Phosphorus: from urine to fire
Part 2. From cold fire to instant lights - the history of the match
Peter E. Childs
University of Limerick, Limerick

Until matches were invented making fire relied on laborious and unreliable methods: flint and steel, a burning glass (if there was sunlight), rubbing dry sticks together .. The discovery of fire was the most important step in the development of civilisation, as it made possible cooking food to increase its nutrition and availability, and the production of glass, pottery, metals ..., as well as providing heat and light when required. It is something we take for granted but lighting a fire was still a difficult and time-consuming task until the beginning of the 19th. century. In many cultures fires were kept in permanently or glowing embers were carried around in pots. Letting the fire out was a major event. It is difficult for us to stand in the shoes of those earlier generations before matches were invented. But this simple, chemical invention enabling anyone to strike a light instantly, was truly revolutionary. The following poem puts this very graphically:

When the last match goes out, O how shall we
Ever recall the proper flint and stone
To create bright and warming flame once more?
When the last match goes out, shall we see
If we are a multitude or alone? ..
Dana E. Scott "Night Song" 19861

            When George Stephenson was making his first trial of 'Locomotion' (another milestone in technology) it was discovered that no one had a light! Just when they were about to send off for a lighted lantern to fire up the boiler, a man offered the use of his burning glass which he used to light his pipe, and with its aid the Locomotion's fire was lit and history was made. For want of a match ...
            Over 150 years elapsed between the discovery of phosphorus and the first useful match, although many attempts were made to use phosphorus' property of instantaneous combustion in air as a source of instantaneous fire. This is the reason that white phosphorus must be stored under water. Sulphur-coated sticks has been used since Roman times for catching the spark from a tinder and flint, as sulphur catches fire readily. The burning splint (or match) could then be used to light a lamp or a fire. Robert Boyle put a small amount of phosphorus between folds of coarse paper and used it to ignite a sulphur match. However, the unique properties of white phosphorus in catching fire were largely ignored for over 100 years.
            Making a safe, workable device that would produce fire on demand was a challenge to the ingenuity of chemists and the venture was truly international. Many solutions were found to the problem before chemists hit upon the right chemistry to produce the friction match: a wooden splint, coated with chemicals, which only catches fire when rubbed or struck against a rough surface.

Some key dates in the history of matches
Early instantaneous lights
            One of the earliest portable devices using phosphorus was an air-tight bottle, coated on the inside with white phosphorus. The top was removed, and a wooden splint rubbed against the sides picking up a small amount of phosphorus. When exposed to the air it caught fire! These were known as phosphorus bottles or pocket luminaries.
            In 1805 Chancel utilised the oxidising power of conc. sulphuric acid to ignite a mixture of potassium chlorate and sugar (first discovered by Berthollet). Cedar-wood splints were coated with the paste and dipped into a small bottle, containing conc. sulphuric acid absorbed on asbestos. On withdrawing the match it burst into flames. They were known as 'instantaneous light boxes'. A man named Heurtner opened a shop in the Strand, called the Lighthouse, where he sold ornamental boxes containing 50 matches and a small bottle of sulphuric acid on asbestos for one shilling. His advertising slogan for these 'Empyrions' (also spelt euperion) was: "To save your knuckles, time and trouble, use Heurtner's Empyrion, price one shilling". They sold well and were known colloquially as the Hugh Perry. They weren't always very reliable as a contemporary account shows:
"Instead of a brilliant flame, the match smouldered only and spurted acid about to the detriment of clothes and a peaceful disposition."
            Samuel Jones patented Prometheans in 1828, which consisted of a cardboard tube containing potassium chlorate and sugar and a sealed glass bead of conc. sulphuric acid. When crushed with a pair of pliers the device burst into flames. (Heurtner also marketed a version of these as Vesuvians.) The sulphuric acid matches were also referred to as Chemical Matches and as Oxymuriated Matches.
            Pyrophoric powders are chemicals in finely-powdered and reactive state which catch fire on exposure to air. Homberg, Hare and D”bereiner all produced their own form of 'pyrophorus', but they were difficult to make and not very successful. A pyrophoric mixture was patented as recently as 1937 based on finely-divided iron or nickel.
            The famous German chemist D”bereiner invented his 'platinum lamp' in 1823, which used spongy platinum as a catalyst to ignite hydrogen gas, generated by the action of dilute sulphuric acid on zinc. Not a very practical device but the principle is used in the flameless hair curlers and blow-lamps of today.
            All these devices were cumbersome, tricky to use, often dangerous and unreliable, and very expensive. The common man or woman still continued to use his or her tinder box.

