Cement is widely used in construction. Anyone who uses cement (or anything containing cement, such as mortar, plaster and concrete) or is responsible for managing its use should be aware that it presents a hazard to health.
Types of modern cement
Portland cement
Cement is made by heating limestone (calcium carbonate), with small quantities of other materials (such as clay) to 1450 °C in a kiln, in a process known as calcination, whereby a molecule of carbon dioxide is liberated from the calcium carbonate to form calcium oxide, or quicklime, which is then blended with the other materials that have been included in the mix . The resulting hard substance, called ‘clinker’, is then ground with a small amount of gypsum into a powder to make ‘Ordinary Portland Cement’, the most commonly used type of cement (often referred to as OPC).
Portland cement is a basic ingredient of concrete, mortar and most non-speciality grout. The most common use for Portland cement is in the production of concrete. Concrete is a composite material consisting of aggregate (gravel and sand), cement, and water. As a construction material, concrete can be cast in almost any shape desired, and once hardened, can become a structural (load bearing) element. Portland cement may be gray or white.
Portland cement blends
Portland cement blends are often available as inter-ground mixtures from cement manufacturers, but similar formulations are often also mixed from the ground components at the concrete mixing plant.
Portland blastfurnace cement contains up to 70 % ground granulated blast furnace slag, with the rest Portland clinker and a little gypsum. All compositions produce high ultimate strength, but as slag content is increased, early strength is reduced, while sulfate resistance increases and heat evolution diminishes. Used as an economic alternative to Portland sulfate-resisting and low-heat cements.
Portland flyash cement contains up to 30 % fly ash. The fly ash is pozzolanic, so that ultimate strength is maintained. Because fly ash addition allows a lower concrete water content, early strength can also be maintained. Where good quality cheap fly ash is available, this can be an economic alternative to ordinary Portland cement.
Portland pozzolan cement includes fly ash cement, since fly ash is a pozzolan, but also includes cements made from other natural or artificial pozzolans. In countries where volcanic ashes are available (e.g. Italy, Chile, Mexico, the Philippines) these cements are often the most common form in use.
Portland silica fume cement. Addition of silica fume can yield exceptionally high strengths, and cements containing 5-20 % silica fume are occasionally produced. However, silica fume is more usually added to Portland cement at the concrete mixer.
Masonry cements are used for preparing bricklaying mortars and stuccos, and must not be used in concrete. They are usually complex proprietary formulations containing Portland clinker and a number of other ingredients that may include limestone, hydrated lime, air entrainers, retarders, waterproofers and coloring agents. They are formulated to yield workable mortars that allow rapid and consistent masonry work. Subtle variations of Masonry cement in the US are Plastic Cements and Stucco Cements. These are designed to produce controlled bond with masonry blocks.
Expansive cements contain, in addition to Portland clinker, expansive clinkers (usually sulfoaluminate clinkers), and are designed to offset the effects of drying shrinkage that is normally encountered with hydraulic cements. This allows large floor slabs (up to 60 m square) to be prepared without contraction joints.
White blended cements may be made using white clinker and white supplementary materials such as high-purity metakaolin.
Colored cements are used for decorative purposes. In some standards, the addition of pigments to produce “colored Portland cement” is allowed. In other standards (e.g. ASTM), pigments are not allowed constituents of Portland cement, and colored cements are sold as “blended hydraulic cements”.
Very finely ground cements are made from mixtures of cement with sand or with slag or other pozzolan type minerals that are extremely finely ground together. Such cements can have the same physical characteristics as normal cement but with 50% less cement particularly due to their increased surface area for the chemical reaction. Even with intensive grinding they can use up to 50% less energy to fabricate than ordinary Portland cements.
Non-Portland hydraulic cements
Pozzolan-lime cements. Mixtures of ground pozzolan and lime are the cements used by the Romans, and can be found in Roman structures still standing (e.g. the Pantheon in Rome). They develop strength slowly, but their ultimate strength can be very high. The hydration products that produce strength are essentially the same as those produced by Portland cement.
