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England M60 1QD
On the Historv . oi Portland 150 Years
Cementitious building materials have a long history, and the date 1824, traditionally taken as the origin of portland cement, is in fact only the date of a patent ( I ) granted to Joseoh Asodin (1778-1855) of Leeds. Eneland. who mav not a t that'time have made portland cemeit a t all. ~ o d a y ; cement is the successor to a line of materials with a historv reaching hack to the ancient world; it has a chemistry o? perhaps unsurpassed complexity amongst major inorganic industrial materials and is still the subject of intense study. At some ~ o i n in t the second quarter of the 19th century, ago, the cement as we know it now was fir& about 150 produced. The very simplest of the mineral cements are those based on gypsum, hydrated calcium sulfate. Gypsum loses its water of crystallization easily on gentle heating to yield various olasters. These dehydrated suhstances when mixed with water reform a crystalline mass of synthetic gypsum, which however is mechanically weak and is slowly dissolved hv water. There is evidence that the ancientEevotians ". . mixed burnt gypsum with sand to make masonry mortars 12). Such mortars were unsuited to less arid climates. and OII [he nurthtm shores of the Xlediterrathe early bu~ldrrs nean dt.wlc>oed the ; k ~ l l ; of lime-hurninr ,conversion of calcium carbonate to the oxide). The quickkme produced is slaked with water to yield a lime putty, to which can he added sand to produce a mortar or coarse mineral to produce a concrete. Such pure lime mortars and concretes harden slowly and often incompletely by reaction with the carbon dioxide of the air to give calcium carbonate once more. The Roman builders could achieve superb quality in pure lime mortars of this kind-many examples remain today-hut these materials did not set from within the mass of the paste, nor did they have the quality of hydraulicily: the capacity to set in contact with water, so valuahle in many engineering situations. Hydraulic limes were produced by hoth Greeks and Romans by adding to the lime putty fine volcanic ash or crushed volcanic minerals, the Romans using the deposits a t Pozzuoli, so that now all such materials are known as pozzolanas. The Romans also discovered that crushed tiles could act as artificial pozzolanas. Both natural and artificial pozzolanas are composed chiefly of silica with some alumina in forms which on mixing with water will react readily with calcium hydroxide from the lime to give hydrated calcium silicates and aluminates. These important suhstances are closely similar to the cementing compounds in portland cements themselves. Because hoth the pozzolana and the lime are present in the mortar, the setting proceeds from within the mass; the extreme insolubility and useful strength of these hydrates leads to the property of hydraulicity. Lime-pozzolana cements were the only cements available for work in contact with water from the Roman period until as late as the 19th century ( 3 ) . In the 18th and 19th centuries, we see the beginnings of an understandine of whv it is that lime-oozzolana mixtures Iln\,e t h r w rcmarknhle hydraulic pr,,ptrries, and !he ;tart of .a I,?horwus ernoiricnl i t r u n ~ l p 1 0 make Iwtter and herter cements. But t h e understanding was a long time coming, and the early pioneers had very little help from the chemists of the day. In 1757 the great engineer John Smeaton
222 1 Journal of Chemical Education
began to build the third Eddystone lighthouse off the southwest coast of Britain ( 4 ) ,apparently a labor of Hercules in the absence of a good hydraulic cement. Smeaton, appreciating the need to obtain the best component materials fur the lime-pozzolana cement he intended to use, examined a number of mixtures, and found that the quality depended on the limestone (5). He made the important discovery that the best mortars were made from limes containing clay impurities. We recognize now that the aluminosilicate clay minerals are closely related to those in the pozzolana, with this essential difference: that they are burned intimately with the lime in the calcining process. I t soon emerged that certain heavily clay-bearing limestones Such were hydraulic in the absence of the pozzolana (6). materials became known as Roman cements. Various natural cements of this kind (whose properties depended in an erratic way on the composition of the mineral taken from the ground) achieved prominence in various places in the earlv vears of the 19th centurv. The essential roles of lime andsikca in producing hydra;lic cements were established some time before 1818 hv the Frenchman Vicat in his scientific studies of innumerable artificial mixtures of limestones and clays (7). Thus about the year 1824, a good many people in several European countries were interested in trying to make their fortunes by perfecting these cements. Some were spurred on by the belief that the Romans had had a secret for making fine cement which had been lost, and many unlikely substances were added in the hope of stumbling upon a missing ingredient. Lacking any clear notion of the nature of the cementing reactions and using the most variable of raw materials.. thev labored lareelv in the dark. Scientifically speaking the nature of portland cement did not emerge until well into the second half of the 19th centurv. Todav's cement is made by heating an intimate mixture of finely eround limestone and clav carefullv . .