupon fast fracture ensues and the
component fails. One of the practical difficulties with SCC is its unexpected nature. Stainless steels, for example, are
employed because under most conditions they are "passive", i.e. effectively inert. Very often one finds a single crack
has propagated while the rest of the metal surface stays apparently unaffected. The crack propagates perpendicular to
the applied stress.
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SCC caused the catastrophic collapse of the Silver Bridge in December 1967, when an eyebar suspension bridge across
the Ohio River at Point Pleasant, West Virginia, suddenly failed. The main chain joint failed and the whole structure fell
into the river, killing 46 people in vehicles on the bridge at the time. Rust in the eyebar joint had caused a stress
corrosion crack, which went critical as a result of high bridge loading and low temperature. The failure was exacerbated
by a high level of residual stress in the eyebar. The disaster led to a nationwide reappraisal of bridges.
Suspended ceilings in indoor swimming pools are safety-relevant components. As was demonstrated by the collapses of
the ceiling of the Uster (Switzerland) indoor swimming pool (1985) and again at Steenwik (Netherlands, 2001),
attention must be paid to selecting suitable materials and inspecting the state of such components. The reason for the
failures was stress corrosion cracking of metal fastening components made of stainless steel. The active chemical was
chlorine added to the water as a disinfectant.
A classic example of SCC is season cracking of brass cartridge cases, a problem experienced by the British army in
India in the early 19th century. It was initiated by ammonia from dung and horse manure decomposing at the higher
temperatures of the spring and summer. There was substantial residual stress in the cartridge shells as a result of cold
forming. The problem was solved by annealing the shells to ameliorate the stress.
Metals Attacked
Certain austenitic stainless steels and aluminium alloys crack in the presence of chlorides, mild steel cracks in the
presence of alkali (boiler cracking) and nitrates, copper alloys crack in ammoniacal solutions (season cracking). This
limits the usefulness of austenitic stainless steel for containing water with higher than little ppm content of chlorides at
temperatures above 50°C. Worse still, high-tensile structural steels crack in an unexpectedly brittle manner in a whole
variety of aqueous environments, especially containing chlorides. With the possible exception of the latter, which is a
special example of hydrogen cracking, all the others display the phenomenon of subcritical crack growth, i.e. small
surface flaws propagate (usually smoothly) under conditions where fracture mechanics predicts that failure should not
occur. That is, in the presence of a corrodent, cracks develop and propagate well below KIc. In fact, the subcritical
value of the stress intensity, designated as KIscc, may be less than 1% of KIc, as the following table shows:
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KIc KIscc
Alloy SCC environment
MN/m3/2 MN/m3/2
13Cr steel 60 3% NaCl 12
18Cr-8Ni 200 42% MgCl2 10
Cu-30Zn 200 NH4OH, pH7 1
Al-3Mg-7Zn 25 Aqueous halides 5
Ti-6Al-1V 60 0.6M KCl 20
Polymers Attacked
A similar process occurs in polymers, when products are exposed to aggressive chemicals such as acids and alkalis. As
with metals, attack is confined to specific polymers and particular chemicals. Thus, polycarbonate is sensitive to attack
by alkalis, but not by acids. On the other hand, acids readily degrade polyesters, and SCC is a likely failure mechanism.
Polymers are also susceptible to environmental stress cracking where attacking agents do not necessarily degrade the
materials chemically. Nylon is sensitive to degradation by acids, a process known as hydrolysis, and nylon mouldings
will crack when attacked by strong acids.
For example, the fracture surface of a fuel connector showed the progressive growth of the crack from acid attack (Ch)
to the final cusp (C) of polymer. In this case, the failure was caused by hydrolysis of the polymer by contact with
sulphuric acid leaking from a car battery. The degradation reaction is the reverse of the synthesis reaction of the
polymer:
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Cracks can be formed in many different elastomers by ozone attack, another form of SCC in polymers. Tiny traces of
the gas in the air will attack double bonds in rubber chains, with natural rubber, Styrene-butadiene rubber and NBR
being most sensitive to degradation. Ozone cracks form in products under tension, but the critical strain is very small.
The cracks are always oriented at right angles to the strain axis, so will form around the circumference in a rubber tube
bent over. Such cracks are very dangerous when they occur in fuel pipes because the cracks will grow from the outside
exposed surfaces into the bore of the pipe, so fuel leakage and fire may follow. The problem of ozone cracking can be
prevented by adding anti-ozonants to the rubber before vulcanisation. Ozone cracks were commonly seen in
automobile tyre sidewalls, but are now seen rarely thanks to the use of these additives. On the other hand, the
problem does recur in unprotected products such as rubber tubing and seals.
7) PAINT
Paint is any liquid, liquefiable, or mastic composition, which, after application to a substrate in a thin layer, is
converted to a solid film. It is most commonly used to protect colour or provide texture to objects.
Components
Binder, vehicle, or resins: The binder, commonly called the vehicle, is the fiL5-Forming component of paint. It is the
only component that must be present. Components listed below are included optionally, depending on the desired
properties of the cured film.
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The binder imparts adhesion and strongly influences such properties as gloss, durability, flexibility, and toughness.
Binders include synthetic or natural resins such as alkyds, acrylics, vinyl-acrylics, vinyl acetate/ethylene (VAE),
polyurethanes, polyesters, melamine resins, epoxy, or oils. Binders can be categorised according to the mechanisms for
drying or curing. Although drying may refer to evaporation of the solvent or thinner, it usually refers to oxidative cross-
linking of the binders and is indistinguishable from curing. Some paints form by solvent evaporation only, but most rely
on cross-linking processes.
Paints that dry by solvent evaporation and contain the solid binder dissolved in a solvent are known as lacquers. A solid
film forms when the solvent evaporates, and because the film can re-dissolve in solvent, lacquers are unsuitable for
applications where chemical resistance is important. Classic nitrocellulose lacquers fall into this category, as do non-
grain raising stains composed of dyes dissolved in solvent and more modern acrylic-based coatings such as 5-ball
Krylon aerosol. Performance varies by formulation, but lacquers generally tend to have better UV resistance and lower
corrosion resistance than comparable systems that cure by polymerisation or coalescence.
The paint type known as Emulsion in the UK and Latex in the USA is a water-borne dispersion of sub-micrometre
polymer particles. The term "latex" in the context of paint in the USA simply means an aqueous dispersion; Latex
rubber (the sap of the rubber tree that has historically been called latex) is not an ingredient. These dispersions are
prepared by emulsion polymerisation. Such paints cure by a process called coalescence where first the water, and then
the trace, or coalescing, solvent, evaporate and draw together and soften the binder particles and fuse them together
into irreversibly bound networked structures, so that the paint will not re-dissolve in the solvent/water that originally
carried it. The residual surfactants in paint as well as hydrolytic effects with some polymers cause the paint to remain
susceptible to softening and, over time, degradation by water. The general term of latex paint is usually used in the
USA, while the term emulsion paint is used for the same products in the UK and the term latex paint is not used at all.
These terms in their respective countries cover all paints that use synthetic polymers such as acrylic, vinyl acrylic
(PVA), styrene acrylic, etc. as binders.
Paints that cure by oxidative crosslinking are generally single package coatings. When applied, the exposure to oxygen
in the air starts a process that crosslinks and polymerises the binder component. Classic alkyd enamels would fall into
this category. Oxidative cure coatings are catalysed by metal complex driers such as cobalt naphthenate.
Paints that cure by polymerisation are generally one or two package coatings that polymerise by way of a chemical
reaction and which cure into a cross-linked film. Depending on composition, they may need to dry first, by evaporation
of solvent. Classic two package epoxies or polyurethanes would fall into this category.
There are paints called plastisols/organosols, which are made by blending PVC granules with a plasticiser. These are
stoved and the mix coalesces.
Other films are formed by cooling of the binder. For example, encaustic or wax paints are liquid when warm, and
harden upon cooling. In many cases, they will re-soften or liquefy if reheated.
Recent environmental requirements restrict the use of volatile organic compounds (VOCs), and alternative means of
curing have been developed, particularly for industrial purposes. In UV curing paints, the solvent is evaporated first,
and hardening is then initiated by ultraviolet light. In powder coatings, there is little or no solvent, and flow and cure
are produced by heating of the substrate after electrostatic application of the dry powder.
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Water is the main diluents for water-borne paints, even the co-solvent types.
Solvent-borne, also called oil-based, paints can have various combinations of organic solvents as the diluents, including
aliphatics, aromatics, alcohols, Ketones and white spirit. Specific examples are organic solvents such as petroleum
distillate, esters, glycol ethers, and the like. Sometimes volatile low-molecular weight synthetic resins also serve as
diluents.