Slag-lime cements. Ground granulated blast furnace slag is not hydraulic on its own, but is “activated” by addition of alkalis, most economically using lime. They are similar to pozzolan lime cements in their properties. Only granulated slag (i.e. water-quenched, glassy slag) is effective as a cement component. ”’Supersulfated cements”’. These contain about 80% ground granulated blast furnace slag, 15 % gypsum or anhydrite and a little Portland clinker or lime as an activator. They produce strength by formation of ettringite, with strength growth similar to a slow Portland cement. They exhibit good resistance to aggressive agents, including sulfate.
Calcium aluminate cements are hydraulic cements made primarily from limestone and bauxite. The active ingredients are monocalcium aluminate CaAl2O4 (CaO · Al2O3 or CA in Cement chemist notation, CCN) and mayenite Ca12Al14O33 (12 CaO · 7 Al2O3 , or C12A7 in CCN). Strength forms by hydration to calcium aluminate hydrates. They are well-adapted for use in refractory (high-temperature resistant) concretes, e.g. for furnace linings.
Calcium sulfoaluminate cements are made from clinkers that include ye’elimite (Ca4(AlO2)6SO4 or C4A3\bar \mathrm{S} in Cement chemist’s notation) as a primary phase. They are used in expansive cements, in ultra-high early strength cements, and in “low-energy” cements. Hydration produces ettringite, and specialized physical properties (such as expansion or rapid reaction) are obtained by adjustment of the availability of calcium and sulfate ions. Their use as a low-energy alternative to Portland cement has been pioneered in China, where several million tonnes per year are produced. Energy requirements are lower because of the lower kiln temperatures required for reaction, and the lower amount of limestone (which must be endothermically decarbonated) in the mix. In addition, the lower limestone content and lower fuel consumption leads to a CO2 emission around half that associated with Portland clinker. However, SO2 emissions are usually significantly higher.
“Natural” cements correspond to certain cements of the pre-Portland era, produced by burning argillaceous limestones at moderate temperatures. The level of clay components in the limestone (around 30-35 %) is such that large amounts of belite (the low-early strength, high-late strength mineral in Portland cement) are formed without the formation of excessive amounts of free lime. As with any natural material, such cements have highly variable properties.
Geopolymer cements are made from mixtures of water-soluble alkali metal silicates and aluminosilicate mineral powders such as fly ash and metakaolin.
The setting of cement
Cement sets when mixed with water by way of a complex series of hydration chemical reactions still only partly understood. The different constituents slowly hydrate and crystallise while the interlocking of their crystals gives to cement its strength. After the initial setting, immersion in warm water will speed up setting. In Portland cement, gypsum is added as a compound preventing cement flash setting. The time it takes for cement to set varies; and can take anywhere from twenty minutes for initial set, to twenty-four hours, or more, for final set.
Environmental Impacts
Cement manufacture causes environmental impacts at all stages of the process. These include emissions of airborne pollution in the form of dust, gases, noise and vibration when operating machinery and during blasting in quarries, and damage to countryside from quarrying. Equipment to reduce dust emissions during quarrying and manufacture of cement is widely used, and equipment to trap and separate exhaust gases are coming into increased use. Environmental protection also includes the re-integration of quarries into the countryside after they have been closed down by returning them to nature or re-cultivating them.
CO2 emissions
Cement manufacturing releases CO2 in the atmosphere both directly when calcium carbonate is heated, producing lime and carbon dioxide, and also indirectly through the use of energy if its production involves the emission of CO2. The cement industry is the second largest CO2 emitting industry behind power generation. The cement industry produces about 5% of global man-made CO2 emissions, of which 50% is from the chemical process, and 40% from burning fuel.The amount of CO2 emitted by the cement industry is nearly 900 kg of CO2 for every 1000 kg of cement produced. In certain applications, lime mortar, reabsorbs the CO2 chemically released in its manufacture, and has a lower energy requirement in production. Newly developed cement types from Novacem and Eco-cement can absorb carbon dioxide from ambient air during hardening.
Heavy metal emissions in the air
In some circumstances, mainly depending on the origin and the composition of the raw materials used, the high-temperature calcination process of limestone and clay minerals can release in the atmosphere gases and dust rich in volatile heavy metals, a.o, thallium, cadmium and mercury are the most toxic. Heavy metals (Tl, Cd, Hg, …) are often found as trace elements in common metal sulfides (pyrite (FeS2), zinc blende (ZnS), galena (PbS), …) present as secondary minerals in most of the raw materials. Environmental regulations exist in many countries to limit these emissions.
