Chapter I: Part 1

Transcriber's notes:

(1) Numbers following letters (without space) like C2 were originally
printed in subscript. Letter subscripts are preceded by an
underscore, like C_n.

(2) Characters following a carat (^) were printed in superscript.

(3) Side-notes were relocated to function as titles of their respective
paragraphs.

(4) Macrons and breves above letters and dots below letters were not
inserted.

ENCYCLOPAEDIA BRITANNICA

A DICTIONARY OF ARTS, SCIENCES, LITERATURE
AND GENERAL INFORMATION

ELEVENTH EDITION

VOLUME V, SLICE VI

Celtes, Konrad to Ceramics

ARTICLES IN THIS SLICE:

CELTES, KONRAD CENTO (town of Italy)
CELTIBERIA CENTO (composition)
CEMENT CENTRAL AMERICA
CEMETERY CENTRAL FALLS
CENCI, BEATRICE CENTRALIA
CENOBITES CENTRAL INDIA
CENOMANI CENTRAL PROVINCES AND BERAR
CENOTAPH CENTUMVIRI
CENSOR CENTURION
CENSORINUS CENTURIPE
CENSUS CENTURY
CENTAUREA CEOS
CENTAURS CEPHALIC INDEX
CENTAURUS CEPHALONIA
CENTAURY CEPHALOPODA
CENTENARY CEPHEUS
CENTERVILLE CEPHISODOTUS
CENTIPEDE CERAM
CENTLIVRE, SUSANNA CERAMICS

CELTES, KONRAD (1459-1508), German humanist and Latin poet, the son of a vintner named Pickel (of which Celtes is the Greek translation), was born at Wipfeld near Schweinfurt. He early ran away from home to avoid being set to his father's trade, and at Heidelberg was lucky enough to find a generous patron in Johann von Dalberg and a teacher in Agricola. After the death of the latter (1485) Celtes led the wandering life of a scholar of the Renaissance, visiting most of the countries of the continent, teaching in various universities, and everywhere establishing learned societies on the model of the academy of Pomponius Laetus at Rome. Among these was the _Sodalitas litteraria Rhenana_ or _Celtica_ at Mainz (1491). In 1486 he published his first book, _Ars versificandi et carminum_, which created an immense sensation and gained him the honour of being crowned as the first poet laureate of Germany, the ceremony being performed by the emperor Frederick III. at the diet of Nuremberg in 1487. In 1497 he was appointed by the emperor Maximilian I. professor of poetry and rhetoric at Vienna, and in 1502 was made head of the new Collegium Poetarum et Mathematicorum, with the right of conferring the laureateship. He did much to introduce system into the methods of teaching, to purify the Latin of learned intercourse, and to further the study of the classics, especially the Greek. But he was more than a mere classicist of the Renaissance. He was keenly interested in history and topography, especially in that of his native country. It was he who first unearthed (in the convent of St Emmeran at Regensburg) the remarkable Latin poems of the nun Hrosvitha of Gandersheim, of which he published an edition (Nuremberg, 1501), the historical poem _Ligurinus sive de rebus gestis Frederici primi imperatoris libri x._ (Augsburg, 1507), and the celebrated map of the Roman empire known as the _Tabula Peutingeriana_ (after Konrad Peutinger, to whom he left it). He projected a great work on Germany; but of this only the _Germania generalis_ and an historical work in prose, _De origine, situ, moribus et institutis Nurimbergae libettus_, saw the light. As a writer of Latin verse Celtes far surpassed any of his predecessors. He composed odes, elegies, epigrams, dramatic pieces and an unfinished epic, the _Theodoriceis_. His epigrams, edited by Hartfelder, were published at Berlin in 1881. His editions of the classics are now, of course, out of date. He died at Vienna on the 4th of February 1508.

For a full list of Celtes's works see Engelbert Klüpfel, _De vita et
scriptis Conradi Celtis_ (2 vols., Freiburg, 1827); also Johann
Aschbach, _Die früheren Wanderjahre des Conrad Celtes_ (Vienna, 1869);
Hartmann, _Konrad Celtes in Nürnberg _(Nuremberg, 1889).

