Pickling (metal)
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Pickling is a
metal A metal (from ancient Greek, Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electrical resistivity and conductivity, e ...
surface treatment used to remove impurities, such as stains, inorganic contaminants, and
rust Rust is an iron oxide, a usually reddish-brown oxide formed by the reaction of iron and oxygen in the catalytic presence of water or air moisture. Rust consists of hydrous iron(III) oxides (Fe2O3·nH2O) and iron(III) oxide-hydroxide (FeO( ...
or scale from ferrous metals,
copper Copper is a chemical element with the symbol Cu (from la, cuprum) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pink ...
, precious metals and
aluminum Aluminium (aluminum in American and Canadian English) is a chemical element with the symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately one third that of steel. It ha ...
alloys. A solution called ''pickle liquor'', which usually contains
acid In computer science, ACID ( atomicity, consistency, isolation, durability) is a set of properties of database transactions intended to guarantee data validity despite errors, power failures, and other mishaps. In the context of databases, a se ...
, is used to remove the surface impurities. It is commonly used to descale or clean
steel Steel is an alloy made up of iron with added carbon to improve its strength and fracture resistance compared to other forms of iron. Many other elements may be present or added. Stainless steels that are corrosion- and oxidation-resistan ...
in various steelmaking processes.


Process

Metal surfaces can contain impurities that may affect usage of the product or further processing like plating with metal or painting. Various chemical solutions are usually used to clean these impurities. Strong acids, such as
hydrochloric acid Hydrochloric acid, also known as muriatic acid, is an aqueous solution of hydrogen chloride. It is a colorless solution with a distinctive pungent smell. It is classified as a strong acid. It is a component of the gastric acid in the dige ...
and
sulfuric acid Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid ( Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen and hydrogen, with the molecular fo ...
are common, but different applications use various other acids. Also
alkaline In chemistry, an alkali (; from ar, القلوي, al-qaly, lit=ashes of the saltwort) is a basic, ionic salt of an alkali metal or an alkaline earth metal. An alkali can also be defined as a base that dissolves in water. A solution of a ...
solutions can be used for cleaning metal surfaces. Solutions usually also contain additives such as wetting agents and
corrosion inhibitors In chemistry, a corrosion inhibitor or anti-corrosive is a chemical compound that, when added to a liquid or gas, decreases the corrosion rate of a material, typically a metal or an alloy, that comes into contact with the fluid. The effectiveness ...
. Pickling is sometimes called acid cleaning if descaling is not needed. Many
hot working In metallurgy, hot working refers to processes where metals are plastically deformed above their recrystallization temperature. Being above the recrystallization temperature allows the material to recrystallize during deformation. This is impo ...
processes and other processes that occur at high temperatures leave a discoloring oxide layer or scale on the surface. In order to remove the scale the workpiece is dipped into a vat of pickle liquor. Prior to cold rolling operation, hot rolled steel is normally passed through a pickling line so as to eradicate the scale from the surface. The primary acid used in steelmaking is hydrochloric acid, although sulfuric acid was previously more common. Hydrochloric acid is more expensive than sulfuric acid, but it pickles much faster while minimizing base metal loss. The speed is a requirement for integration in automatic steel mills that run production at speeds as high as 800 ft/min (≈243 metres/min).
Carbon steel Carbon steel is a steel with carbon content from about 0.05 up to 2.1 percent by weight. The definition of carbon steel from the American Iron and Steel Institute (AISI) states: * no minimum content is specified or required for chromium, coba ...
s, with an alloy content less than or equal to 6%, are often pickled in hydrochloric or sulfuric acid. Steels with an alloy content greater than 6% must be pickled in two steps and other acids are used, such as phosphoric, nitric and
hydrofluoric acid Hydrofluoric acid is a solution of hydrogen fluoride (HF) in water. Solutions of HF are colourless, acidic and highly corrosive. It is used to make most fluorine-containing compounds; examples include the commonly used pharmaceutical antidepres ...
. Rust- and acid-resistant chromium-nickel steels are pickled traditionally in a bath of hydrofluoric and nitric acid. Most
copper Copper is a chemical element with the symbol Cu (from la, cuprum) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pink ...
alloys are pickled in dilute sulfuric acid, but
brass Brass is an alloy of copper (Cu) and zinc (Zn), in proportions which can be varied to achieve different mechanical, electrical, and chemical properties. It is a substitutional alloy: atoms of the two constituents may replace each other wi ...
is pickled in concentrated sulfuric and nitric acid mixed with
sodium chloride Sodium chloride , commonly known as salt (although sea salt also contains other chemical salts), is an ionic compound with the chemical formula NaCl, representing a 1:1 ratio of sodium and chloride ions. With molar masses of 22.99 and 35. ...
and soot. In jewelry making, pickling is used to remove the copper oxide layer that results from heating copper and sterling silver during soldering and annealing. A diluted sulfuric acid pickling bath is traditionally used, but may be replaced with
citric acid Citric acid is an organic compound with the chemical formula HOC(CO2H)(CH2CO2H)2. It is a colorless weak organic acid. It occurs naturally in citrus fruits. In biochemistry, it is an intermediate in the citric acid cycle, which occurs in ...
. Sheet steel that undergoes acid pickling will oxidize (rust) when exposed to atmospheric conditions of moderately high humidity. For this reason, a thin film of oil or similar waterproof coating is applied to create a barrier to moisture in the air. This oil film must later be removed for many fabrication, plating or painting processes.


