Concrete degradation
Encyclopedia
Concrete degradation may have various causes. Concrete
Concrete
Concrete is a composite construction material, composed of cement and other cementitious materials such as fly ash and slag cement, aggregate , water and chemical admixtures.The word concrete comes from the Latin word...

 can be damaged by fire, aggregate expansion, sea water effects, bacterial corrosion, calcium leaching, physical damage and chemical damage (from carbonation, chlorides, sulfates and distilled water). This process adversely affects concrete exposed to these damaging stimuli.

Aggregate expansion

Various types of aggregate undergo chemical reactions in concrete, leading to damaging expansive phenomena.
The most common are those containing reactive silica, that can react (in the presence of water) with the alkalis in concrete (K2O and Na2O, coming principally from cement). Among the more reactive mineral components of some aggregates are opal
Opal
Opal is an amorphous form of silica related to quartz, a mineraloid form, not a mineral. 3% to 21% of the total weight is water, but the content is usually between 6% to 10%. It is deposited at a relatively low temperature and may occur in the fissures of almost any kind of rock, being most...

, chalcedony
Chalcedony
Chalcedony is a cryptocrystalline form of silica, composed of very fine intergrowths of the minerals quartz and moganite. These are both silica minerals, but they differ in that quartz has a trigonal crystal structure, while moganite is monoclinic...

, flint
Flint
Flint is a hard, sedimentary cryptocrystalline form of the mineral quartz, categorized as a variety of chert. It occurs chiefly as nodules and masses in sedimentary rocks, such as chalks and limestones. Inside the nodule, flint is usually dark grey, black, green, white, or brown in colour, and...

 and strained quartz
Quartz
Quartz is the second-most-abundant mineral in the Earth's continental crust, after feldspar. It is made up of a continuous framework of SiO4 silicon–oxygen tetrahedra, with each oxygen being shared between two tetrahedra, giving an overall formula SiO2. There are many different varieties of quartz,...

. Following the alkali-silica reaction
Alkali Silica Reaction
The alkali–silica reaction is a reaction which occurs over time in concrete between the highly alkaline cement paste and reactive non-crystalline silica, which is found in many common aggregates....

 (ASR), an expansive gel forms, that creates extensive cracks and damage on structural members. On the surface of concrete pavements the ASR can cause pop-outs, i.e. the expulsion of small cones (up to 3 cm (1 in) about in diameter) in correspondence of aggregate particles.
When some aggregates containing dolomite
Dolomite
Dolomite is a carbonate mineral composed of calcium magnesium carbonate CaMg2. The term is also used to describe the sedimentary carbonate rock dolostone....

 are used, a dedolomitization reaction occurs where the magnesium carbonate
Magnesium carbonate
Magnesium carbonate, MgCO3, is a white solid that occurs in nature as a mineral. Several hydrated and basic forms of magnesium carbonate also exist as minerals...

 compound reacts with hydroxyl ions and yields magnesium hydroxide
Magnesium hydroxide
Magnesium hydroxide is an inorganic compound with the chemical formula Mg2. As a suspension in water, it is often called milk of magnesia because of its milk-like appearance. The solid mineral form of magnesium hydroxide is known as brucite....

 and a carbonate ion
Carbonate
In chemistry, a carbonate is a salt of carbonic acid, characterized by the presence of the carbonate ion, . The name may also mean an ester of carbonic acid, an organic compound containing the carbonate group C2....

. The resulting expansion may cause destruction of the material. Far less common are pop-outs caused by the presence of pyrite
Pyrite
The mineral pyrite, or iron pyrite, is an iron sulfide with the formula FeS2. This mineral's metallic luster and pale-to-normal, brass-yellow hue have earned it the nickname fool's gold because of its resemblance to gold...

, an iron sulfide that generates expansion by forming iron oxide and ettringite
Ettringite
Ettringite is a hydrous calcium aluminium sulfate mineral with formula: Ca6Al2312·26H2O. It is a colorless to yellow mineral crystallizing in the trigonal system...

.
Other reactions and recrystallizations, e.g. hydration of clay minerals
Clay minerals
Clay minerals are hydrous aluminium phyllosilicates, sometimes with variable amounts of iron, magnesium, alkali metals, alkaline earths, and other cations. Clays have structures similar to the micas and therefore form flat hexagonal sheets. Clay minerals are common weathering products and low...

 in some aggregates, may lead to destructive expansion as well.