CELTIBERIA, a term used by Greek and Roman writers to denote, sometimes the whole north-east of Spain, and sometimes the north-east part of the central plateau of the peninsula. The latter was probably the correct use. The Celtiberi, in this narrower sense, were not so much one tribe as a group of cantons--Arevaci, Pelendones, Berones and four or five others. They were the most warlike people in Spain, and for a long time offered a stubborn resistance to the Romans. Originally Carthaginian mercenaries, they were induced to serve the Romans in a similar capacity, and Livy (xxiv. 49) distinctly states that they were the first mercenaries in the Roman army. They did not, however, keep faith, and several campaigns were undertaken against them. In 179 B.C. the whole country was subdued by T. Sempronius Gracchus, who by his generous treatment of the vanquished gained their esteem and affection. In 153 they again revolted, and were not finally overcome until the capture of Numantia (133). The twenty years' war waged round this city, and its siege and destruction by Scipio the Younger (133 B.C.) form only the most famous episode in the long struggle, which has left its mark in entrenchments near Numantia excavated in 1906-1907 by German archaeologists. After the fall of Numantia, and still more after the death of Sertorius (72 B.C.), the Celtiberians became gradually romanized, and town life grew up among their valleys; Clunia, for instance, became a Roman municipality, and ruins of its walls, gates and theatre testify to its civilization; while Bilbilis (Bambola), another municipality, was the birthplace of the eminently Roman poet Martial. The Celtiberians may have been so called because they were thought to be the descendants of Celtic immigrants from Gaul into Iberia (Spain), or because they were regarded (cf. Lucan iv. 9) as a mixed race of Celts and Spaniards (Iberians); in either case the name represents a geographer's theory rather than an ascertained fact. That a strong Celtic element existed in Spain is proved both by numerous traditions and by the more trustworthy evidence of place-names. The Celtic place-names of Spain, however, are not confined to Celtiberia or even to the north and east; they occur even in the south and west.

A long description of the manners and customs of the Celtiberi is
given by Diodorus Siculus (v. 33, 34). Their country was rough and
unfruitful as a whole (barley, however, was cultivated), being chiefly
used for the pasture of sheep. Its inhabitants either led a nomadic
life or occupied small villages; large towns were few. Their infantry
and cavalry were both excellent. In battle, they adopted the
wedge-shaped formation of the column. They carried double-edged swords
and short daggers for use hand to hand, the steel of which was
hardened by being buried underground; their defensive armour was a
light Gallic shield or a round wicker buckler, and greaves of felt
round their legs. They wore brazen helmets with purple crests, and
rough-haired black cloaks, in which they slept on the bare ground.
Like the Cantabri, they washed themselves with urine instead of water.
They were said to offer sacrifice to a nameless god (Strabo iii. p.
164) at the time of the full moon when all the household danced
together before the doors of the houses. Although cruel to their
enemies, they were hospitable to strangers. They ate meat of all
kinds, and drank a kind of mead. E. Hübner's article in
Pauly-Wissowa's _Realencyclopadie_, iii. (1886-1893), collects all the
ancient references, which are almost all brief. Strabo's notice (bk.
iii.), based perhaps on Poseidonius, is fullest. (F. J. H.)

CEMENT (from Lat. _caementum_, rough pieces of stone, a shortened form of _caedimentum_, from _caedere_, to cut), apparently first used of a mixture of broken stone, tiles, &c., with some binding material, and hence of any material capable of adhering to, and uniting into a coherent mass, fragments of a substance not in itself adhesive. The term is often applied to adhesive mixtures employed to unite objects or parts of objects (see below), but in engineering, when used without qualification, it means Portland cement, its modifications and congeners; these are all hydraulic cements, i.e. when set they resist the action of water, and can, under favourable conditions, be allowed to set under water.

