Cold water pitting of copper tube
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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 Pitting corrosion, or pitting, is a form of extremely localized corrosion that leads to the random creation of small holes in metal. The driving power for pitting corrosion is the depassivation of a small area, which becomes anodic (oxidation re ...
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 describes any effect that appears to pass or travel (whether it actually moves or not) through a surface or substance. Flux is a concept in applied mathematics and vector calculus which has many applications to physics. For transport ph ...
left in the bore after assembly of
soldered Solder (; NA: ) is a fusible metal alloy used to create a permanent bond between metal workpieces. Solder is melted in order to wet the parts of the joint, where it adheres to and connects the pieces after cooling. Metals or alloys suitable ...
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 () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent In chemistry, the valence (US spelling) or valency (British spelling) of an element is the measure of its combining capacity with o ...
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.


Copper water tubes

Copper tubes have been used to distribute
potable Drinking water is water that is used in drink or food preparation; potable water is water that is safe to be used as drinking water. The amount of drinking water required to maintain good health varies, and depends on physical activity level, a ...
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
corrosion Corrosion is a natural process that converts a refined metal into a more chemically stable oxide. It is the gradual deterioration of materials (usually a metal) by chemical or electrochemical reaction with their environment. Corrosion engine ...
rate of copper in most potable waters is less than 2.5 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 12.5 µm/year, but even at this rate it would take over 50 years to perforate the same tube. Despite the
reliability Reliability, reliable, or unreliable may refer to: Science, technology, and mathematics Computing * Data reliability (disambiguation), a property of some disk arrays in computer storage * High availability * Reliability (computer networking), a ...
of copper and copper
alloy An alloy is a mixture of chemical elements of which at least one is a metal. Unlike chemical compounds with metallic bases, an alloy will retain all the properties of a metal in the resulting material, such as electrical conductivity, ductility, ...
s, in some cold
hard water Hard water is water that has high mineral content (in contrast with "soft water"). Hard water is formed when water percolates through deposits of limestone, chalk or gypsum, which are largely made up of calcium and magnesium carbonates, bicarbo ...
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 Copper(I) oxide or cuprous oxide is the inorganic compound with the formula Cu2O. It is one of the principal oxides of copper, the other being or copper(II) oxide or cupric oxide (CuO). This red-coloured solid is a component of some antifouling p ...
and green
cuprous chloride Copper(I) chloride, commonly called cuprous chloride, is the lower chloride of copper, with the formula CuCl. The substance is a white solid sparingly soluble in water, but very soluble in concentrated hydrochloric acid. Impure samples appear gre ...
. 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 wedetermined 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 compound In chemistry, organic compounds are generally any chemical compounds that contain carbon-hydrogen or carbon-carbon bonds. Due to carbon's ability to catenate (form chains with other carbon atoms), millions of organic compounds are known. 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 The sulfate or sulphate ion is a polyatomic anion with the empirical formula . Salts, acid derivatives, and peroxides of sulfate are widely used in industry. Sulfates occur widely in everyday life. Sulfates are salts of sulfuric acid and many ar ...
,
chloride The chloride ion is the anion (negatively charged ion) Cl−. It is formed when the element chlorine (a halogen) gains an electron or when a compound such as hydrogen chloride is dissolved in water or other polar solvents. Chloride salts ...
,
nitrate Nitrate is a polyatomic ion A polyatomic ion, also known as a molecular ion, is a covalent bonded set of two or more atoms, or of a metal complex, that can be considered to behave as a single unit and that has a net charge that is not zer ...
and
sodium Sodium is a chemical element with the symbol Na (from Latin ''natrium'') and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 of the periodic table. Its only stable iso ...
ion An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by conven ...
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.


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 scale The Mohs scale of mineral hardness () is a Qualitative property, qualitative ordinal scale, from 1 to 10, characterizing scratch hardness, scratch resistance of various minerals through the ability of harder material to scratch softer material. ...
. 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 films

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.BS EN 1057: 1996, Copper and Copper Alloys — Seamless, round copper tubes for water and gas in sanitary and heating applications All copper tubes for water service are treated, usually by sand (or other nonferrous medium) 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 through 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 chloride and
zinc chloride Zinc chloride is the name of inorganic chemical compounds 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. This salt is hygroscopic and ev ...
in a binder such as
petroleum jelly Petroleum jelly, petrolatum, white petrolatum, soft paraffin, or multi-hydrocarbon, CAS number 8009-03-8, is a semi-solid mixture of hydrocarbons (with carbon numbers mainly higher than 25), originally promoted as a topical ointment for its h ...
. 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 1057. Tubes greater than 10 mm in
diameter In geometry, a diameter of a circle is any straight line segment that passes through the center of the circle and whose endpoints lie on the circle. It can also be defined as the longest chord of the circle. Both definitions are also valid for ...
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.


See also

*
Erosion corrosion of copper water tubes Erosion corrosion, also known as impingement damage, is the combined effect of corrosion and erosion caused by rapid flowing turbulent water. It is probably the second most common cause of copper tube failures behind Type 1 pitting which is also k ...


References

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External links


NACE International
-Professional society for corrosion engineers ( NACE )
Copper Pipe Corrosion
Theory and information on Corrosion of Copper Pipe Corrosion Copper Water