Pigment or Filler: Pigments are granular solids incorporated in the paint to contribute colour. Fillers are granular
solids incorporated to impart toughness, texture, give the paint special properties, or to reduce the cost of the paint.
Alternatively, some paints contain dyes instead of or in combination with pigments.
Pigments can be classified as either natural or synthetic types. Natural pigments include various clays, calcium
carbonate, mica, silica, and talcs. Synthetics would include engineered molecules, calcined clays, blanc fixe,
precipitated calcium carbonate, and synthetic pyrogenic silica.
Hiding pigments, in making paint opaque, also protect the substrate from the harmful effects of ultraviolet light. Hiding
pigments include titanium dioxide, phthalo blue, red iron oxide, and many others.
Fillers are a special type of pigment that serve to thicken the film, support its structure and increase the volume of the
paint. Fillers are usually cheap and inert materials, such as diatomaceous earth, talc, lime, barytes, clay, etc. Floor
paints that will be subjected to abrasion may contain fine quartz sand as filler. Not all paints include fillers. On the
other hand, some paints contain large proportions of pigment/filler and binder.
Some pigments are toxic, such as the lead pigments that are used in lead paint. Paint manufacturers began replacing
white lead pigments with the less toxic substitute, titanium white (titanium dioxide), before the US Consumer Product
Safety Commission banned lead in paint for residential use in 1978. The titanium dioxide used in most paints today is
often coated with silica/alumina/zirconium for various reasons, such as better exterior durability, or better hiding
performance (opacity) promoted by more optimal spacing within the paint film.
Additives: Besides the three main categories of ingredients, paint can have a wide variety of miscellaneous additives,
which are usually added in small amounts, yet provide a significant effect on the product. Some examples include
additives to modify surface tension, improve flow properties, improve the finished appearance, increase wet edge,
improve pigment stability, impart anti-freeze properties, control foaming, control skinning, etc. Other types of additives
include catalysts, thickeners, stabilisers, emulsifiers, texturisers, adhesion promoters, UV stabilisers, flatteners (de-
glossing agents), biocides to fight bacterial growth, and the like.
Additives normally do not significantly alter the percentages of individual components in a formulation.
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Colour changing paints can also be made by adding halochrome compounds or other organic pigments. One patent
cites use of these indicators for wall coating applications for light coloured paints. When the paint is wet, it is pink in
colour but upon drying, it regains its original white colour. As cited in patent, this property of the paint enabled two or
multiple coats to be applied on a wall properly and evenly. The previous coat(s) having dried would be white whereas
the new wet coat would be distinctly pink. Ashland Inc. introduced foundry refractory coatings with similar principle in
2005 for use in foundries.
Electrochromic paints change colour in response to an applied electric current. Car manufacturer Nissan has been
reportedly working on an electrochromic paint, based on particles of paramagnetic iron oxide. When subjected to an
electromagnetic field the paramagnetic particles change spacing, modifying their colour and reflective properties. The
electromagnetic field would be formed using the conductive metal of the car body. Electrochromic paints can be
applied to plastic substrates as well, using a different coating chemistry. The technology involves using special dyes
that change conformation when an electric current is applied across the film itself. Recently, this new technology has
been used to achieve glare protection at the touch of a button in passenger airplane windows.
Application
Paint can be applied as a solid, a gaseous suspension (aerosol) or a liquid. Techniques vary depending on the practical
or artistic results desired.
As a solid (usually used in industrial and automotive applications), the paint is applied as a very fine powder, and then
baked at a high temperature. This melts the powder and causes it to adhere to the surface. The reasons for doing this
involve the chemistries of the paint, the surface itself, and perhaps even the chemistry of the substrate (the object
being painted). This is called "powder coating" an object.
As a gas or as a gaseous suspension, the paint is suspended in solid or liquid form in a gas that is sprayed on an
object. The paint sticks to the object. This is called "spray painting" an object. The reasons for doing this include:
The application mechanism is air and thus no solid object touches the object being painted;
The distribution of the paint is uniform, so there are no sharp lines;
It is possible to deliver very small amounts of paint;
A chemical (typically a solvent) can be sprayed along with the paint to dissolve together both the delivered
paint and the chemicals on the surface of the object being painted;
Some chemical reactions in paint involve the orientation of the paint molecules.
The application of the paint is fairly easy if done correctly. It is the prep work and order of operations that is tedious
and detailed. The first step when painting is to make sure that all furniture, pictures, tables, etc. are moved out of the
room and most importantly out of the work space. Next is to lay down tarps or drop cloths to protect flooring,
particularly from spills or splashes of paint. The next step, the wall preparation, is a detailed process, which could
involve anything from skim coating, sparkling, caulking, sanding, priming, taping, etc. After the prep work has been
completed, painting can begin. Usually the first step in painting should be the "cutting in phase". This phase includes
the brushwork around the edges, windows, doors, trims, mouldings, the ceiling and wall line, etc. It is up to the painter
what order the wall spaces are completed in. For instance, it does not matter if you cut in the ceiling or paint the
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In the liquid application, paint can be applied by direct application using brushes, paint rollers, blades, other
instruments, or body parts such as fingers and thumbs.
Rollers generally have a handle that allows for different lengths of poles to be attached, allowing painting at different
heights. Generally, roller application requires two coats for even colour. A roller with a thicker nap is used to apply
paint on uneven surfaces. Edges are often finished with an angled brush.
Using the finish flat one would most likely use a 1/2" nap roller
Using the finish eggshell one would most likely use a 3/8" nap roller
Using the finish satin or pearl one would most likely use a 3/8" nap roller
Using the finish semi-gloss or gloss one would most likely use a 3/16" nap roller
After liquid paint is applied, there is an interval during which it can be blended with additional painted regions (at the
"wet edge") called "open time." Adding white spirit, similar glycols such as Dowanol (propylene glycol ether) or open
time prolongers can extend the open time of an oil or alkyd-based emulsion paint. This can also facilitate the mixing of
different wet paint layers for aesthetic effect. Latex and acrylic emulsions require the use of drying retardants suitable
for water-based coatings.
Paint application by spray is the most popular method in the industry. In this method, paint is atomised by the force of
compressed air or by the action of high-pressure compression of the paint itself, and the paint is turned into small
droplets, which travel to the article, which is to be painted. Alternate methods are airless spray, hot spray, hot airless
spray, and any of these with an electrostatic spray included. There are numerous electrostatic methods available.
Dipping used to be the norm for objects such as filing cabinets, but this has been replaced by high-speed air turbine
driven bells with electrostatic spray. Car bodies are primed using cathodic elephoretic primer, which is applied by
charging the body depositing a layer of primer. The unchanged residue is rinsed off and the primer stoved.
Many paints tend to separate when stored, the heavier components settling to the bottom, and require mixing before
use. Some paint outlets have machines for mixing the paint by shaking the can vigorously for a few minutes.
The opacity and the film thickness of paint may be measured using a drawdown card.
Water-based paints tend to be the easiest to clean up after use; the brushes and rollers can be cleaned with soap and
water.
Proper disposal of left over paint is a challenge. Sometimes it can be recycled: Old paint may be usable for a primer
coat or an intermediate coat, and paints of similar chemistry can be mixed to make a larger amount of a uniform
colour.
To dispose of paint it can be dried and disposed of in the domestic waste stream, if it contains no prohibited
substances (see container). Disposal of liquid paint usually requires special handling and should be treated as
hazardous waste, and disposed of according to local regulations.
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Product Variants
Primer: a preparatory coating put on materials before painting. Priming ensures better adhesion of paint to the
surface, increases paint durability, and provides additional protection for the material being painted. It can also
be used to block and seal stains, or to hide a colour that is to be painted over.
Emulsion paint: a water-based paint used for painting interior or exterior surfaces.
Flat Finish: this is generally used on ceilings or walls that are in bad shape. This finish is more forgiving in
terms of hiding imperfections in your walls and covers greatly. However this finish provides no washability if
the wall becomes stained.
Matte Finish: this is very similar if not the same to the flat finish, but has washability and good coverage.
Eggshell Finish: this finish has some sheen to it, the equivalence to a shell on an egg. This finish provides great
washability, but shows some imperfections on walls. It is ideal for bathrooms because it offers not only
washability, but has enough shine so water will not stick to it and make it peel.
Pearl (Satin) Finish: this is very durable in terms of washability and resistance to moisture. It will offer the user
the full protection on their walls from dirt, moisture, stains, etc. This finish is ideal for bathrooms, furniture,
and kitchens, but will show even more imperfections on walls because of its strong shine (this finish is shinier
then eggshell).
Semi-Gloss Finish: this finish is typically used on trim to add detail, elegance, and to show off the wood work.