_Hydraulic Cements_.--It was well known to builders in the earliest historic times that certain limes would, when set, resist the action of water, i.e. were hydraulic; it was also known that this property could be conferred on ordinary lime by admixture of silicious materials such as pozzuolana or tufa. We have here the two classes into which hydraulic cements are divided.

Pozzuolanic cement.

When pure chalk or limestone is "burned," i.e. heated in a kiln until its carbonic acid has been driven off, it yields pure lime. This slakes violently with water, giving slaked lime, which can be made into a smooth paste with water and mixed with sand to form common mortar. The setting of the mortar is due to the drying of the lime (a purely physical phenomenon, no chemical action occurring between the lime and the sand). The function of the sand is simply that of a diluent to prevent undue shrinkage and cracking in drying. Subsequent hardening of the mortar is caused by the gradual absorption of carbonic acid from the air by the lime, a skin of carbonate of lime being formed; but the action is superficial. Mortar made from pure or "fat" lime cannot withstand the action of water, and is only used for work done above water-level. If, however, such "fat" lime is mixed in the presence of water, not with sand but with silica in an active form, i.e. amorphous and (generally) hydrated, or with a silicate containing silica in an active condition, it will unite with the silica and form a silicate of lime capable of resisting the action of water. The mixture of the lime and active silica or silicate is a pozzuolanic cement. The simplest of all pozzuolanic cements would be a mixture of pure lime and hydrated silica, but though the latter is prepared artificially for various purposes, it is too expensive to be used as a cement material. A similar obstacle lies in the way of using a certain native form of active silica, viz. kieselguhr, for it is too valuable as an absorbent of nitroglycerine, for the manufacture of dynamite, to be available for making pozzuolanic cement. There are, however, many silicious substances occurring abundantly in nature which can thus be used. They are mostly of volcanic origin, and include pumice, tufa, santorin earth, trass and pozzuolana itself. The following analyses show their general composition:--

+-----------------------------+-----------+-----------+-----------+
| |Neapolitan | Roman | |
| | Pozzuo- | Pozzuo- | Trass |
| | lana | lana |(per cent) |
| |(per cent) |(per cent) | |
+-----------------------------+-----------+-----------+-----------|
| Soluble silica (SiO2) | 27.80 | 32.64 | 19.32 |
| Insoluble silicious residue | 35.38 | 25.94 | 50.40 |
| Alumina (Al2O3) | / 19.80 | / 22.74 | 13.86 |
| Ferric oxide (Fe2O3) | \ | \ | 3.10 |
| Lime (CaO) | 5.68 | 4.06 | · · |
| Magnesia (MgO) | 0.35 | 1.37 | 0.13 |
| Sulphuric anhydride (SO3) | Trace | Trace | · · |
| Combined water (H2O) | / 4.27 | / 8.92 | 7.57 |
| Carbonic anhydride (CO2) | \ | \ | · · |
| Moisture | · · | · · | 5.04 |
| Alkalis and loss | 6.72 | 4.33 | 0.58 |
| +-----------+-----------+-----------+
| | 100.00 | 100.00 | 100.0 |
+-----------------------------+-----------+-----------+-----------+

An artificial product which serves perfectly as a pozzuolana is granulated blast-furnace slag. The slag, which must contain a high percentage of lime, is granulated by being run while fused into abundance of water. This granulated slag differs from the same slag allowed to cool slowly, in that a portion of the energy which it possesses while fused is retained after it has solidified. It bears to ordinary slowly-cooled slag a similar relation to that borne by plastic sulphur to ordinary crystalline sulphur. This potential energy becomes kinetic when the slag is brought into contact with lime in the presence of water, and causes the formation of a true hydraulic silicate of lime. The following analysis shows the composition of a typical slag:--

Per Cent.
Insoluble residue 1.04
Silica (SiO2) 31.50
Alumina (Al2O3) 18.56
Manganous oxide (MnO) 0.44
Lime (CaO) 42.22
Magnesia (MgO) 3.18
Soda (Na2O) 0.70
Sulphuric anhydride (SO3) 0.45
Sulphur (S) 2.21
------
100.30
Deduct oxygen equivalent to sulphur 1.10
------
99.20