Corrosion of reinforcement bars

The expansion of the corrosion
Corrosion
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...

 products (iron oxide
Iron oxide
Iron oxides are chemical compounds composed of iron and oxygen. All together, there are sixteen known iron oxides and oxyhydroxides.Iron oxides and oxide-hydroxides are widespread in nature, play an important role in many geological and biological processes, and are widely utilized by humans, e.g.,...

s) of carbon steel reinforcement structures may induce mechanical stress that can cause the formation of cracks and disrupt the concrete structure. If the rebars have been poorly installed and are located too close to the concrete surface in contact with the air, spalling can easily occur: flat fragments of concrete are detached from the concrete mass by the rebar
Rebar
A rebar , also known as reinforcing steel, reinforcement steel, rerod, or a deformed bar, is a common steel bar, and is commonly used as a tensioning device in reinforced concrete and reinforced masonry structures holding the concrete in compression...

s corrosion and may fall down.

Carbonation

Carbon dioxide
Carbon dioxide
Carbon dioxide is a naturally occurring chemical compound composed of two oxygen atoms covalently bonded to a single carbon atom...

 from air can react with the calcium hydroxide
Calcium hydroxide
Calcium hydroxide, traditionally called slaked lime, is an inorganic compound with the chemical formula Ca2. It is a colourless crystal or white powder and is obtained when calcium oxide is mixed, or "slaked" with water. It has many names including hydrated lime, builders lime, slack lime, cal, or...

 in concrete to form calcium carbonate
Calcium carbonate
Calcium carbonate is a chemical compound with the formula CaCO3. It is a common substance found in rocks in all parts of the world, and is the main component of shells of marine organisms, snails, coal balls, pearls, and eggshells. Calcium carbonate is the active ingredient in agricultural lime,...

. This process is called carbonation, which is essentially the reversal of the chemical process of calcination
Calcination
Calcination is a thermal treatment process applied to ores and other solid materials to bring about a thermal decomposition, phase transition, or removal of a volatile fraction. The calcination process normally takes place at temperatures below the melting point of the product materials...

 of lime
Calcium carbonate
Calcium carbonate is a chemical compound with the formula CaCO3. It is a common substance found in rocks in all parts of the world, and is the main component of shells of marine organisms, snails, coal balls, pearls, and eggshells. Calcium carbonate is the active ingredient in agricultural lime,...

 taking place in a cement kiln
Cement kiln
Cement kilns are used for the pyroprocessing stage of manufacture of Portland and other types of hydraulic cement, in which calcium carbonate reacts with silica-bearing minerals to form a mixture of calcium silicates...

. Carbonation of concrete is a slow and continuous process progressing from the outer surface inward, but slows down with increasing diffusion depth. Carbonation has two effects: it increases mechanical strength of concrete, but it also decreases alkalinity
Alkalinity
Alkalinity or AT measures the ability of a solution to neutralize acids to the equivalence point of carbonate or bicarbonate. The alkalinity is equal to the stoichiometric sum of the bases in solution...

, which is essential for corrosion
Corrosion
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...

 prevention of the reinforcement steel. Below a 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...

 of 10, the steel's thin layer of surface passivation dissolves and corrosion is promoted. For the latter reason, carbonation is an unwanted process in concrete chemistry. Carbonation can be tested by applying Phenolphthalein
Phenolphthalein
Phenolphthalein is a chemical compound with the formula C20H14O4 and is often written as "HIn" or "phph" in shorthand notation. Often used in titrations, it turns colorless in acidic solutions and pink in basic solutions...

 solution, a pH indicator
PH indicator
A pH indicator is a halochromic chemical compound that is added in small amounts to a solution so that the pH of the solution can be determined visually. Hence a pH indicator is a chemical detector for hydronium ions or hydrogen ions in the Arrhenius model. Normally, the indicator causes the...

, over a fresh fracture surface, which indicates non-carbonated and thus alkaline areas with a violet color.

Chlorides

Chlorides, particularly calcium chloride
Calcium chloride
Calcium chloride, CaCl2, is a salt of calcium and chlorine. It behaves as a typical ionic halide, and is solid at room temperature. Common applications include brine for refrigeration plants, ice and dust control on roads, and desiccation...