It is also used on doors and furniture. This is a very high shine, but provides the most protection from moisture
and stains on your walls. Obviously, this finish will show the imperfections on the wall tremendously. This finish
is generally used in schools and factories where washability and durability are the only considerations.
Varnish and shellac provide a protective coating without changing the colour. They are paints without pigment.
Wood stain: this is a type of paint that is very "thin," that is, low in viscosity, and formulated so that the
pigment penetrates the surface rather than remaining in a film on the surface. Stain is predominantly pigment
or dye and solvent with little binder, designed primarily to add colour without providing a surface coating.
Lacquer: this is usually a fast-drying solvent-based paint or varnish that produces an especially hard, durable
finish.
Enamel paint: this is a paint that dries to an especially hard, usually glossy, finish. Enamel paints sometimes
contain glass powder or tiny metal flake fragments instead of the colour pigments found in standard oil-based
paints. Enamel paint is sometimes mixed with varnish or urethane to increase shine as well as assist in its
hardening process.
A glaze is an additive used with paint to slow drying time and increase translucency, as in faux painting and art
painting.
A roof coating is a fluid applied membrane which has elastic properties that allows it to stretch and return to its
original shape without damage. It provides UV protection to polyurethane foam and is widely used as part of a
roof restoration system.
Inks are similar to paints, except they are typically made using finely ground pigments or dyes, and are
designed so as not to leave a thick film of binder.
Anti-graffiti coatings are used to defeat graffiti artists to deter the marking of surfaces. There are two
categories, sacrificial and non-bonding. Sacrificial coatings are clear coatings that allow the removal of graffiti,
usually by pressure washing the surface with high-pressure water, removing the graffiti, and the coating
(hence, sacrificed). They must be re-applied afterward for continued protection. This is most commonly used
on natural-looking masonry surfaces, such as statuary and marble walls, and on rougher surfaces that are
difficult to clean. Non-bonding coatings are clear, high-performance coatings, usually catalysed polyurethanes,
that allow the graffiti very little to bond to. After the graffiti is discovered, it can be removed with the use of a
solvent wash, without damaging the underlying substrate or protective coating. These work best when used on
smoother surfaces, and especially over other painted surfaces, including murals.
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EPOXY
Epoxy is a term used to denote both the basic components and the cured end products of epoxy resins, as well as a
colloquial name for the epoxide functional group. Epoxy resins, also known as polyepoxides are a class of reactive
prepolymers and polymers, which contain epoxide groups. Epoxy resins may be reacted (cross-linked) either with
themselves through catalytic homopolymerisation, or with a wide range of co-reactants including polyfunctional
amines, acids (and acid anhydrides), phenols, alcohols and thiols. These co-reactants are often referred to as
hardeners or curatives, and the cross-linking reaction is commonly referred to as curing. Reaction of polyepoxides with
themselves or with polyfunctional hardeners forms a thermosetting polymer, often with high mechanical properties,
temperature and chemical resistance. Epoxy has a wide range of applications, including metal coatings, use in
electronics/electrical components, high tension electrical insulators, fibre-reinforced plastic materials and structural
adhesives.
Epoxy Resin Chemistry: Epoxy resins are low molecular weight pre-polymers or higher molecular weight polymers,
which normally contain at least two epoxide groups. The epoxide group is also sometimes referred to as a Glycidyl or
Oxirane Group.
A wide range of epoxy resins are produced industrially. The raw materials for epoxy resin production are today largely
petroleum derived; although some plant derived sources are now becoming commercially available (e.g. plant derived
glycerol used to make epichlorohydrin).
Epoxy resins are polymeric or semi-polymeric materials, and as such rarely exist as pure substances, since variable
chain length results from the polymerisation reaction used to produce them. High purity grades can be produced for
certain applications, e.g. using a distillation purification process. One downside of high purity liquid grades is their
tendency to form crystalline solids due to their highly regular structure, which require melting to enable processing.
An important criterion for epoxy resins is the epoxide content. This is commonly expressed as the epoxide number,
which is the number of epoxide equivalents in 1kg of resin (Eq/kg), or as the equivalent weight, which is the weight in
grams of resin containing 1 mole equivalent of epoxide (g/mol). One measure may be simply converted to another:
The equivalent weight or epoxide number is used to calculate the amount of co-reactant (hardener) to use when curing
epoxy resins. Epoxies are typically cured with stoichiometric or near-stoichiometric quantities of curative to achieve
maximum physical properties.
As with other classes of thermoset polymer materials, blending different grades of epoxy resin, as well as use of
additives, plasticisers or fillers is common to achieve the desired processing and/or final properties, or to reduce cost.
Use of blending, additives and fillers is often referred to as formulating.
Bisphenol A Epoxy Resin: The most common and important class of epoxy resins are formed from reacting
epichlorohydrin with Bisphenol A to form diglycidyl ethers of Bisphenol A. The simplest resin of this class is formed
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Structure of bisphenol-A diglycidyl ether epoxy resin: n denotes the number of polymerised sub-units and is typically in the range
of 0 to 25
Increasing the ratio of Bisphenol A to epichlorohydrin during manufacture produces higher molecular weight linear
polyethers with glycidyl end groups, which are semi-solid to hard crystalline materials at room temperature depending
on the molecular weight achieved. As the molecular weight of the resin increases, the epoxide content reduces and the
material behaves more and more like a thermoplastic. Very high molecular weight polycondensates (ca. 30,000 –
70,000 g/mol) form a class known as phenoxy resins and contain virtually no epoxide groups (since the terminal epoxy
groups are insignificant compared to the total size of the molecule). These resins do however contain hydroxyl groups
throughout the backbone, which may also undergo other cross-linking reactions, e.g. with aminoplasts, phenoplasts
and isocyanates.
Bisphenol F Epoxy Resin: Bisphenol F may also undergo epoxidation in a similar fashion to bisphenol A. Compared
to DGEBA, bisphenol F epoxy resins have lower viscosity and a higher mean epoxy content per gram, which (once
cured) gives them increased chemical resistance.
Novolac Epoxy Resin: Reaction of phenols with formaldehyde and subsequent glycidylation with epichlorhydrin
produces epoxidised novolacs, such as Epoxy Phenol Novolacs (EPN) and Epoxy Cresol Novolacs (ECN). These are
highly viscous to solid resins with typical mean epoxide functionality of around 2 to 6. The high epoxide functionality of
these resins forms a highly cross-linked polymer network displaying high temperature and chemical resistance, but low
flexibility.
Aliphatic Epoxy Resin: Aliphatic epoxy resins are typically formed by glycidylation of aliphatic alcohols or polyols.
The resulting resins may be monofunctional (e.g. dodecyl glycidyl ether), difunctional (butanediol diglycidyl ether), or
higher functionality (e.g. trimethylolpropane triglycidyl ether). These resins typically display low viscosity at room
temperature (10-200mPa) and are often referred to as reactive diluents. They are rarely used alone, but are rather
employed to modify (reduce) the viscosity of other epoxy resins. This has led to the term ‘modified epoxy resin’ to
denote those containing viscosity-lowering reactive diluents. A related class is cycloaliphatic epoxy resin, which contains
one or more cycloaliphatic rings in the molecule (e.g. 3, 4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate).
This class also displays low viscosity at room temperature, but offers significantly higher temperature resistance than
the aliphatic epoxy diluents. However, reactivity is rather low compared to other classes of epoxy resin, and high
temperature curing using suitable accelerators is normally required.
Glycidyl Amine Epoxy Resin: Glycidyl amine epoxy resins are higher functionality epoxies, which are formed when
aromatic amines are reacted with epichlorohydrin. Important industrial grades are triglycidyl-p-aminophenol
(functionality 3) and N,N,N,N-tetraglycidyl-4,4-methylenebis benzylamine (functionality 4). The resins are low to
medium viscosity at room temperature, which makes them easier to process than EPN or ECN resins. This coupled with
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Curing may be achieved by the reaction of an epoxy with itself (homopolymerisation) or by forming a polymer with
polyfunctional curatives or hardeners. In principle, any molecule containing a reactive hydrogen atom may react with
the epoxide groups of the epoxy resin. Common classes of hardeners for epoxy resins include amines, acids, acid
anhydrides, phenols, alcohols and thiols. Relative reactivity (lowest first) is approximately in the order: phenol <
anhydride < aromatic amine < cycloaliphatic amine < aliphatic amine < thiol.
Whilst some epoxy resin/hardener combinations will cure at ambient temperature, many require heat, with
temperatures up to 150°C being common, and up to 200°C for some specialist systems. Insufficient heat during cure
will result in a network with incomplete polymerisation, and thus reduced mechanical, chemical and heat resistance.