Disadvantages

Acid cleaning has limitations in that it is difficult to handle because of its corrosiveness, and it is not applicable to all steels.
Hydrogen embrittlement Hydrogen embrittlement (HE), also known as hydrogen-assisted cracking or hydrogen-induced cracking (HIC), is a reduction in the ductility of a metal due to absorbed hydrogen. Hydrogen atoms are small and can permeate solid metals. Once absorbe ...
becomes a problem for some alloys and high-carbon steels. The hydrogen from the acid reacts with the surface and makes it brittle, causing cracks. Because of its high reactivity with treatable steels, acid concentrations and solution temperatures must be kept under control to ensure desired pickling rates.


Waste products

Pickling sludge is the waste product from pickling, and includes acidic rinse waters, iron chlorides, and metallic salts and waste acid. Spent pickle liquor is considered a hazardous waste by the
EPA The Environmental Protection Agency (EPA) is an independent executive agency of the United States federal government tasked with environmental protection matters. President Richard Nixon proposed the establishment of EPA on July 9, 1970; it be ...
. Pickle sludge from steel processes is usually neutralized with lime and disposed of in a
landfill A landfill site, also known as a tip, dump, rubbish dump, garbage dump, or dumping ground, is a site for the disposal of waste materials. Landfill is the oldest and most common form of waste disposal, although the systematic burial of the wast ...
since the EPA no longer deems it a hazardous waste after neutralization. The lime neutralization process raises the pH of the spent acid. The waste material is subject to a waste determination to ensure no characteristic or listed waste is present. Since the 1960s, hydrochloric pickling sludge is often treated in a hydrochloric acid regeneration system, which recovers some of the hydrochloric acid and
ferric oxide Iron(III) oxide or ferric oxide is the inorganic compound with the formula Fe2O3. It is one of the three main oxides of iron, the other two being iron(II) oxide (FeO), which is rare; and iron(II,III) oxide (Fe3O4), which also occurs naturall ...
. The rest must still be neutralized and disposed of in land fills or managed as a hazardous waste based on the waste profile analysis. The by-products of nitric acid pickling are marketable to other industries, such as
fertilizer A fertilizer (American English) or fertiliser (British English; see spelling differences) is any material of natural or synthetic origin that is applied to soil or to plant tissues to supply plant nutrients. Fertilizers may be distinct from ...
processors.


Alternatives

Smooth clean surface Smooth clean surface (SCS) is a process applied to hot rolled sheet metal and coils to remove nearly all mill scale and clean the steel surface. The SCS process feeds hot rolled sheet steel, either as individual blanks or as a continuous strip ...
(SCS) and
eco pickled surface Eco pickled surface (EPS) is a process applied to hot rolled sheet steel to remove all surface oxides ( mill scale) and clean the steel surface. Steel which has undergone the EPS process acquires a high degree of resistance to subsequent develop ...
(EPS) are more recent alternatives. In the SCS process, surface oxidation is removed using an engineered abrasive and the process leaves the surface resistant to subsequent oxidation without the need for oil film or other protective coating. EPS is a more direct replacement for acid pickling. Acid pickling relies on chemical reactions while EPS uses mechanical means. The EPS process is considered "environmentally friendly" compared with acid pickling and it imparts to carbon steel a high degree of rust resistance, eliminating the need to apply the oil coating that serves as a barrier to oxidation for acid-pickled carbon steel. Alternative methods include also mechanical cleaning such as
abrasive blasting Sandblasting, sometimes known as 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 su ...
, grinding, wire brushing, hydrocleaning and
Laser cleaning Laser ablation or photoablation (also called laser blasting) is the process of removing material from a solid (or occasionally liquid) surface by irradiating it with a laser beam. At low laser flux, the material is heated by the absorbed laser ...
. These methods generally do not provide as clean a surface as pickling does


References

{{Reflist Metalworking Steelmaking