, have been used to shorten the setting time of concrete.
However, calcium chloride and (to a lesser extent) sodium chloride
Sodium chloride
Sodium chloride, also known as salt, common salt, table salt or halite, is an inorganic compound with the formula NaCl. Sodium chloride is the salt most responsible for the salinity of the ocean and of the extracellular fluid of many multicellular organisms...

 have been shown to leach calcium hydroxide
Calcium hydroxide
Calcium hydroxide, traditionally called slaked lime, is an inorganic compound with the chemical formula Ca2. It is a colourless crystal or white powder and is obtained when calcium oxide is mixed, or "slaked" with water. It has many names including hydrated lime, builders lime, slack lime, cal, or...

 and cause chemical changes in Portland cement, leading to loss of strength, as well as attacking the steel reinforcement
Rebar
A rebar , also known as reinforcing steel, reinforcement steel, rerod, or a deformed bar, is a common steel bar, and is commonly used as a tensioning device in reinforced concrete and reinforced masonry structures holding the concrete in compression...

 present in most concrete.

Sulfates

Sulfates in solution in contact with concrete can cause chemical changes to the cement, which can cause significant microstructural effects leading to the weakening of the cement binder.

Leaching

When water flows through crack
Fracture
A fracture is the separation of an object or material into two, or more, pieces under the action of stress.The word fracture is often applied to bones of living creatures , or to crystals or crystalline materials, such as gemstones or metal...

s present in concrete, water may dissolve various mineral
Mineral
A mineral is a naturally occurring solid chemical substance formed through biogeochemical processes, having characteristic chemical composition, highly ordered atomic structure, and specific physical properties. By comparison, a rock is an aggregate of minerals and/or mineraloids and does not...

s present in the hardened cement
Cement
In the most general sense of the word, a cement is a binder, a substance that sets and hardens independently, and can bind other materials together. The word "cement" traces to the Romans, who used the term opus caementicium to describe masonry resembling modern concrete that was made from crushed...

 paste or in the aggregates
Construction Aggregate
Construction aggregate, or simply "aggregate", is a broad category of coarse particulate material used in construction, including sand, gravel, crushed stone, slag, recycled concrete and geosynthetic aggregates. Aggregates are the most mined material in the world...

, if the solution is unsaturated with respect to them. Dissolved ions, such as calcium (Ca2+), are leached out and transported in solution on a some distance. If the physico-chemical conditions prevailing in the seeping water evolve with distance along the water path and water becomes supersaturated with respect to certain minerals, they can further precipitate, making deposits
Deposition (chemistry)
In chemistry, deposition is the settling of particles or sediment from a solution, suspension and mixture or vapor onto a pre-existing surface...

 or efflorescence
Efflorescence
In chemistry, efflorescence is the loss of water of crystallization from a hydrated or solvated salt to the atmosphere on exposure to air.-Examples:...

s inside the cracks, or at the concrete outer surface. This process can cause the self-healing
Self-healing
Self-healing is a phrase applied to the process of recovery , motivated by and directed by the patient, guided often only by instinct. Such a process encounters mixed fortunes due to its amateur nature, although self-motivation is a major asset...

 of fractures in particular conditions.

Decalcification

Distilled water can wash out calcium content in concrete, leaving the concrete in brittle
Brittle
A material is brittle if, when subjected to stress, it breaks without significant deformation . Brittle materials absorb relatively little energy prior to fracture, even those of high strength. Breaking is often accompanied by a snapping sound. Brittle materials include most ceramics and glasses ...

 condition. A common source of distilled water can be condensed steam
Steam
Steam is the technical term for water vapor, the gaseous phase of water, which is formed when water boils. In common language it is often used to refer to the visible mist of water droplets formed as this water vapor condenses in the presence of cooler air...

. Distilled water leaches out the calcium better because undistilled water contains some calcium ions already, and does not dissolve them.