(in ~rouortions . . " adiusted by reference to analyses of raw materials) to a temperaThe ture sufficientlv . high . for oartial meltine " to occur (8). cooled granular product, a complex multiphase clinker, is ground to a powder of large surface area. This is portland cement. It consists primarily of a number of calcium silicate and aluminate comoounds. When mixed with water it forms a hydraulic paste which sets and hardens to a strong solid, larpelv c o m ~ o s e d of hydrates of calcium silicates but with a remarkahfy intricate physical microstructure. The critical variables closely controlled in manufacture are the composition of the feed (chalk:clay, 7525) and clinkering temperature (over 1400°C). Neither Aspdin nor anyone else for a long time after 1824 fully understood these basic facts. What then is the basis of Aspdin's claim to be the inventor of portland cement? On November 6, 1824, the gossip column of the newspaper the Leeds Mercury was preoccupied with its usual business of warning the honest citizens about the dishonest ("Last Saturdav. - . three females. handsomelv dressed. and having the appearance of respectable ladies, paid a five . . . hnnknote.. . to a haberdasher in Leeds, which is ~ound not worth a farthing") and gave only a single passing sentence to Aspdin's news. "We hear that Joseph Aspdin, bricklayer of this town, has obtained a patent for a superior
. 3 4 3 7 (1861.117 11962). even by the standards of the day. optical and electron micr©. 2. are not specified. London.... His product may simply have been yet another artificial hydraulic lime (excess lime) or Roman cement (excess silica). London. today regarded as essential to cement formation. 33. thev . R. F. ~ N." B r i t ~ irh Patent 5022:1824.R.NICOI.. The scanty records have been examined with great Aspdin was carrying on business as care by Halstead (6.'' Academic Presi. LSbd. No specimens appear to he available. By thk 1890's however the ~ m e r i c a n cements was expanding so rapidly that the indigenous portland cement industry was able to establish dominance. (91 Goading. and spent the rest of his rather short life in the cement industry. Conemla. T r o w Necueomen Sor . hut the claim made by a commentator much later in the century that he used a glass-making kiln rather than the cooler lime-hurnine kiln a t least holds out the possihility that he attained the temperatures necessarv for clinkerine (that is. Edward Arnold Ltd. reprint of the 1862 ed. There is no suggestion that the son made any innovations to his father's process. 1837. and Kentucky and Illinois. patent portland cement manufacturer a t times during the next ten years both in Leeds and Wakefield." John Weale. .A narrative of the buildins and a description of the construction of (41 Smeaton. especialiy the suns . (21 Lea.. 1970. No record has been found of his early kiln. The ~ u r o p e a nindustry at thisdate was well established." His patent B P 5022: 1824. and later in a number of other Eastern seaboard states. I81 For a de~criptionof the modern manufacturing process.. Professor Skempton's detailed studies (11) of the cements of the middle of the 19th century (including those produced by William Aspdin) provide the basis for making a case that Joseph Aspdin had stumbled upon the essential facts of manufacture. London. 27. Maude. velopment of the techniques and structural theory of reinforced concrete construction were its full potentialities realized. ~ ~ n d 1791. A.. M. W. . of Rotherhithe. for more complete reaction of . Samuel. w Literature Cited i l l Aspdin. At this time work was under way on the building of the new Houses of Parliament following the fire of 1834 and in 1843 the contractors carried out tests to compare Maude's new cement with the available Roman cement..I. T. Volume 53. If William Aspdin's Rotherhithe cement i n 1843 was a portland. Testing and Uses.. diffeiential thermal analysis. 