Cold Water Pitting of Copper Tube
Encyclopedia
Cold water pitting of copper tube occurs in only a minority of installations. Copper water tubes are usually guaranteed by the manufacturer against manufacturing defects for a period of 50 years. The vast majority of copper systems far exceed this time period but a small minority may fail after a comparatively short time.
The majority of failures seen are the result of poor installation or operation of the water system. The most common failure seen in the last 20 years is pitting corrosion
in cold water tubes, also known as Type 1 pitting. These failures are usually the result of poor commissioning practice although a significant number are initiated by flux
left in the bore after assembly of soldered
joints. Prior to about 1970 the most common cause of Type 1 pitting was carbon films left in the bore by the manufacturing process.
Research and manufacturing improvements in the 1960s virtually eliminated carbon
as a cause of pitting with the introduction of a clause in the 1971 edition of BS 2871
requiring tube bores to be free of deleterious films. Despite this, carbon is still regularly blamed for tube failures without proper investigation.
rate of copper in most potable waters is less than 25 µm/year, at this rate a 15 mm tube with a wall thickness of 0.7 mm would last for about 280 years. In some soft waters the general corrosion rate may increase to 125 µm/year, but even at this rate it would take over 50 years to perforate the same tube. Despite the reliability
of copper and copper alloy
s, in some cold hard water
s pits may form in the bore of a tube. If these pits form, failure times can be expected between 6 months and 2 years from initiation. The mechanism that leads to the pitting of copper in cold hard waters is complex, it requires a water with a specific chemistry that is capable of supporting pit growth and a mechanism for the initiation of the pits.
s that inhibit the formation of Type 1 pits, unless a deflocculation treatment has been carried out that removes organic material. Type 1 pitting is relatively uncommon in North America and this may be a result of the lower population density allowing a significant proportion of the potable water to be obtained from surface derived sources. In addition to being cold hard and organically pure, the water needs a specific chemistry. The effect of the water chemistry can be empirically determined though use of the Pitting Propensity Rating (PPR) a number that takes into account the sulfate
, chloride
, nitrate
and sodium
ion
concentrations of the water as well as its acidity or pH
. A water with a positive PPR has been shown to be capable of propagating Type 1 pits.
. If any pitting of the tube is to occur then this film must be locally disrupted. There are three mechanisms that allow the disruption of the protective deposits. The most well known, although now the least common, is the presence of carbon films on the bore. Stagnation and flux residues are the most common initiation mechanisms that have led to Type 1 pitting failures in the last ten years.
In each of the areas that the scale has been disrupted there is the possibility of the initiation of Type 1 pitting. Once pitting has initiated, then even after the tube has been put back into service, the pit will continue to develop until the wall has perforated. This form of attack is often associated with the commissioning of a system. Once a system has been commissioned it should be either put immediately into service or drained down and dried by flushing with compressed air otherwise pitting may initiate. If either of these options is not possible then the system should be flushed though regularly until it is put into use.
and zinc chloride
in a binder such as petroleum jelly
. If too much flux is applied to the joint then the excess will melt and run down the bore of a vertical tube or pool in the bottom of a horizontal tube. Where the bore of the tube is covered in a layer of flux it may be locally protected from corrosion but at the edges of the flux pits often initiate. If the tube is put into service in a water that supports Type 1 pitting then these pits will develop and eventually perforate the sides of the tube.
. Tubes greater than 10 mm in diameter
made to this standard will always be marked the number of the standard, the nominal size, wall thickness and temper of the tube, the manufacturer’s identification mark and the date of production at least every 600 mm. Tubes less than 10 mm in diameter will be similarly marked at each end.
Once a system has been commissioned it should be either put immediately into service or drained down and dried. If either of these options is not possible then the system should be flushed though regularly until it is put into use. It should not be left to stand for more than a week. At present stagnation
is the most common cause of Type 1 pitting.
Flux should be used sparingly. A small quantity should be painted over the areas to be joined and any excess removed after the joint has been made. Some fluxes are marked as water-soluble but under some circumstances they are not removed before pitting has initiated.