Sea water

Concrete exposed to seawater
Seawater
Seawater is water from a sea or ocean. On average, seawater in the world's oceans has a salinity of about 3.5% . This means that every kilogram of seawater has approximately of dissolved salts . The average density of seawater at the ocean surface is 1.025 g/ml...

 is susceptible to its corrosive effects. The effects are more pronounced above the tidal zone than where the concrete is permanently submerged. In the submerged zone, magnesium and hydrogen carbonate
Bicarbonate
In inorganic chemistry, bicarbonate is an intermediate form in the deprotonation of carbonic acid...

 ions precipitate a layer of brucite
Brucite
Brucite is the mineral form of magnesium hydroxide, with the chemical formula Mg2. It is a common alteration product of periclase in marble; a low-temperature hydrothermal vein mineral in metamorphosed limestones and chlorite schists; and formed during serpentinization of dunites...

, about 30 micrometers thick, on which a slower deposition of calcium carbonate as aragonite
Aragonite
Aragonite is a carbonate mineral, one of the two common, naturally occurring, crystal forms of calcium carbonate, CaCO3...

 occurs. These layers somewhat protect the concrete from other processes, which include attack by magnesium, chloride and sulfate ions and carbonation. Above the water surface, mechanical damage may occur by erosion
Erosion
Erosion is when materials are removed from the surface and changed into something else. It only works by hydraulic actions and transport of solids in the natural environment, and leads to the deposition of these materials elsewhere...

 by waves themselves or sand and gravel they carry, and by crystallization of salts from water soaking into the concrete pores and then drying up. Pozzolan
Pozzolan
A pozzolan is a material which, when combined with calcium hydroxide, exhibits cementitious properties. Pozzolans are commonly used as an addition to Portland cement concrete mixtures to increase the long-term strength and other material properties of Portland cement concrete, and in some cases...

ic cements and cements using more than 60% of slag as aggregate are more resistant to sea water than pure Portland cement. Sea water corrosion contains elements of both chloride and sulfate corrosion.

Bacterial corrosion

Bacteria themselves do not have noticeable effect on concrete. However, anaerobic bacteria
Anaerobic organism
An anaerobic organism or anaerobe is any organism that does not require oxygen for growth. It could possibly react negatively and may even die if oxygen is present...

 (Thiobacillus) in untreated sewage tend to produce hydrogen sulfide
Hydrogen sulfide
Hydrogen sulfide is the chemical compound with the formula . It is a colorless, very poisonous, flammable gas with the characteristic foul odor of expired eggs perceptible at concentrations as low as 0.00047 parts per million...

, which is then oxidized by aerobic bacteria
Aerobic organism
An aerobic organism or aerobe is an organism that can survive and grow in an oxygenated environment.Faculitative anaerobes grow and survive in an oxygenated environment and so do aerotolerant anaerobes.-Glucose:...

 present in biofilm
Biofilm
A biofilm is an aggregate of microorganisms in which cells adhere to each other on a surface. These adherent cells are frequently embedded within a self-produced matrix of extracellular polymeric substance...

 on the concrete surface above the water level to sulfuric acid
Sulfuric acid
Sulfuric acid is a strong mineral acid with the molecular formula . Its historical name is oil of vitriol. Pure sulfuric acid is a highly corrosive, colorless, viscous liquid. The salts of sulfuric acid are called sulfates...

. The sulfuric acid dissolves the carbonates in the cured cement and causes strength loss, as well as producing sulfates which are harmful to concrete. Concrete floors lying on ground that contains pyrite
Pyrite
The mineral pyrite, or iron pyrite, is an iron sulfide with the formula FeS2. This mineral's metallic luster and pale-to-normal, brass-yellow hue have earned it the nickname fool's gold because of its resemblance to gold...

 (iron(II) sulfide) are also at risk. Using limestone
Limestone
Limestone is a sedimentary rock composed largely of the minerals calcite and aragonite, which are different crystal forms of calcium carbonate . Many limestones are composed from skeletal fragments of marine organisms such as coral or foraminifera....

 as the aggregate makes the concrete more resistant to acids, and the sewage may be pretreated by ways increasing pH or oxidizing or precipitating the sulfides in order to inhibit the activity of sulfide utilizing bacteria.

Physical damage

Damage can occur during the casting and de-shuttering processes. For instance, the corners of beams can be damaged during the removal of shuttering because they are less effectively compacted by means of vibration (improved by using form-vibrators). Other physical damage can be caused by the use of steel shuttering without base plates. The steel shuttering pinches the top surface of a concrete slab due to the weight of the next slab being constructed.