Friction lights
            In 1827 John Walker, a chemist/druggist from Stockton-on-Tees, was selling his friction matches in boxes of 100. He dipped wooden splints in sulphur and tipped them with a paste made from potassium chlorate, sugar and antimony trisulphide. The match was ignited by drawing through a fold of sandpaper. Sometimes it didn't work and sometimes a flaming ball flew off and landed on the carpet or a dress. Some reports suggest that Walker discovered the idea of a friction match by accident when some 'percussion powder' (a mixture of potassium chlorate and antimony sulphide) that he was making fell on a stone hearth and ignited. The first record of a sale is in 1827 but he could well have been making them a year earlier. These matches were prohibited in Germany and France because they were thought to be too dangerous. Walker is often credited with inventing the friction match, although his matches contained no phosphorus. The idea of using friction to generate the heat needed to ignite the match has been followed ever since, rather than using spontaneous chemical reactions to produce a flame.

Commemorative tablet on Walker's house in Stockton

            In 1830 Samuel Jones sold his version of Walker's 'friction lights' in London and called tham Lucifers, later used to describe phosphoric matches. He was the first person to sell matches in small, rectangular cardboard boxes. Lucifer became a popular, generic name for matches - named not for their devilish properties but because they were light-bearing! The sulphur-based matches gave off copious and noxious fumes, and the following warning was printed on the box of Jone's lucifers:
"If possible, avoid inhalng gas that escapes from the combustion of the black composition. Persons whose lungs are delicate should by no means use the lucifers."
            Although these friction matches worked they were soon to be replaced by phosphorus-based matches which ignited more reliably.2
            Between 1830 and 1834 several people in different countries invented white phosphorus-based matches, which became known as Congreves or Lucifers. J.F. Kammerer (Germany) is often credited with the first P-based friction match, although Charles Sauria had made them two years earlier in France, and Hungary also claims J nos Irinyi as the inventor!. The first US patent was granted to A.D. Philips in 1836. Friction matches were often called LocoFoco in the United States.
            In the early 19th. century the race to invent the best match was hotly contested as there were fortunes to be made. The matches often had a sulphur tip, which was tipped again with the phosphorus-oxidiser composition. In America the matches were often kept in metal match safes, as there was always a risk of the matches igniting. The articles by Crass and Thorpe give much detail on the early match compositions.
            The fuzee (fusee) was also invented by Samuel Jones in 1832 and consisted of a friction head on a cardboard splint soaked in potassium nitrate, which would keep smouldering after ignition. It was intended specifically for lighting cigars! Later they were used for setting off explosives safely. The original Vesta match (William Newton, 1832) was a wax taper tipped with a friction composition, giving a long-burning taper. The later Swan Vestas had wooden splint soaked in wax.

From white to red phosphorus
            The harmful effects of white phosphorus became known quite early, particularly for those making matches who suffered from phosphorus necrosis or 'phossy jaw'. Red phosphorus was first made by Anton Schr”tter in 1844 by heating white phosphorus. It was non-toxic and much less flammable. Various attempts were made to produce a safety match using red P (e.g. R. B”ttger, 1845) and in 1851 Albright developed an improved method for making red P on a commercial scale in the U.K.. In 1855 the first successful safety match was produced in Sweden by J.E. Lundstr”m. As well as using red phosphorus instead of white, the phosphorus was confined to a strip on the box and the oxidiser was used to tip the matches. Such 'safety' matches could only be ignited by striking on the box, whereas earlier matches were could be struck anywhere on a rough surface. Albright and Wilson promoted the safety matches but it was to take over 50 years before the use of white phosphorus in matches was finally outlawed worldwide.
            In 1906 an International Convention was signed in Berne to ban white phosphorus, although many countries had already done so. The phosphorus matches also glowed in the dark when warm and Alexander Finlay3 records:
"We can all recall these matches, which had a fascination for us in our younger days through the glow of phosphorescent light which they emitted when slightly warmed by rubbing on the hand."3