The majority of failures seen are the result of poor installation or operation of the water system. The most common failure seen in the last 20 years is pitting corrosion
Pitting corrosion
Pitting corrosion, or pitting, is a form of extremely localized corrosion that leads to the creation of small holes in the metal. The driving power for pitting corrosion is the depassivation of a small area, which becomes anodic while an unknown but potentially vast area becomes cathodic, leading...
in cold water tubes, also known as Type 1 pitting. These failures are usually the result of poor commissioning practice although a significant number are initiated by flux
Flux (metallurgy)
In metallurgy, a flux , is a chemical cleaning agent, flowing agent, or purifying agent. Fluxes may have more than one function at a time...
left in the bore after assembly of soldered
Soldering
Soldering is a process in which two or more metal items are joined together by melting and flowing a filler metal into the joint, the filler metal having a lower melting point than the workpiece...
joints. Prior to about 1970 the most common cause of Type 1 pitting was carbon films left in the bore by the manufacturing process.
Research and manufacturing improvements in the 1960s virtually eliminated carbon
Carbon
Carbon is the chemical element with symbol C and atomic number 6. As a member of group 14 on the periodic table, it is nonmetallic and tetravalent—making four electrons available to form covalent chemical bonds...
as a cause of pitting with the introduction of a clause in the 1971 edition of BS 2871
British Standards
British Standards are the standards produced by BSI Group which is incorporated under a Royal Charter...
requiring tube bores to be free of deleterious films. Despite this, carbon is still regularly blamed for tube failures without proper investigation.
Copper water tubes
Copper tubes have been used to distribute potable water within building for many years and hundreds of miles are installed throughout Europe every year. The long life of copper when exposed to natural waters is a result of its thermodynamic stability, its high resistance to reacting with the environment, and the formation of insoluble corrosion products that insulate the metal from the environment. The corrosionCorrosion
Corrosion is the disintegration of an engineered material into its constituent atoms due to chemical reactions with its surroundings. In the most common use of the word, this means electrochemical oxidation of metals in reaction with an oxidant such as oxygen...
rate of copper in most potable waters is less than 25 µm/year, at this rate a 15 mm tube with a wall thickness of 0.7 mm would last for about 280 years. In some soft waters the general corrosion rate may increase to 125 µm/year, but even at this rate it would take over 50 years to perforate the same tube. Despite the reliability
Reliability engineering
Reliability engineering is an engineering field, that deals with the study, evaluation, and life-cycle management of reliability: the ability of a system or component to perform its required functions under stated conditions for a specified period of time. It is often measured as a probability of...
of copper and copper alloy
Alloy
An alloy is a mixture or metallic solid solution composed of two or more elements. Complete solid solution alloys give single solid phase microstructure, while partial solutions give two or more phases that may or may not be homogeneous in distribution, depending on thermal history...
s, in some cold hard water
Hard water
Hard water is water that has high mineral content . Hard water has high concentrations of Ca2+ and Mg2+ ions. Hard water is generally not harmful to one's health but can pose serious problems in industrial settings, where water hardness is monitored to avoid costly breakdowns in boilers, cooling...
s pits may form in the bore of a tube. If these pits form, failure times can be expected between 6 months and 2 years from initiation. The mechanism that leads to the pitting of copper in cold hard waters is complex, it requires a water with a specific chemistry that is capable of supporting pit growth and a mechanism for the initiation of the pits.