Heavy metals present in the clinker
The presence of heavy metals in the clinker arises both from the natural raw materials and from the use of recycled by-products or alternative fuels. The high pH prevailing in the cement porewater (12.5 < pH < 13.5) limits the mobility of many heavy metals by decreasing their solubility and increasing their sorption onto the cement mineral phases. Nickel, zinc and lead are commonly found in cement in non-negligible concentrations.
Use of alternative fuels and by-products materials
A cement plant consumes 3 to 6 GJ of fuel per tonne of clinker produced, depending on the raw materials and the process used. Most cement kilns today use coal and petroleum coke as primary fuels, and to a lesser extent natural gas and fuel oil. Selected waste and by-products with recoverable calorific value can be used as fuels in a cement kiln, replacing a portion of conventional fossil fuels, like coal, if they meet strict specifications. Selected waste and by-products containing useful minerals such as calcium, silica, alumina, and iron can be used as raw materials in the kiln, replacing raw materials such as clay, shale, and limestone. Because some materials have both useful mineral content and recoverable calorific value, the distinction between alternative fuels and raw materials is not always clear. For example, sewage sludge has a low but significant calorific value, and burns to give ash containing minerals useful in the clinker matrix.
Tests
Cement can be tested on site or in a laboratory depending on the scope and use of the cement. The number of samples that should be taken depends on the importance of the work but it is chiefly important that the sample should represent a fair average of the contents.
Concrete Tests.
– Sampling of Trial Mix ( at Batching Plant )
– Sampling of Aggregates ( at stockpile )
– Sampling of Reinforcement
– Speedy Test ( for moisture content )
– Slump Test ( for workability of concrete )
– Compacting Factor Test ( for self compaction of concrete )
– Temperature Test ( for green concrete )
– Compression Test ( for Compression Test )
– Sand Patch Test ( for surface texture of rigid pavement )
– Rolling Edge Test ( for surface profile of rigid or flexible pavement )
– Test cores ( for hardened concrete / asphalt concrete )
– Cover metre test ( for reinforced concrete structure )
– Schimdt Hammer Test ( for structural concrete )
Safety
Health effects
Cement can cause ill health mainly by:
- skin contact;
- inhalation of dust; and
- manual handling.
Skin contact
Contact with wet cement can cause both dermatitis and burns.
Dermatitis
Skin affected by dermatitis feels itchy and sore, and looks red, scaly and cracked. Cement is capable of causing dermatitis by two mechanisms – irritancy and allergy.
Irritant dermatitis is caused by the physical properties of cement that irritate the skin mechanically. The fine particles of cement, often mixed with sand or other aggregates to make mortar or concrete, can abrade the skin and cause irritation resulting in dermatitis. With treatment, irritant dermatitis will usually clear up. But if exposure continues over a longer period the condition will get worse and the individual is then more susceptible to allergic dermatitis.
Allergic dermatitis is caused by sensitisation to the hexavalent chromium (chromate) present in cement. The way this works is quite distinct from that of irritancy. Sensitisers penetrate the barrier layer of the skin and cause an allergic reaction. Hexavalent chromium is known to be the most common cause of allergic dermatitis in men. Research has shown that between 5% and 10% of construction workers may be sensitised to cement and that plasterers, concreters and bricklayers are particularly at risk. Once someone has become sensitised to hexavalent chromium, any future exposure may trigger dermatitis. Some skilled tradesmen have been forced to change their trade because of this. The longer the duration of skin contact with a sensitiser, the more it will penetrate the skin, and the greater the risk of sensitisation will become. Therefore, if cement is left on the skin throughout the working day, rather than being washed off at intervals, the risk of contact sensitisation to hexavalent chromium will be increased. Both irritant and allergic dermatitis can affect a person at the same time.
Cement burns
Wet cement can cause burns. The principal cause is thought to be the alkalinity of the wet cement. If wet cement becomes trapped against the skin, for example by kneeling in it or if cement falls into a boot or glove, a serious burn or ulcer can rapidly develop. These often take months to heal, and in extreme cases will need skin grafts or can even lead to amputation. Serious chemical burns to the eyes can also be caused following a splash of cement.
