Calcium carbonate has been used from as early as 40,000 BC to present day.
The history of calcium carbonate illustrates how we have been able to utilise the unique properties of this mineral in applications ranging from prehistoric cave paintings to modern paper and plastic manufacturing.
40,000 – 10,000 BC.
The major prehistoric use was the flints within the chalk, which are known to have been used as tools by prehistoric man.
Calcium carbonate has been detected in nearly all prehistoric cave paintings in the period between 40,000 and 10,000 BC, though it was only right at the end of this epoch that chalk and limestone powders were actually used by the caveman artists.
100 – 500 AD.
Chalk, flint and gravel were used by the Romans to construct road systems. They utilised chalk in many other ways including in coffins to preserve bodies and in cosmetics worn by Roman women.
Anglo-Saxon Britain – Middle Ages
In Roman Britain, Anglo-Saxons times and in the Middle Ages, chalk was applied to the land as a fertiliser – a practice still routinely carried out by farmers today. Regular calcium carbonate applications help reduce soil acidity and help optimise conditions for crop growth. Old Norman leases often contained covenants to ensure that chalk was regularly applied to the land, and a statute of Henry III in 1225 gave every man the right to sink a marl pit on his own land.
Other uses for chalk in the Middle Ages include medicinal purposes in the fight against scurvy, probably unsuccessfully, and in the mid to late 14th century Welsh market traders used to try to pass chalk off as a hard cheese on unsuspecting customers, hence the popular term 'chalk & cheese'!
Industrial Revolution - 18th Century
Glazing putty, a mixture of chalk and linseed oil was believed to have been introduced as a sealing material for glass windows.
The first historical reference to a putty formulation is in a book on 'building art' published by Johann Friedrich Penther in 1745. The formulation is believed to have originated from Britain. However, it wasn't until the beginning of the 20th Century that industrially manufactured glazing putty was introduced.
Industrial Revolution - 19th Century
The large increase in the construction of brick and stone buildings in the 18th and 19th centuries increased the use of calcium carbonate in limewash and paints. The industrial revolution also created a demand for calcium carbonate powders from dyehouses and printers. Calcium carbonate suppliers also started adopting industrial production methods.
1841: Precipitated calcium carbonates (PCC) were first produced commercially in 1841. The first producer was the English company, John E. Sturge Ltd., which treated the residual calcium chloride from their potassium chlorate manufacture with soda ash and carbon dioxide to form what they called precipitated chalk. In 1898, a new factory was built in Birmingham using the milk of lime process - a process still used today
1860: Fredrick Walton invented linoleum in 1860 and it quickly become very popular as a home flooring material because of its flexibility and resilience. Linoleum is made from linseed oil and natural resin mixed with cork, wood flour and chalk or ground limestone. It remained a major application for calcium carbonate until production all but ceased by 1965 as it was replaced by vinyl flooring. However, in more recent time times it has been enjoying something of a renaissance.
1880: Chalk was used in cleaning powders, pastes, detergents, liquid metal cleaning agents, cleaning stones and a wide variety of 'cleaning formulations' that were commercially produced. However, after the 2nd world war this market steadily declined and, just as the case with toothpaste, chalk was rapidly superseded by improved materials.
1900: The secret of glass making came to Britain with the Romans. In Britain, there is evidence of a glass industry round Jarrow and Wearmouth dating back to 680AD. However, until the 18th and 19th centuries glass were very expensive and was used for limited applications, such as stained-glass windows for churches. Large-scale glass manufacture and use of limestone began with the industrial revolution with the mass production of glass containers beginning at the onset of the 20th century.
20th Century
Early 1900s: Modern toothpaste was invented to aid in the removal foreign particles and food substances, as well as clean the teeth. When originally marketed to consumers, toothpaste was packaged in jars. Natural chalk was commonly used as the abrasive in formulations in the early part of the twentieth century but was almost entirely replaced by precipitated calcium carbonate (PCC) by the 1930's. PCC remained the most widely used cleaning agent in tooth care until the 1960's.
1930s: As early as the 19th century fillers and reinforcing agents were incorporated into rubber and the first plastic materials. Cork and wood flour were added to rubber floor-coverings and asbestos, scrap paper and wood fibres were added to Bakelite. However, the addition of mineral fillers, such as calcium carbonate, to natural rubber didn't become standard practice until the 1930's.
1940s: It was decided that Calcium ("Chalk") should be added to British wartime bread after an outbreak of rickets in Dublin in 1940. At that time, it was thought that a drop in calcium intake caused by the rationing of normal calcium-rich foods such as milk and cheese would cause more children to develop rickets, and some adults to develop the bone disease, osteomalacia. So, in 1943 the Calcium Flour Order was passed making the addition of chalk (Creta praeparata) a mandatory flour additive.
1950s: The first thermoplastic was Polyvinyl Chloride. Originally developed in the 1870's it did not become a commercial reality until plasticisers were developed in the early 1930's. However, it wasn't until the 1950's when production methods became cheaper and simpler that PVC use increased significantly. Plastics production in Western Europe increased 10-fold in a decade and the use of calcium carbonate grew with it.
The paint-making industry also began to change in the 1950's. Rapid industrial growth and high demands on the properties of surface coatings awakened interest in extenders. Paints were required for an ever-increasing range of industrial and household applications and the ability to tailor calcium carbonate to almost any desired particle size distribution and fineness made it by far the most important extender.
1960s/1970s: Calcium carbonate was not introduced into modern printing papers until around the mid 20th century and subsequently transformed paper making by prompting the switch from acid to neutral sizing. This opened the door to widely available GCC as well as PCC, both are now used as fillers in uncoated woodfree paper and are the most commonly used pigments in graphic papers and paperboard today.
1980s: Flue gas desulphurisation technology introduced for major sulphur dioxide (S02) emitters, like power plants. The technology has significantly reduced 'acid-rain' and employs a sorbent, usually lime or limestone, to remove sulphur dioxide from the gases produced by burning fossil fuels.
1995: Prior to the 1990's the use of fillers in polyolefins was limited but that changed with the next generation of ultrafine, extremely consistent surface-treated calcium carbonates. The first 'mineral modifiers' based on calcium carbonates were developed for 'breathable' films for the booming hygiene market - particularly for diapers. These highly functional fillers increase productivity as well as improving the physical properties of the polyethylene (PE) film. Similar products are now used in PE and BOPP (Biaxially-orientated polypropylene) films for bags, printed films and packaging.
21st Century
The calcium carbonate industry will be shaped by the 3 big E's dominating the early 21st century landscape: the Economy, Energy and Ecology. This will lead to the decline of some traditional markets and the emergence of new ones but what is certain is that calcium carbonate will continue to play a significant role in products used in everyday life.