Cure temperature should typically attain the glass transition temperature (T g) of the fully cured network in order to
achieve maximum properties. Temperature is sometimes increased in a step-wise fashion to control the rate of curing
and prevent excessive heat build-up from the exothermic reaction.
Hardeners which show only low or limited reactivity at ambient temperature, but which react with epoxy resins at
elevated temperatures are referred to as latent hardeners. When using latent hardeners, the epoxy resin and hardener
may be mixed and stored for some time prior to use, which is advantageous for many industrial processes. Very latent
hardeners enable one-component (1K) products to be produced, whereby the resin and hardener are supplied pre-
mixed to the end user and only require heat to initiate curing. One-component products generally have shorter shelf-
lives than standard 2-component systems, and products may require cooled storage and transport.
The epoxy curing reaction may be accelerated by addition of small quantities of accelerators. Tertiary amines,
carboxylic acids and alcohols (especially phenols) are effective accelerators. Bisphenol A is a highly effective and widely
used accelerator, but is now increasingly replaced due to health concerns with this substance.
Homopolymerisation: Epoxy resin may be reacted with itself in the presence of an anionic catalyst (a Lewis base
such as tertiary amines or imidazoles) or a cationic catalyst (a Lewis acid such as a boron trifluoride complex) to form a
cured network. This process is known as catalytic homopolymerisation. The resulting network contains only ether
bridges, and exhibits high thermal and chemical resistance, but is brittle and often requires elevated temperature to
effect curing, so finds only niche applications industrially. Epoxy homopolymerisation is often used when there is a
requirement for UV curing, since cationic UV catalysts may be employed (e.g. for UV coatings).
Amines: Polyfunctional primary amines form an important class of epoxy hardeners. Primary amines undergo an
addition reaction with the epoxide group to form a hydroxyl group and a secondary amine. The secondary amine can
further react with an epoxide to form a tertiary amine and an additional hydroxyl group. Kinetic studies have shown the
reactivity of the primary amine to be approximately double that of the secondary amine. Use of a difunctional or
polyfunctional amine forms a three-dimensional cross-linked network. Aliphatic, cycloaliphatic and aromatic amines are
all employed as epoxy hardeners. Amine type will alter both the processing properties (viscosity, reactivity) and the
final properties (mechanical, temperature and heat resistance) of the cured copolymer network. Thus, amine structure
is normally selected according to the application. Reactivity is broadly in the order aliphatic amines > cycloaliphatic
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Structure of TETA, a typical hardener. The amine (NH2) groups react with the epoxide groups of the resin during polymerisation.
Anhydrides: Epoxy resins may be cured with cyclic anhydrides at elevated temperatures. Reaction occurs only after
opening of the anhydride ring, e.g. by secondary hydroxyl groups in the epoxy resin. A possible side reaction may also
occur between the epoxide and hydroxyl groups, but this may be suppressed by addition of tertiary amines. The low
viscosity and high latency of anhydride hardeners makes them suitable for processing systems which require addition
of mineral fillers prior to curing, e.g. for high voltage electrical insulators.
Phenols: Polyphenols, such as bisphenol A or novolacs can react with epoxy resins at elevated temperatures (130-
180°C), normally in the presence of a catalyst. The resulting material has ether linkages and displays higher chemical
and oxidation resistance than typically obtained by curing with amines or anhydrides. Since many novolacs are solids,
this class of hardeners is often employed for powder coatings.
Thiols: Also known as mercaptans, thiols contain hydrogen which reacts very readily with the epoxide group, even at
ambient or sub-ambient temperatures. Whilst the resulting network does not typically display high temperature or
chemical resistance, the high reactivity of the thiol group makes it useful for applications where heated curing is not
possible, or very fast cure is required e.g. for domestic DIY adhesives and chemical rock bolt anchors. Thiols have a
characteristic odour, which can be detected in many two-component household adhesives.
History: The first commercial attempts to prepare resins from epichlorohydrin were made in 1927 in the United States.
Credit for the first synthesis of bisphenol-A-based epoxy resins is shared by Dr Pierre Castan of Switzerland and Dr S O
Greenlee of the United States in 1936. Ciba, Ltd. of Switzerland, which went on to become one of the three major
epoxy resin producers worldwide, licensed Dr Castan’s work. Ciba's epoxy business was spun off and later sold in the
late 1990s and is now the Advanced Materials business unit of Huntsman Corporation of the United States. Dr
Greenlee's work was for the firm of Devoe-Reynolds of the United States. Devoe-Reynolds, which was active in the
early days of the epoxy resin industry, was sold to Shell Chemical (now Momentive Specialty Chemicals, formerly
Hexion, Resolution Polymers and others).
Applications: The applications for epoxy-based materials are extensive and include coatings, adhesives and
composite materials such as those using carbon fibre and fibreglass reinforcements (although polyester, vinyl ester,
and other thermosetting resins are also used for glass-reinforced plastic). The chemistry of epoxies and the range of
commercially available variations allow cure polymers to be produced with a very broad range of properties. In general,
epoxies are known for their excellent adhesion, chemical and heat resistance, good-to-excellent mechanical properties
and very good electrical insulating properties. Many properties of epoxies can be modified (for example silver-filled
epoxies with good electrical conductivity are available, although epoxies are typically electrically insulating). Variations
offering high thermal insulation, or thermal conductivity combined with high electrical resistance for electronics
applications, are available.
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Polyester epoxies are used as powder coatings for washers, driers and other "white goods". Fusion Bonded Epoxy
Powder Coatings (FBE) are extensively used for corrosion protection of steel pipes and fittings used in the oil and gas
industry, potable water transmission pipelines (steel), and concrete reinforcing rebar. Epoxy coatings are also widely
used as primers to improve the adhesion of automotive and marine paints especially on metal surfaces where corrosion
(rusting) resistance is important. Metal cans and containers are often coated with epoxy to prevent rusting, especially
for foods like tomatoes that are acidic. Epoxy resins are also used for decorative flooring applications such as terrazzo
flooring, chip flooring, and coloured aggregate flooring.
Adhesives: Epoxy adhesives are a major part of the class of adhesives called "structural adhesives" or "engineering
adhesives" (that includes polyurethane, acrylic, cyanoacrylate, and other chemistries.) These high-performance
adhesives are used in the construction of aircraft, automobiles, bicycles, boats, golf clubs, skis, snowboards, and other
applications where high strength bonds are required. Epoxy adhesives can be developed to suit almost any application.
They can be used as adhesives for wood, metal, glass, stone, and some plastics. They can be made flexible or rigid,
transparent or opaque/coloured, fast setting or slow setting. Epoxy adhesives are better in heat and chemical
resistance than other common adhesives. In general, epoxy adhesives cured with heat will be more heat- and
chemical-resistant than those cured at room temperature. The strength of epoxy adhesives is degraded at
temperatures above 350 °F (177 °C).
Some epoxies are cured by exposure to UV light. Such epoxies are commonly used in optics, fibre optics, and
optoelectronics.
Industrial tooling and composites: Epoxy systems are used in industrial tooling applications to produce moulds,
master models, laminates, castings, fixtures, and other industrial production aids. This "plastic tooling" replaces metal,
wood and other traditional materials, and generally improves the efficiency and either lowers the overall cost or
shortens the lead-time for many industrial processes. Epoxies are also used in producing fibre-reinforced or composite
parts. They are more expensive than polyester resins and vinyl ester resins, but usually produce stronger and more
temperature-resistant composite parts.
An epoxy encapsulated hybrid circuit The interior of a pocket calculator. The dark lump of epoxy
on a printed circuit board in the centre covers the processor chip
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Flexible epoxy resins are used for potting transformers and inductors. By using vacuum impregnation on uncured
epoxy, winding-to-winding, winding-to-core, and winding-to-insulator air voids are eliminated. The cured epoxy is an
electrical insulator and a much better conductor of heat than air. Transformer and inductor hot spots are greatly
reduced, giving the component a stable and longer life than unspotted product.
Consumer and Marine Applications: Epoxies are sold in hardware stores, typically as a pack containing separate
resin and hardener, which must be mixed immediately before use. They are also sold in boat shops as repair resins for
marine applications. Epoxies typically are not used in the outer layer of a boat because they deteriorate by exposure to
UV light.
They are often used during boat repair and assembly, and then overcoated with conventional or two-part polyurethane
paint or marine-varnishes that provide UV protection.
There are two main areas of marine use. Because of the better mechanical properties relative to the more common
polyester resins, epoxies are used for commercial manufacture of components where a high strength/weight ratio is
required. The second area is that their strength, gap filling properties and excellent adhesion too many materials
including timber have created a boom in amateur building projects including aircraft and boats.