Inhalation of dust
High levels of dust can be produced when cement is handled, for example when emptying or disposing of bags. In the short term, exposure to high levels of cement dust irritates the nose and throat. Scabbling or concrete cutting can also produce high levels of dust which may contain silica. Advice on the health effects of exposure to silica can be found in Construction Information Sheet 36 (rev1).
Manual handling
Working with cement also poses risks such as sprains and strains, particularly to the back, arms and shoulders from lifting and carrying cement bags, mixing mortar etc. More serious damage to the back can be caused in the long term if workers are continually lifting heavy weights.
Skin contact
You should first consider using elimination or substitution to prevent the possibility of contact with cement. Otherwise, you should apply control measures which minimise contact with the skin either directly or indirectly from contaminated surfaces in the working environment.
An important way of controlling cement dermatitis is by washing the skin with warm water and soap, or other skin cleanser, and drying the skin afterwards. Sinks should be large enough to wash the forearms and have both hot and cold (or warm) running water. Soap and towels should be provided. Facilities for drying clothes and changing clothes should also be available.
Gloves may help to protect skin from cement, but they may not be suitable for all aspects of construction site work. Caution is advised when using gloves as cement trapped against the skin inside the glove can cause a cement burn. You should provide protective clothing, including overalls with long sleeves and long trousers. Employers are required to arrange for employees to receive suitable health surveillance where there is exposure to a substance known to be associated with skin disease and where there is a reasonable likelihood that the disease may occur. This means you should provide health surveillance for workers who will be working with wet cement on a regular basis.
Health surveillance is needed to:
- protect individuals;
- identify as early as possible any indicators of skin changes related to exposure, so that steps can be taken to treat their condition and to advise them about the future; and
- give early warning of lapses in control.
Health surveillance must never be regarded as reducing the need to control exposure or to wash cement off the skin.
Simple health surveillance will usually be sufficient. Skin inspections should be done at regular intervals by a competent person, and the results recorded. Employers will probably need the help of an occupational health nurse or doctor to devise a suitable health surveillance regime and they will need to train a ‘responsible person’, for instance a supervisor, to carry out the skin inspections.
A responsible person is someone appointed by the employer who, following instruction from an occupational health physician or nurse, is competent to recognise the signs and symptoms of cement-related dermatitis. The responsible person should report any findings to the employer, and will need refer cases to a suitably qualified person (eg an occupational health nurse).
The employer must keep health records containing the particulars set out in the Appendix to the General COSHH Approved Code of Practice (see References). Employers are also required to provide employees with information, instruction and training on the nature of the risk to health, and the precautions to be taken. This should include characteristic signs and symptoms of dermatitis.
Employees should be encouraged to examine their own skin for any such signs and report them. Reports should be made to the ‘responsible person’ or to the occupational health nurse.
Inhalation of dust
Exposure to dust should be eliminated where possible, for example, by purchasing ready mixed concrete. Where this is not possible, the risk should be assessed and appropriate control measures implemented.
Manual handling
Manual handling of heavy loads should be avoided. In particular, cement should be supplied in 25 kg bags or ordered in bulk supply. Where manual handling does take place, you should assess the risks and adopt appropriate risk control measures.
Legal provisions
United Kingdom
The Control of Substances Hazardous to Health Regulations 1999 and the Management of Health and Safety at Work Regulations 1999 require the employer to assess health risks and prevent or control exposure.
The Construction (Health, Safety and Welfare) Regulations 1996 require those in control of construction sites to ensure that suitable and sufficient welfare facilities are provided. This includes providing adequate washing facilities with hot and cold (or warm) running water and facilities for changing and drying clothing.
The Personal Protective Equipment at Work Regulations 1992 require employers to provide suitable personal protective equipment for their employees, to make sure it is maintained (and replaced, where necessary) and to inform, instruct and train employees required to use it.
The Manual Handling Operations Regulations 1992 require employers to avoid manual handling where reasonably practicable and undertake risk assessment of the remaining manual handling tasks.