Thermal damage

Due to its low thermal conductivity
Thermal conductivity
In physics, thermal conductivity, k, is the property of a material's ability to conduct heat. It appears primarily in Fourier's Law for heat conduction....

, a layer of concrete is frequently used for fireproofing
Fireproofing
Fireproofing, a passive fire protection measure, refers to the act of making materials or structures more resistant to fire, or to those materials themselves, or the act of applying such materials. Applying a certification listed fireproofing system to certain structures allows these to have a...

 of steel structures. However, concrete itself may be damaged by fire.

Up to about 300 °C, the concrete undergoes normal thermal expansion
Thermal expansion
Thermal expansion is the tendency of matter to change in volume in response to a change in temperature.When a substance is heated, its particles begin moving more and thus usually maintain a greater average separation. Materials which contract with increasing temperature are rare; this effect is...

. Above that temperature, shrinkage occurs due to water loss; however, the aggregate continues expanding, which causes internal stresses. Up to about 500 °C, the major structural changes are carbonation and coarsening of pores. At 573 °C, quartz
Quartz
Quartz is the second-most-abundant mineral in the Earth's continental crust, after feldspar. It is made up of a continuous framework of SiO4 silicon–oxygen tetrahedra, with each oxygen being shared between two tetrahedra, giving an overall formula SiO2. There are many different varieties of quartz,...

 undergoes rapid expansion due to Phase transition
Phase transition
A phase transition is the transformation of a thermodynamic system from one phase or state of matter to another.A phase of a thermodynamic system and the states of matter have uniform physical properties....

, and at 900 °C calcite
Calcite
Calcite is a carbonate mineral and the most stable polymorph of calcium carbonate . The other polymorphs are the minerals aragonite and vaterite. Aragonite will change to calcite at 380-470°C, and vaterite is even less stable.-Properties:...

 starts shrinking due to decomposition. At 450-550 °C the cement hydrate decomposes, yielding calcium oxide. Calcium carbonate
Calcium carbonate
Calcium carbonate is a chemical compound with the formula CaCO3. It is a common substance found in rocks in all parts of the world, and is the main component of shells of marine organisms, snails, coal balls, pearls, and eggshells. Calcium carbonate is the active ingredient in agricultural lime,...

 decomposes at about 600 °C. Rehydration of the calcium oxide on cooling of the structure causes expansion, which can cause damage to material which withstood fire without falling apart. Concrete in buildings that experienced a fire and were left standing for several years shows extensive degree of carbonation from carbon dioxide which is reabsorbed.

Concrete exposed to up to 100 °C is normally considered as healthy. The parts of a concrete structure that is exposed to temperatures above approximately 300 °C (dependent of water/cement ratio) will most likely get a pink color. Over approximately 600 °C the concrete will turn light grey, and over approximately 1000 °C it turns yellow-brown.
One rule of thumb is to consider all pink colored concrete as damaged that should be removed.

Fire will expose the concrete to gases and liquids that can be harmful to the concrete, among other salts and acids that occur when gases produced by a fire come into contact with water.

If concrete is exposed to very high temperatures very rapidly, explosive spalling of the concrete can result. In a very hot, very quick fire the water inside the concrete will boil before it evaporates. The steam inside the concrete exerts expansive pressure and can initiate and forcibly expel a spall.

Radiation damages

Exposure of concrete structures to neutron
Neutron
The neutron is a subatomic hadron particle which has the symbol or , no net electric charge and a mass slightly larger than that of a proton. With the exception of hydrogen, nuclei of atoms consist of protons and neutrons, which are therefore collectively referred to as nucleons. The number of...

s and gamma radiations in nuclear power plant
Nuclear power plant
A nuclear power plant is a thermal power station in which the heat source is one or more nuclear reactors. As in a conventional thermal power station the heat is used to generate steam which drives a steam turbine connected to a generator which produces electricity.Nuclear power plants are usually...

s and high-flux material testing reactor can induce radiation damage
Radiation damage
Radiation damage is a term associated with ionizing radiation.-Causes:This radiation may take several forms:*Cosmic rays and subsequent energetic particles caused by their collision with the atmosphere and other materials....

s in their concrete structures. Paramagnetic defects and optical centers are easily formed, but very high fluxes are necessary to displace a sufficiently high number of atoms in the crystal lattice of minerals present in concrete before significant mechanical damages are observed.
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