Normal gelcoat formulated for use with polyester resins and vinylester resins does not adhere to epoxy surfaces,
though epoxy adheres very well if applied to polyester resin surfaces. "Flocoat" that is normally used to coat the
interior of polyester fibreglass yachts is also compatible with epoxies.
Epoxy materials tend to harden somewhat more gradually, while polyester materials tend to harden quickly, particularly
if a lot of catalyst is used. The chemical reactions in both cases are exothermic. Large quantities of mix will generate
their own heat and greatly speed the reaction, so it is usual to mix small amounts, which can be used quickly.
While it is common to associate polyester resins and epoxy resins, their properties are sufficiently different that they
are properly treated as distinct materials. Polyester resins are typically low strength unless used with a reinforcing
material like glass fibre, are relatively brittle unless reinforced, and have low adhesion. Epoxies, by contrast, are
inherently strong, somewhat flexible and have excellent adhesion. However, polyester resins are much cheaper.
Epoxy resins typically require a precise mix of two components which form a third chemical. Depending on the
properties required, the ratio may be anything from 1:1 to over 10:1, but in every case, they must be mixed exactly.
The final product is then a precise thermosetting plastic. Until they are mixed, the two elements are relatively inert,
although the 'hardeners' tend to be more chemically active and should be protected from the atmosphere and
moisture. The rate of the reaction can be changed by using different hardeners, which may change the nature of the
final product, or by controlling the temperature.
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Aerospace Applications: In the aerospace industry, epoxy is used as a structural matrix material, which is then
reinforced by fibre. Typical fibre reinforcements include glass, carbon, Kevlar, and boron. Epoxies are also used as
structural glue. Materials like wood and others that are 'low-tech' are glued with epoxy resin.
Industry
As of 2006, the epoxy industry amounts to more than US$5 billion in North America and about US$15 billion worldwide.
The Chinese market has been growing rapidly, and accounts for more than 30% of the total worldwide market. It is
made up of approximately 50–100 manufacturers of basic or commodity epoxy resins and hardeners.
These commodity epoxy manufacturers mentioned above typically do not sell epoxy resins in a form usable to smaller
end users, so there is another group of companies that purchase epoxy raw materials from the major producers and
then compounds (blends, modifies, or otherwise customises) epoxy systems from these raw materials. These
companies are known as "formulators". These formulators produce the majority of the epoxy systems sold and they
comprise over 60% of the dollar value of the epoxy market. There are hundreds of ways that these formulators can
modify epoxies—by adding mineral fillers (talc, silica, alumina, etc.), by adding flexibilisers, viscosity reducers,
colorants, thickeners, accelerators, adhesion promoters, etc. These modifications are made to reduce costs, to improve
performance, and to improve processing convenience. As a result, a typical formulator sells dozens or even thousands
of formulations — each tailored to the requirements of a particular application or market.
Impacted by the global economic slump, the epoxy market size declined to $15.8 billion in 2009, almost to the level of
2005. In some regional markets, it even decreased nearly 20%. The current epoxy market is experiencing growth as
the global economy revives. With an annual growth rate of 3.5 - 4% the epoxy market is expected to reach $17.7
billion by 2012 and $21.35 billion by 2015. Higher growth rate is foreseen thereafter due to stronger demands from
epoxy composite market and epoxy adhesive market.
Health Risks: The primary risk associated with epoxy use is often related to the hardener component and not to the
epoxy resin itself. Amine hardeners in particular are generally corrosive, but may also be classed toxic and/or
carcinogenic/mutagenic. Aromatic amines present a particular health hazard (most are known or suspected
carcinogens), but their use is now restricted to specific industrial applications, and safer aliphatic or cycloaliphatic
amines are commonly employed.
Liquid epoxy resins in their uncured state are mostly classed as irritants to the eyes and skin, as well as being toxic to
aquatic organisms. Solid epoxy resins are generally safer than liquid epoxy resins, and many are classified non-
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Failure of Paint
The main reasons of paint failure after application on surface are the applicator and improper treatment of surface.
Application Defects can be attributed to:
Dilution
This usually occurs when the dilution of the paint is not done as per the manufacturer’s recommendation.
There can be a case of over dilution and under dilution, as well as dilution with the incorrect diluents.
Contamination
Foreign contaminants added without the manufacturer’s consent which results in various film defects.
Peeling/Blistering
Most commonly due to improper surface treatment before application and inherent moisture/dampness being
present in the substrate
Chalking
Chalking is the progressive powdering of the paint film on the painted surface. The primary reason for the
problem is polymer degradation of the paint matrix due to exposure of UV radiation in sunshine and
condensation from dew. The degree of chalking varies as epoxies react quickly while acrylics and
polyurethanes can remain unchanged for long periods. The degree of chalking can be assessed according to
International Standard ISO 4628 Part 6 or 7 or American Society of Testing and Materials (ASTM) Method
D4214 (Standard Test Methods for Evaluating the Degree of Chalking of Exterior Paint Films).
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Chalking Images
• Cracking
Cracking of paint film is due to the unequal expansion or contraction of paint coats. It usually happens when
the coats of the paint are not allowed to cure/dry completely before the next coat is applied. The degree of
cracking can be assessed according to International Standard ISO 4628 Part 4 or ASTM Method D661
(Standard Test Method for Evaluating Degree of Cracking of Exterior Paints).
• Erosion
Erosion is very quick chalking. It occurs due to external agents like air, water etc. It can be evaluated using
ASTM Method ASTM D662 (Standard Test Method for Evaluating Degree of Erosion of Exterior Paints).
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Dangers
Volatile Organic Compounds (VOCs) in paint are considered harmful to the environment and especially for people
who work with them on a regular basis. Exposure to VOCs has been related to organic solvent syndrome, although this
relation has been somewhat controversial.
In the US, environmental regulations, consumer demand, and advances in technology led to the development of low-
VOC and zero-VOC paint and finishes. These new paints are widely available and meet or exceed the old high-VOC
products in performance and cost-effectiveness while having significantly less impact on human and environmental
health.
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The resin and hardener part together is known as the "Binder". As the name indicates, in Fusion bonded epoxy
coatings the resin part is an "epoxy" type resin. “Epoxy” or “Oxirane” structures contain a three membered cyclic ring
— one oxygen atom connected to two carbon atoms - in the resin molecule. This part is the most reactive group in the
epoxy resins. Most commonly used FBE resins are derivatives of bisphenol and epichlorohydrin. However, other types
of resins (for example bisphenol F type) are also commonly used in FBE formulations to achieve various properties,
combinations or additions. Resins are also available in various molecular lengths, to provide unique properties to the
final coating.
The second most important part of FBE coatings is the curing agent or hardener. Curing agents react either with the
epoxy ring or with the hydroxyl groups, along the epoxy molecular chain. Various types of curing agents, used in FBE
manufacture, include dicyandiamide, aromatic amines, aliphatic diamines, etc. The selected curing agent determines
the nature of the final FBE product — its cross linking density, chemical resistance, brittleness, flexibility etc. The ratio
of epoxy resins and curing agents in a formulation is determined by their relative equivalent weights.
In addition to these two major components, FBE coatings include fillers, pigments, extenders and various additives, to
provide desired properties. These components control characteristics such as permeability, hardness, colour, thickness,
gouge resistance etc. All of these components are normally dry solids, even though small quantities of liquid additives
may be used in some FBE formulations. If used, these liquid components are sprayed into the formulation mix during
pre-blending in the manufacturing process.
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The components of the FBE formulation are weighed and pre-blended in high-speed mixers. The mix is then
transferred to a high-shear extruder. FBE extruders incorporate a single or dual screw setup, rotating within a fixed
clamshell barrel. A temperature range from 50°C to 100°C is used within the extruder barrel. This setup compresses
the FBE blend, while heating and melting it to a semi-liquid form. During this process, the ingredients of the molten
mix are dispersed thoroughly. Because of the fast operation of the extruder and relatively low temperature within the
barrel, the epoxy and hardener components will not undergo a significant chemical reaction. The molten extrudate then
passes between cold-rollers and becomes a solid, brittle sheet. It then moves to a “Kibbler”, which chops it into smaller
chips. These chips are ground, using high speed grinders (classifiers) to a particle size of less than 150 µm (standard
specifications requires 100% pass through in 250µm sieves and maximum 3% retains in 150 µm sieve). The final
product is packaged in closed containers, with particular care given to avoid moisture contamination. Normal storage
temperatures of FBE powder coatings are below 25°C (77°F) in air-conditioned warehouses.