Pitting
The pits that penetrate the bore are usually covered in a hard pale green nodule of copper sulfate and copper hydroxide salts. If the nodule is removed a hemispherical pit is revealed filled with coarse crystals of red cuprous oxide and green cuprous chloride. The pits are often referred to as Type 1 pits and the form of attack as Type 1 pitting.Water
The characteristics capable of supporting Type 1 pits were determined empirically by Lucey after examining the compositions of waters in which the pitting behaviour was known. They should be cold, less than 30°C, hard or moderately hard, 170 to 300 mg/l carbonate hardness, and organically pure. Organically pure waters usually originate from deep wells, or boreholes. Surface waters from rivers or lakes contain naturally occurring organic compoundOrganic compound
An organic compound is any member of a large class of gaseous, liquid, or solid chemical compounds whose molecules contain carbon. For historical reasons discussed below, a few types of carbon-containing compounds such as carbides, carbonates, simple oxides of carbon, and cyanides, as well as the...
s that inhibit the formation of Type 1 pits, unless a deflocculation treatment has been carried out that removes organic material. Type 1 pitting is relatively uncommon in North America and this may be a result of the lower population density allowing a significant proportion of the potable water to be obtained from surface derived sources. In addition to being cold hard and organically pure, the water needs a specific chemistry. The effect of the water chemistry can be empirically determined though use of the Pitting Propensity Rating (PPR) a number that takes into account the sulfate
Sulfate
In inorganic chemistry, a sulfate is a salt of sulfuric acid.-Chemical properties:...
, chloride
Chloride
The chloride ion is formed when the element chlorine, a halogen, picks up one electron to form an anion Cl−. The salts of hydrochloric acid HCl contain chloride ions and can also be called chlorides. The chloride ion, and its salts such as sodium chloride, are very soluble in water...
, nitrate
Nitrate
The nitrate ion is a polyatomic ion with the molecular formula NO and a molecular mass of 62.0049 g/mol. It is the conjugate base of nitric acid, consisting of one central nitrogen atom surrounded by three identically-bonded oxygen atoms in a trigonal planar arrangement. The nitrate ion carries a...
and sodium
Sodium
Sodium is a chemical element with the symbol Na and atomic number 11. It is a soft, silvery-white, highly reactive metal and is a member of the alkali metals; its only stable isotope is 23Na. It is an abundant element that exists in numerous minerals, most commonly as sodium chloride...
ion
Ion
An ion is an atom or molecule in which the total number of electrons is not equal to the total number of protons, giving it a net positive or negative electrical charge. The name was given by physicist Michael Faraday for the substances that allow a current to pass between electrodes in a...
concentrations of the water as well as its acidity or pH
PH
In chemistry, pH is a measure of the acidity or basicity of an aqueous solution. Pure water is said to be neutral, with a pH close to 7.0 at . Solutions with a pH less than 7 are said to be acidic and solutions with a pH greater than 7 are basic or alkaline...
. A water with a positive PPR has been shown to be capable of propagating Type 1 pits.
Initiation
Many waters in both the UK and Europe are capable of supporting Type 1 pitting but no problems will be experienced unless a pit is initiated in the wall of the tube. When a copper tube is initially filled with a hard water salts deposit on the wall and the copper slowly reacts with the water producing a thin protective layer of mixed corrosion products and hardness scaleLimescale
Limescale is the hard, off-white, chalky deposit found in kettles, hot-water boilers and the inside of inadequately maintained hot-water central heating systems...
. If any pitting of the tube is to occur then this film must be locally disrupted. There are three mechanisms that allow the disruption of the protective deposits. The most well known, although now the least common, is the presence of carbon films on the bore. Stagnation and flux residues are the most common initiation mechanisms that have led to Type 1 pitting failures in the last ten years.