Composition mixing room, Bryant & May, Liverpool
            Matches containing white phosphorus were not only a health hazard to the match makers, but also to those using them as when warm they could give off phosphorus fumes. Swallowing match heads was also a common method of committing suicide and small children were often poisoned by swallowing match heads. In 1899 a Parliamentary Commission reported on the Use of phosphorus in the manufacture of lucifer matches, which gave a comprehensive account of the manufacture, health hazards and safety precautions being taken by manufacturers. Phosphorus vapour is oxidised in air to phosphorus(V) oxide (P4O10) and it the oxide that is dangerous. It is taken into the body through cavities in the teeth and destroys the jaw, causing 'phossy jaw' or phosphorus necrosis. It does not attack people with sound teeth and the match manufacturers introduced free dental treatment and regular inspections to protect their workers. The replacement of white phosphorus, first by red phosphorus and from 1898 by phosphorus sesquisulphide (P4S3), was the only satisfactory solution to the problem. In 1910 legislation in the U.K. banned the manufacture and sale of white phosphorus-based matches. The Americans were among the last to get rid of white phosphorus, not by legislation but by raising the tax to make them prohibitively expensive.
            Phosphorus sesquisulphide was first made in 1864 by Lemoine in France by heating white phosphorus with sulphur in the absence of air. In 1898 Henri Sévène and Emile Cahen patented a new match composition using phosphorus sesquisulphide. Crass refers to this historic event:
"The successful adaptation of the sesquisulphide to the match manufacturing industry was perhaps the most outstanding contribution to the history of fire-making since Brandt's discovery of phosphorus, and its use as the active ingredient in friction match compositions was rapidly adopted by most civilised countries."4


US Patent for safety matches (1898)
            Manufacture started in France in 1898 and in the UK in 1900 by Bryant and May, the largest UK match manufacturer. The USA were one of the last countries to adopt safer match compositions, as the original phosphoric friction matches were very cheap. It was not possible to outlaw their production in the USA as Congress did not have such powers. However, the safety case had been made and in 1910 President Taft said in his annual address to Congress:
"I invite attention to the very serious injury caused to all those who are employed in the manufacture of phosphorus matches. The diseases incident to this are frightful, and as the matches can be made from other materials entirely innocuous, I believe that the injurious manufacture could be discontinued and ought to be discontinued by the imposition of a heavy federal tax. I recommend the adoption of this method of stamping out a very serious abuse." However, it was not until 1913 that a bill taxing white phosphorus in matches out of existence was made law.

Conclusion
Sadly no matches are made any more in Ireland or the U.K., after over a century of manufacture. Maguire & Paterson closed down their Irish manufacturing operation in 1989. They had been making matches in Hammond Lane, Dublin since 1882. Bryant & May closed down their last plant in Liverpool in 1992, having sytarted production in London in 1861. Both are owned by the Swedish Match Co., the world's largest manufacturer of matches, and all matches are now imported. The rise in use of the disposable gas lighter for cigarettes undermined a major market for matches, and production was no longer viable. The same brands are sold but they are made abroad.

References
1. quoted in M.K. Wren, A Gift Upon the Shore, London: Penguin Books, 1991, p. 120
2. H.G. Hubbard, Scientific American, June 16, 1934, reprinted in The Rushlight vol.1, no. 1, 1934, the magazine of The Rushlight Club, an American association evoted to the history of lighting.
3. A. Findlay, (Chemistry in the Service of Man, London: Longmans, Green & Co., 1920, p. 28
4. M. F. Crass, 'A history of the match industry', part IX, J. Chem. Educ., 18, 428-431

Bibliography
M.F. Crass, A History of the Match Industry, J. Chem. Educ., 18, part 1 116-120, part 2 277-282, part 3 316-319, part 4 380-384, part 5 428-431, 1941
Edward Thorpe, 'Matches' in A Dictionary of Applied Chemistry, vol. III, London: Longmans, Green & Co., 1916, p. 404-424
The Science Museum in London houses the Bryant & May Museum of fire-making devices, including matches.

Websites
www.seita.fr/artdufeu/gb/files/hist.html
History of matches by the Franch company Seita and at the same site a description and pictures of match manufacture.
www.adh.bton.ac.uk/schoolofdesign/MA.COURSE/16/BM/awelcome.html
A photographic record of match production at Bryant & May's Speke factory in 1985, now closed.

A match machine (from Thorpe, 1916)