The advantage of pipe and rebar is that their round shape allows continuous linear application over the exterior
surface, while the parts are moved in a conveyor through the powder application booth, ensuring high throughput. On
fittings, etc., the coating is applied by manual spray guns. Another method of application is "fluid-dip" process, in which
the heated components are dipped in a fluidised powder bed (see below).
It is important to remove grease or oil contamination prior to blast cleaning. Solvent cleaning, burn-off, etc., are
commonly used for this purpose. In the blast cleaning process, compressed air (90 to 110psi/610 to 760kPa) is used to
force an abrasive onto the surface to be cleaned. Aluminium oxide, steel grit, steel shot, garnet, coal slag, etc. are the
frequently used abrasives. Another method of blast cleaning is centrifugal blast cleaning, which is especially used in
cleaning the exterior of pipe. In this method, abrasive is thrown to the rotating pipe body, using a specially designed
wheel, which is rotated at high speed, while the abrasive is fed from the centre of the wheel.
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Standard coating thickness range of stand-alone FBE coatings is between 250 to 500µm, even though lower or higher
thickness ranges might be specified, depending on service conditions. The molten powder ‘flows’ into the profile and
bonds with the steel. The molten powder will become a solid coating, when the ‘geltime’ is over, which usually occurs
within a few seconds after coating application. The resin part of coating will undergo cross-linking, which is known as
“curing” under the hot condition. Complete curing is achieved either by the residual heat on the steel, or by the help of
additional heating sources. Depending on the FBE coating system, full cure can be achieved in less than one minute or
a few minutes in case of long cure FBEs, which are used for internal pipe coating applications.
Rebars are coated in a similar manner to a coating application, on the exterior of pipes. For FBE coating applications on
the interior of pipe surface, a lance is used. The lance enters into the pre-heated pipe, and starts spraying the powder
from the opposite end, while the pipe is being rotated on its axis and the lance pulls out in a pre-determined speed.
On fittings such as Tees, elbows, bends, etc., powder can be sprayed using handheld spray guns. Small sized fittings
can also be coated by dipping in a fluidised bed of powder, after heating the steel to the required powder application
temperature. After field welding of the pipe ends, FBE can be applied on the weld area as well.
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POWDER COATING
Typical powder coating process for pipe Powder coated bicycle frames and parts
Powder coating is a type of coating that is applied as a free-flowing, dry powder. The main difference between a
conventional liquid paint and a powder coating is that the powder coating does not require a solvent to keep the binder
and filler parts in a liquid suspension form. The coating is typically applied electrostatically and is then cured under heat
to allow it to flow and form a "skin". The powder may be a thermoplastic or a thermoset polymer. It is usually used to
create a hard finish that is tougher than conventional paint. Powder coating is mainly used for coating of metals, such
as household appliances, aluminium extrusions, and automobile and bicycle parts. Newer technologies allow other
materials, such as MDF (medium-density fibreboard) to be powder coated using different methods.
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While powder coatings have many advantages over other coating processes, there are some disadvantages to the
technology. While it is relatively easy to apply thick coatings, which have smooth, texture-free surfaces, it is not as
easy to apply smooth thin films. As the film thickness is reduced, the film becomes more and more orange peeled in
texture due to the particle size and glass transition temperature (T G) of the powder. On smaller jobs, the cost of
powder coating will be higher than spray painting.
For optimum material handling and ease of application, most powder coatings have a particle size in the range of 30 to
50μm and a TG around 200°C. For such powder coatings, film build-ups of greater than 50μm may be required to
obtain an acceptably smooth film. The surface texture, which is considered desirable or acceptable, depends on the
product. Many manufacturers actually prefer to have a certain degree of orange peel since it helps to hide metal
defects that have occurred during manufacture, and the resulting coating is less prone to showing fingerprints.
There are specialised operations where powder coatings of less than 30μm or with a TG below 40°C are used in order
to produce smooth thin films. One variation of the dry powder coating process, the Powder Slurry process, combines
the advantages of powder coatings and liquid coatings by dispersing very fine powders of 1 – 5μm particle size into
water, which then allows very smooth, low film thickness coatings to be produced.
Powder coatings have a major advantage in that the overspray can be recycled. However, if multiple colours are being
sprayed in a single spray booth, this may limit the ability to recycle the overspray.
The most common polymers used are polyester, polyurethane, polyester-epoxy (known as hybrid), straight epoxy
(fusion-bonded epoxy) and acrylics.
Production:
1. The polymer granules are mixed with hardener, pigments and other powder ingredients in a mixer
2. The mixture is heated in an extruder
3. The extruded mixture is rolled flat, cooled and broken into small chips
4. The chips are milled and sieved to make a fine powder
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Chemical pre-treatments involve the use of phosphates or chromates in submersion or spray application. These often
occur in multiple stages and consist of degreasing, etching, de-smutting, various rinses and the final phosphating or
chromating of the substrate. The pre-treatment process both cleans and improves bonding of the powder to the metal.
Recent additional processes have been developed that avoid the use of chromates, as these can be toxic to the
environment. Titanium zirconium and silcates offer similar performance against corrosion and adhesion of the powder.
In many high-end applications, the part is electro-coated following the pre-treatment process, and subsequent to the
powder coating application. This has been particularly useful in automotive and other applications requiring high-end
performance characteristics.
Another method of preparing the surface prior to coating is known as abrasive blasting or sandblasting and shot
blasting. Blast media and blasting abrasives are used to provide surface texturing and preparation, etching, finishing,
and degreasing for products made of wood, plastic, or glass. The most important properties to consider are chemical
composition and density; particle shape and size; and impact resistance.
Silicon carbide grit blast medium is brittle, sharp, and suitable for grinding metals and low-tensile strength, non-metallic
materials. Plastic media blast equipment uses plastic abrasives that are sensitive to substrates such as aluminium, but
still suitable for de-coating and surface finishing. Sand blast medium uses high-purity crystals that have low-metal
content. Glass bead blast medium contains glass beads of various sizes.
Cast steel shot or steel grit is used to clean and prepare the surface before coating. Shot blasting recycles the media
and is environmentally friendly. This method of preparation is highly efficient on steel parts such as I-beams, angles,
pipes, tubes and large fabricated pieces.
Different powder coating applications can require alternative methods of preparation such as abrasive blasting prior to
coating. The online consumer market typically offers media blasting services coupled with their coating services at
additional costs.
The most common way of applying the powder coating to metal objects is to spray the powder using an electrostatic
gun, or corona gun. The gun imparts a negative electric charge to the powder, which is then sprayed towards the
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Another type of gun is called a tribo gun, which charges the powder by (triboelectric) friction. In this case, the powder
picks up a positive charge while rubbing along the wall of a Teflon tube inside the barrel of the gun. These charged
powder particles then adhere to the grounded substrate. Using a tribo gun requires a different formulation of powder
than the more common corona guns. Tribo guns are not subject to some of the problems associated with corona guns
however, such as back ionisation and the Faraday cage effect.
Another method of applying powder coating, called the fluidised bed method, is by heating the substrate and then
dipping it into an aerated, powder-filled bed. The powder sticks and melts to the hot object. Further heating is usually
required to finish curing the coating. This method is generally used when the desired thickness of coating is to exceed
300µm. This is how most dishwasher racks are coated.
Curing
When a thermoset powder is exposed to elevated temperature, it begins to melt, flows out, and then chemically reacts
to form a higher molecular weight polymer in a network-like structure. This cure process, called crosslinking, requires a
certain temperature for a certain length of time in order to reach full cure and establish the full film properties for
which the material was designed. Normally the powders cure at 200°C (390°F) for 10 minutes. The curing schedule
could vary according to the manufacturer's specifications. The application of energy to the product to be cured can be
accomplished by convection cure ovens infrared cure ovens, or by laser curing process. The latter demonstrates
significant reduction of curing time.
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Adhesion Testing
In the paint and coating industries, paint adhesion testing is often used to determine if the paint or coating will adhere
properly to the substrates to which they are applied. There are three different tests to measure the resistance of paints
and coatings from substrates: cross-cut test, scrape adhesion, and pull-off test.
Cross-Cut Test
A right angle lattice pattern or X-cut (contingent on paint thickness) is used to measure the resistance of paints and
coatings to separation from substrates. The pattern is cut into the coating and penetrates through to the substrate. An
uncalibrated pressure sensitive tape is applied to the sample and pulled off. This testing method is usually used to
establish whether the adhesion of a coating to a substrate is at a generally adequate level. If this test is used on a
multi-coated sample, assessment of the resistance to separation of individual layers of the coating from each other can
be made.
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Scrape Adhesion
The scrape adhesion test measures the determination of the adhesion of organic coatings when applied to smooth, flat
panel surfaces. It is helpful in giving relative ratings for a number of coated panels showing significant differences in
adhesion. The materials being tested are applied at uniform thickness to flat panels, mainly some sort of sheet metal.