18i1974).2). (11) Skempton. (31 D . and the materials science of cement and concrete remains an active and important area of study. W.lamer and William. moving from one venture to the next without ever apparently really prospering (10)... H. W. Trons. has been eathered toeether in a recent ertic1e bv Bari0ot. lime and clay). p. 1962.Number 4. The product was reliable and auicklv earned a market for good name. should be rega. Saylor was eranted his US patent (14). Briefly the argument is this. (10) Much interesting information an the history of the Aspdin iamily. compelling evidence that this was indeed a true portland cement. and so on (13). 35. '"Livesof the Engineers: vol. (61 Halstead. especially for strength.29 (1974. 1905. in East London to make the Aspdin cement.. Landon and ~ & Y o r k . Unfortunately little is known of Aspdin's manufacturing activities at this time. J. 1954. the Edystone 1i~hthou~e:'C. (71 Vicat.. W. in Tsylor. though it to establish his connection with some may yet he existing building of that period. The question of whether what Aspdin made in the early davs of his business. England.-such as X-ray diffraction techniques for compound identification. ~ a t u r a hydrauliE l cement had been discovered as earlv as 1818 in New York State. The understandine of the nature of the cement reactions-both the composition and phase relationships in the clinker and the details of the hvdration reactionshave been more recent. However. as are all details of the kiln which might have helped to establish this. Newton Abbot.9). Symposium on the Chemistry of Cement. P. there can be little doubt that Joseph Aspdin's product at that time was also. London.." Soon. as did the refinement of methods of chemical analysis of raw materials and changes in kiln de- - sign (12).ded as a true portland cement is a debated but still open auestion. Endenuour. Information about the burning temperature is of course also absent. whether this was the same cement as that which he was producing as earlv as 1824 we cannot at present say. "The Chemistrv of Cements. The natural cement rocks were found much more abundantly in these areas than in Europe and many of the products established good reputations in the middle of the 19th century. ~ : 52. Once the comparative tests of the 1840's showed publicly the superiority of portland cements over the other calcareous cements production began in a number of places in Europe and the gradual empirical improvement of the process and the material gathered speed. J. They were used in huge quantities in the great canal construction projects of those years-starting with the Erie Canal in the 1820's. There is no doubt that for the first few decades the production of portland cement was a primitive manufacturing enterprise. April 1976 / 223 . "Treatise on Calcareous Mortars and Cements.. The results of these tests seem definitely to show that the new cement was almost twice as strong . see Pollitt.. In 1841 William Aspdin entered into an agreement with a firm of Roman cement manufacturers. E. 6. His son William entered the business. Son & Co. hut few details have come to light. and certainly later in Wakefield. 112) A v i e r of the s a t e of cement msnufaeture at the heginning of this century is provided by Butlor. Turner. . H. "The Chemistry of Cement and Concrete: 3rd Ed. (51 For a life of Smeaton. and indeed not until the de". see Smiles. Cement and Concrete Annociation. The material took a considerable time to penetrate into constructional and civil eneineerine nractice. Aspdin did introduce the name portland cement.Londonand New York.. L.. F. The development of sound test methods. "Portland Cement: its Manufacture. The importation of European portland cements started in the later 1860's. P i o r Thirdlnli. The trade was viable only because the cement could travel free of charge westwards across the Atlantic as ballast in tramp careo ships seekine erain or cotton cargoes. m . His Drocess calls for the use of a "specific quantityGf limestoneand of clav hut sadlv . adsorption isotherm techniques. "An Improvement in the Modes of Producing an Artificial Stone" consisted of two hrief pages and the roughness of his manufacturine methods is apparent."An lmprovemenlin the Modes of Produeinpan Artif~eial Stone. pl. N ~ w c o m s n Soc. P. These facts help explain why portland cement was not produced in the US until 1871 when David 0. The earlv American portland cement manufac&ers had to face strong dual competition from the natural cement industry and from the portland cements imported from Europe. '. David and Charles.. 1968. a shrewd idea to link the unproven qualities of his new cement with those of a fine building stone. Other evidence which bears on whether Aspdin's early cement should be considered a portland is inferential. Ltd. J .cement representing Portland stone. played an important part in this. Advances in knowledae have been brought about by a number of modern experimental methods. sav from 1824 to 1830.. D. and Halstead.193 (197"). However. P. S& ~ ~ Enainaar. .in compression as the finest Roman cements available.
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