Carbon rilms
Copper tubes are made from the large billets of copper that are gradually worked and drawn down to the required size. As the tubes are drawn they are heat treated to produce the correct mechanical properties. The organic oils and greases used to lubricate the tubes during the drawing processes are broken down during the heat treatment and gradually coat the tube with a film of carbon. If the carbon is left in the bore of the tube then it disrupts the formation of the protective scale and allows the initiation of pits in the wall. The presence of deleterious films, such as carbon, has been prohibited by the British Standards in copper tubes since 1969. All copper tubes for water service are treated, usually by grit blasting or acid pickling, to remove any films produced during manufacture with the result that Type 1 pitting initiated by carbon films is now very rare.Stagnation
If water is left to stand in a tube for an extended period, the chemical characteristics of the water change as the mixed scale and corrosion products are deposited. In addition any loose scale that is not well adhered to the wall will not be flushed away and air dissolved in the water will form bubbles, producing air pockets. These processes can lead to a number of problems mainly on horizontal tube runs. Particles of scale that do not adhere to the walls and are not washed away tend to fall into the bottom of the tube producing a coarse porous deposit. Air pockets that develop in horizontal runs disrupt the formation of protective scales in two areas. The water lines at the sides and the air space at the top of the tube.In each of the areas that the scale has been disrupted there is the possibility of the initiation of Type 1 pitting. Once pitting has initiated, then even after the tube has been put back into service, the pit will continue to develop until the wall has perforated. This form of attack is often associated with the commissioning of a system. Once a system has been commissioned it should be either put immediately into service or drained down and dried by flushing with compressed air otherwise pitting may initiate. If either of these options is not possible then the system should be flushed though regularly until it is put into use.
Flux
In plumbing systems fluxes are used to keep the mating surfaces clean during soldering operations. The fluxes often consist of corrosive chemicals such as ammonium chlorideAmmonium chloride
Ammonium chloride NH4Cl is an inorganic compound with the formula NH4Cl. It is a white crystalline salt that is highly soluble in water. Solutions of ammonium chloride are mildly acidic. Sal ammoniac is a name of natural, mineralogical form of ammonium chloride...
and zinc chloride
Zinc chloride
Zinc chloride is the name of chemical compound with the formula ZnCl2 and its hydrates. Zinc chlorides, of which nine crystalline forms are known, are colorless or white, and are highly soluble in water. ZnCl2 itself is hygroscopic and even deliquescent. Samples should therefore be protected from...
in a binder such as petroleum jelly
Petroleum jelly
Petroleum jelly, petrolatum, white petrolatum or soft paraffin, CAS number 8009-03-8, is a semi-solid mixture of hydrocarbons , originally promoted as a topical ointment for its healing properties...
. If too much flux is applied to the joint then the excess will melt and run down the bore of a vertical tube or pool in the bottom of a horizontal tube. Where the bore of the tube is covered in a layer of flux it may be locally protected from corrosion but at the edges of the flux pits often initiate. If the tube is put into service in a water that supports Type 1 pitting then these pits will develop and eventually perforate the sides of the tube.
Recommendations
In most cases Type 1 pitting can be avoided by good working practices. Always use tubes that have been manufactured to BS EN 1057British Standards
British Standards are the standards produced by BSI Group which is incorporated under a Royal Charter...
. Tubes greater than 10 mm in diameter
Diameter
In geometry, a diameter of a circle is any straight line segment that passes through the center of the circle and whose endpoints are on the circle. The diameters are the longest chords of the circle...
made to this standard will always be marked the number of the standard, the nominal size, wall thickness and temper of the tube, the manufacturer’s identification mark and the date of production at least every 600 mm. Tubes less than 10 mm in diameter will be similarly marked at each end.
Once a system has been commissioned it should be either put immediately into service or drained down and dried. If either of these options is not possible then the system should be flushed though regularly until it is put into use. It should not be left to stand for more than a week. At present stagnation
Stagnation
Stagnation may refer to one of the following*Economic stagnation, slow or no economic growth*Era of Stagnation, a period of economic stagnation in Soviet Union*Stagnation in fluid dynamics, see "Stagnation point"*Water stagnation*Air stagnation...
is the most common cause of Type 1 pitting.
Flux should be used sparingly. A small quantity should be painted over the areas to be joined and any excess removed after the joint has been made. Some fluxes are marked as water-soluble but under some circumstances they are not removed before pitting has initiated.
External links
- NACE International -Professional society for corrosion engineers ( NACENACE InternationalNACE International is a professional organization for the corrosion control industry established in 1943. As of 2010, there are approximately 22,312 NACE members in over 100 countries. NACE International is involved in every industry and area of corrosion prevention and control, from chemical...
) - Copper Pipe Corrosion Theory and informations on Corrosion of Copper Pipe