When the materials have dried, the adhesion is determined by pressing panels under a rounded stylus that is loaded
with increasing amounts of weight until the coating is removed from the substrate surface.
Pull-off Test
The adhesion of a coating or several-coated sample of any paint product is measured by assessing the minimum tensile
stress needed to detach or rupture the coating perpendicular to the substrate. Unlike the other methods, this method
maximises the tensile stress; therefore, results may not be comparable to the others. The test is done by securing
loading fixtures (dollies) perpendicular to the surface of a coating with an adhesive. Then the testing apparatus is
attached to the loading fixture and is then aligned to apply tension perpendicular to the test surface. The force that is
applied gradually increases and is monitored until a plug of coating is detached, or a previously specified value is
reached.
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The coating material can be applied by various methods, from brushing, spraying and dipping, or, due to the increasing
complexities of the electronic boards being designed and with the “process window” becoming smaller and smaller, by
selectively coating via robot. Different methods of curing/drying are available depending on the conformal coating
material.
Brush Coating
This works by flow coating the material onto the board and is suitable for low volume application, finishing and repair.
The finish tends to be inferior cosmetically and can be subject to many defects such as bubbles. The coating also tends
to be thicker and unless skilled operators applied the coating, highly subjective in quality.
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The process quality of dip or dam-and-fill coating and non-atomised spray technology can be improved when necessary
by applying and then releasing a vacuum while the assembly is submerged in the liquid resin. This forces the liquid
resin into all crevices, eliminating uncoated surfaces in interior cavities.
The differences in application methods can be seen in a comparison presentation. Choice of method is dependent on
the complexity of the substrate to be conformally coated, the required coating performance, and the throughput
requirements.
Water based conformal coatings can be treated in the same manner but with more care with the application of the
heat due to the slower drying times.
This increase in the popularity of UV curable conformal coatings is due to its rapid cure speed, level of processing ease,
environmental friendliness and thermal cycling resistance, which have never before been achieved with UV conformal
coating materials.
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Applying too much coating can be expensive. In addition, wet film measurements are useful for conformal coatings
where the dry film thickness can only be measured destructively or over application of conformal coating could be
problematic.
The wet film gauges are applied to the wet conformal coating and the teeth indicate the thickness of the conformal
coating. The dry film thickness can then be calculated from the measurement.
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Thicker coatings or better-applied coatings may be required when liquid water is present due to potential microscopic
pinhole formation in the coating or when the coating material is too thin on the sharp edges of components due to
poor application techniques. The former effect is a defect and can be eliminated by appropriate steps and the latter has
been mentioned previously. These techniques effectively "pot" or "conform" to the components by completely covering
them.
The most common standards for conformal coating are IPC A-610 and IPC-CC-830. These standards list indications of
good and bad coverage and describe various failure mechanisms such as dewetting and orange peel.
Conformal coating inspection is a critical factor in determining successful coating application and long-term reliability of
PCBs. Using the IPC standards allows the coating operator to monitor the coating application performance. The
operator in an inspection booth can do this manually by examining the PCB under white and UVA light or it can be
done automatically by a conformal coating inspection system.
Another type of coating called Parylene is applied with a vacuum deposition process versus a spray or needle
application. The Parylene is applied at the molecular level by a vacuum deposition process at ambient temperature.
Film coatings from 0.100 to 76μm can be easily applied in a single operation. The advantage of Parylene coatings is
that they cover hidden surfaces and other areas where spray and needle applications are not possible. Coating
thickness is uniform, even on irregular surfaces. The three main disadvantages are:
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Coating Chemistries
There is much chemistry of conformal coatings out on the market today. While the "Material Considerations" section
below is very important to finding the correct conformal coating, it is also important to find a coating chemistry
meeting the application needs. Below are five common strengths for each conformal coating chemistry:
Acrylic
• Ease of rework
• Simple drying process
• Good moisture resistance
• High fluorescence level
• Ease of viscosity adjustment
Epoxy
• Useful to about 150°C (302°F)
• Harder durometer, abrasion resistance
• CTE closer to epoxy PCB substrate
• Higher Tg (Glass transition)
• Good dielectric properties
Polyurethane
• Good dielectric properties
• Good moisture resistance
• Solvent resistance
• Less reversion potential
• Abrasion resistance
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Amorphous Fluoropolymer
• Low dielectric constant
• High glass transition temperature
• Low surface energy
• Low water absorption
• Solvent resistance
The basics of conformal coating processing can be understood from a presentation available giving a summary of the
areas covered above.
Material Considerations
Selection of the correct choice of coating material (lacquer) is one of the Process Engineer's most critical decisions.
Criteria for selection must be based on answering many questions, which will include:
• What is being protected against? (e.g., moisture, chemicals)
• What temperature range will the electrical device encounter?
• What are the physical, electrical, and chemical requirements for the coating material itself?
• Electrical, chemical, and mechanical compatibility with the parts and substances to be coated (for instance,
does it need to match the coefficient of expansion of chip components?)
The answers will determine the suitability of a particular material, be it acrylic polyurethane, silicone, epoxy, etc.
Process, production and commercial issues will then enter the equation:
• How easily can the material be reworked once applied?
• How fast does the material dry (cure)?
• How fast can the material be applied and dried (throughput time)?
• What type of process and equipment is necessary to achieve the required coating quality (uniformity and
repeatability)?
• Price of the material per litre?
• Quality of the material supplier (two acrylic material manufacturers will not make equal quality of material).
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Abrasive Blasting
Abrasive blasting is the operation of forcibly propelling a stream of abrasive material against a surface under high
pressure to smooth a rough surface, roughen a smooth surface, shape a surface, or remove surface contaminants. A
pressurised fluid, typically air, or a centrifugal wheel is used to propel the media. Benjamin Chew Tilghman patented
the first abrasive blasting process on 18 October 1870.
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There are several variants of the process, such as bead blasting, sandblasting, and soda blasting, and shot blasting.
Types
Wet Abrasive Blasting
Common features include:
The ability to use extremely fine or coarse media with densities ranging from plastic to steel
The ability to use hot water and soap to allow simultaneous degreasing and blasting, elimination of dust – so
silicacious materials can be used without worry, and hazardous material or waste can be removed without
danger – e.g. removal of asbestos, radioactive, or other poisonous products from components and structures
leading to effective decontamination.
The process is available in all conventional formats including hand cabinets, walk-in booths, automated production
machinery and total loss portable blasting units.
Process speeds can be as fast as conventional dry sand blasting when using the equivalent size and type of media.
However, the presence of water between the media and the substrate being processed creates a lubricating cushion
that can protect both the media and the surface from excess damage. This has the dual advantage of lowering media
breakdown rates and preventing impregnation of foreign materials into the surface. Hence, surfaces after wet blasting
are extremely clean, there is no embedded secondary contamination from the media or from previous blasting
processes, and there is no static cling of dust to the blasted surface. Subsequent coating or bonding operations are
always better after wet blasting than dry blasting because of the cleanliness levels achieved. The lack of surface
recontamination also allows the use of single equipment for multiple blasting operations – e.g. stainless steel and
carbon (mild) steel items can be processed in the same equipment with the same media without problems.
Bead Blasting
Bead blasting is the process of removing surface deposits by applying fine glass beads at a high pressure without
damaging the surface.
It is used to clean calcium deposits from pool tiles or any other surfaces, and removes embedded fungus and brighten
grout colour. It is also used in auto body work to remove paint.
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Hydro-blasting
Hydro-blasting, commonly known as water blasting, is used because it usually requires only one operator. In hydro-
blasting, a highly pressured stream of water is used to remove old paint, chemicals, or build-up without damaging the
original surface. This method is ideal for cleaning internal and external surfaces because the operator is generally able
to send the stream of water into places that are difficult to reach using other methods. Another benefit of hydro-
blasting is the ability to recapture and reuse the water, reducing waste and the impact on the environment.
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The most common micro-abrasive blasting systems are commercial bench-mounted units consisting of a power supply
and mixer; exhaust hood, nozzle and gas supply. The nozzle can be handheld or fixture mounted for automatic
operation. Either the nozzle or part can be moved in automatic operation.
Automated Blasting
A fully automated blasting system usually includes contained surface preparation and coating applications.
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Bristle Blasting
Bristle Blasting is, unlike other blasting methods, a process not needing any blast media. A brush-like rotary power tool
made of dynamically tuned high-carbon steel wire bristles treats the surface. Repeated contact of the sharp bristle tips
rotating against the surface results in localised impact, rebound, and the formation of craters, thereby simultaneously
cleaning and coarsening the surface.
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In wet blasting, the abrasive is introduced into a pressurised stream of water or other liquid, creating slurry. Wet
blasting is often used in applications where the minimal dust generation is desired. Portable applications may or may
not recycle the abrasive.
Blast Cabinet
A blast cabinet is essentially a closed loop system that allows the operator to blast the part and recycle the abrasive. It
usually consists of four components; the containment (cabinet), the abrasive blasting system, the abrasive recycling
system and the dust collection. The operator blasts the parts from the outside of the cabinet by placing his/her arms in
gloves attached to glove holes on the cabinet, viewing the part through a view window, turning the blast on and off
using a foot pedal or treadle. Automated blast cabinets are also used to process large quantities of the same
component and may incorporate multiple blast nozzles and a part conveyance system.
There are three systems typically used in a blast cabinet. Two, siphon and pressure, are dry and one is wet:
A siphon blast system (suction blast system) uses the compressed air to create a vacuum in a chamber (known
as the blast gun). The negative pressure pulls abrasive into the blast gun where the compressed air directs the
abrasive through a blast nozzle. The abrasive mixture travels through a nozzle that directs the particles toward
the surface or work piece.
Nozzles come in a variety of shapes, sizes, and materials. Tungsten carbide is the liner material most often used for
mineral abrasives. Silicon carbide and boron carbide nozzles are more wear resistant and are often used with harder
abrasives such as aluminium oxide. Inexpensive abrasive blasting systems and smaller cabinets use ceramic nozzles.
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Blast Room
A blast room is a larger version of a blast cabinet and the blast operator works inside the room. A blast room includes
three of the four components of a blast cabinet: the containment structure, the abrasive blasting system and the dust
collector. Most blast rooms have recycling systems ranging from manual sweeping and shovelling the abrasive back
into the blast pot to full reclaim floors that convey the abrasive pneumatically or mechanically to a device that cleans
the abrasive prior to recycling.
Media
In the early 1900s, it was assumed that sharp-edged grains provided the best performance, but this was later
demonstrated not to be correct.
Mineral
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Another common mineral abrasive is garnet. Garnet is more expensive than silica sand, but if used correctly, will offer
equivalent production rates while producing less dust and no safety hazards from ingesting the dust. Magnesium
sulphate (kieserite) is often used as an alternative to baking soda.
Agricultural
This is typically, crushed nut shells or fruit kernels. These soft abrasives are used to avoid damaging the underlying
material such as when cleaning brick or stone, removing graffiti or the removal of coatings from printed circuit boards
being repaired.
Synthetic
This category includes corn/wheat starch, sodium bicarbonate, and dry ice. These "soft" abrasives are also used to
avoid damaging the underlying material such as when cleaning brick or stone, removing graffiti or the removal of
coatings from printed circuit boards being repaired. Soda blasting uses baking soda (sodium bicarbonate) which is
extremely friable. The micro fragmentation on impact explodes away surface materials without damage to the
substrate.
Additional synthetic abrasives include process by-products e.g. copper slag, nickel slag and coal slag, engineered
abrasives e.g. aluminium oxide, silicon carbide aka carborundum, glass beads, ceramic shot/grit and recycled products
e.g. plastic abrasive, glass grit.
Metallic
Steel shot, steel grit, stainless steel shot, cut wire, copper shot, aluminium shot, zinc shot.
Many coarser media used in sandblasting often result in energy being given off as sparks or light on impact. The
colours and size of the spark or glow varies significantly, with heavy bright orange sparks from steel shot blasting, to a
faint blue glow (often invisible in sunlight or brightly lit work areas) from garnet abrasive.
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Safety
Cleaning operations using abrasive blasting can present risks for workers' health and safety, specifically in portable air
blasting or blast room (booth) applications. Although many abrasives used in blasting rooms are not hazardous in
themselves, (steel shot and grit, cast iron, aluminium oxide, garnet, plastic abrasive and glass bead), other abrasives
(silica sand, copper slag, nickel slag, and staurolite) have varying degrees of hazard (typically free silica or heavy
metals). However, in all cases their use can present serious danger to operators, such as burns due to projections (with
skin or eye lesions), falls due to walking on round shots scattered on the ground, exposure to hazardous dusts, heat
exhaustion, creation of an explosive atmosphere, and exposure to excessive noise. Blasting rooms and portable
blaster's equipment have been adapted to these dangers. Blasting lead-based paint can fill the air with lead particles,
which can be harmful to the nervous system.
OSHA (Occupational Safety and Health Administration) mandates engineered solutions to potential hazards. However,
silica sand continues to be allowed even though most commonly used blast helmets are not sufficiently effective at
protecting the Blast Operator if ambient levels of dust exceed allowable limits. The National Institute approves
respiratory protection in the United States for Occupational Safety and Health.
• Positive pressure blast hood or helmet: The hood or helmet includes a head suspension system to allow the
device to move with the Operator's head, a view window with replaceable lens or lens protection and an air
feed hose.
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• Body protection: Body protection varies by application but usually consists of gloves and overalls or a
leather coat and chaps. Professionals would wear a cordura/canvas blast suit (unless blasting with
steel abrasives, then they would use a leather suit).
In the past, when sandblasting was performed as an open-air job, the worker was exposed to risk of injury from the
flying material and lung damage from inhaling the dust. The silica dust produced in the sandblasting process would
cause silicosis after sustained inhalation of the dust. In 1918, the first sandblasting enclosure was built, which
protected the worker with a viewing screen, revolved around the work piece, and used an exhaust fan to draw dust
away from the worker's face.
Sandblasting also may present secondary risks, such as falls from scaffolding and absorption of lead particles when
removing lead-based paint from infrastructure.
Several countries and territories now regulate sandblasting such that it may only be performed in a controlled
environment using ventilation, protective clothing and breathing air supply.
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General
This list of standards is provided for guidance only and is not intended to be comprehensive. It is included to assist the
Inspector in selecting suitable sources of information where a Client’s specific requirements do not exist.
• BS En ISO 3861: Rubber hoses for sand and grit blasting – specification
• ASTM C418: Standard test method for abrasion resistance of concrete by sandblasting
• ANSI 29.4: Abrasive-blasting operations - ventilation and safe practices for fixed location
• ASTM D4940: Standard test method for conduct metric analysis of water soluble ionic contamination
of blasting abrasives
• ASTM F1330: Standard guide for metallic abrasive blasting to descale the interior of pipe.
• BS EN 2497: Specification for dry abrasive blasting of titanium and titanium alloys
• BS EN ISO 14877: Protective clothing for abrasive blasting operations using granular abrasives
• BS EN 271 Respiratory devices - compressed air line or powered fresh air hose breathing
apparatus incorporating a hood for use in abrasive blasting operations - requirements, testing, marking ** w/d
s/s by BS en 14593-1, BS En 14593-2 and BS En 14594 **
• ASTME1681: Standard test method for determining threshold stress intensity factor for environment-
assisted cracking of metallic materials
• ASTM G36: Standard practice for evaluating stress-corrosion-cracking resistance of metals and
alloys in a boiling magnesium chloride solution
• ISO 17641-1: Destructive tests on welds in metallic materials - hot cracking tests for weldments – arc
welding processes - part 1: general
• ISO DIS 7539.11: Corrosion of metals and alloys - stress corrosion cracking – part 11: guidelines for testing
the resistance of metals and alloys to hydrogen embrittlement and hydrogen-assisted cracking
• NACE TM177: Laboratory testing of metals for resistance to sulphide stress cracking and stress
corrosion cracking in h2s environments
• ANSI/NACE MR0175/ISO 15156, Petroleum and natural gas industries — Materials for use in H2S-containing
environments in oil and gas production
• BS ISO 15324: Corrosion of metals and alloys - evaluation of stress corrosion cracking by the drop
evaporation test
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• ASTM D1731: Standard practices for preparation of hot-dip aluminium surfaces for painting
• ASTM D2200: Standard practice for use of pictorial surface preparation standards and guides for
painting steel surfaces
• ASTM D6237: Standard guide for painting inspectors (concrete and masonry substrates)
BS EN ISO 8502-3: Preparation of steel substrates before application of paints and related products - Tests
for the assessment of surface cleanliness- part 3: assessment of dust on steel surface prepared for painting
(Pressure-sensitive tape method)
• SSPC QP-1: Standard procedure for evaluating painting contractors (field application to complex
industrial structures)
• Svensk Standard SIS 05 59 00: Pictorial surface preparation standards for painting steel surfaces.
ISO 8501-1 2007: Preparation of steel substrates before application of paints and related products -
Visual assessment of surface cleanliness – Part 1: Rust grades and preparation grades of uncoated steel
substrates and of steel substrates after overall removal of previous coatings
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