Granulated slag of this character is ground with slaked lime until both materials are in a state of fine division and intimately mixed. The usual proportions are three of slag to one of slaked lime by weight. The product termed slag cement sets slowly, but ultimately attains a strength scarcely inferior to that of Portland cement. Although it is cheap and suitable for many purposes, its use is not large and tends to decrease. Pozzuolanic cements are little used in England. Generally speaking, they are only of local importance, their cheapness depending largely on the nearness and abundance of some suitable volcanic deposit of the trass or tufa class. They are not usually manufactured by the careful grinding together of the pozzuolana and the lime, but are mixed roughly, a great excess of pozzuolana being employed. This excess does no harm, for that part which fails to unite with the lime serves as a diluent, much as does sand in mortar. In fact, ordinary pozzuolanic cement made on the spot where it is to be used may be regarded as a better kind of common mortar having hydraulic qualities. Good hydraulic mortars may be made from lime mixed with furnace ashes or burnt clay as the pozzuolanic constituent.

Portland Cement

Cements of the Portland type differ in kind from those of the pozzuolanic class; they are not mechanical mixtures of lime and active silica ready to unite under suitable conditions, but consist of definite chemical compounds of lime and silica and lime and alumina, which, when mixed with water, combine therewith, forming crystalline substances of great mechanical strength, and capable of adhering firmly to clean inert material, such as stone and sand. They are made by heating to a high temperature an intimate mixture of a calcareous substance and an argillaceous substance. The commonest of such substances in England are chalk and clay, but where local conditions demand it, limestone, marl, shale, slag or any similar material may be used, provided that the correct proportions of lime, silica and alumina are maintained. The earliest forms of cements of the Portland class were the hydraulic limes. These are still largely used, and are prepared by burning limestones containing clayey matter. Some of these naturally possess a composition differing but little from that of the mixture of raw materials artificially prepared for the manufacture of Portland cement itself. Although hydraulic limes have been in use from the most ancient times, their true nature and the reason of their resistance to water have only become known since 1791. Next in antiquity to hydraulic lime is Roman cement, prepared by heating an indurated marl occurring naturally in nodules. Its name must not be taken to imply that it was used by the ancients; in point of fact the manufacture of this substance dates back only to 1796.

With the growth of engineering in the early part of the 19th century arose a great demand for hydraulic cement. The supply of materials containing naturally suitable proportions of calcium carbonate and clay being limited, attempts were made to produce artificial mixtures which would serve a similar end. Among those who experimented in this direction was Joseph Aspdin, of Leeds, who added clay to finely ground limestone, calcined the mixture, and ground the product, which he called Portland cement. The only connexion between Portland cement and the place Portland is that the cement when set somewhat resembles Portland stone in colour. True, it is possible to manufacture Portland cement from Portland stone (after adding a suitable quantity of clay), but this is merely because Portland stone is substantially carbonate of lime; any other limestone would serve equally well. Although Portland cement is later in date than either Roman cement or hydraulic lime, yet on account of its greater industrial importance, and of the fact that, being an artificial product, it is of approximately uniform composition and properties, it may conveniently be treated of first. The greater part of the Portland cement made in England is manufactured on the Thames and Medway. The materials are chalk and Medway mud; in a few works the latter is replaced by gault.

The composition of typical samples of chalk and clay is shown in the
following analyses:--

+-----------------------------------+----------------------------------------------------------------------------+
| Chalk. | Clay. |
+-------------------------+---------+----------------------------+---------+------------------+-------+----------+
| |Per cent.| |Per cent.| | | |
|Silica (SiO2) | 0.92 | Insoluble silicious matter | 26.67 |Consisting of | | |
|Alumina+ferric oxide | | Silica (SiO2) | 31.24 | Quartz (SiO2) | 19.33 | |
| (Al2O2 + Fe2O3) | 0.24 | Alumina (Al2O3) | 16.60 | Silica (SiO2) | 5.19 |\ |
|Lime (CaO) | 55.00 | Ferric Oxide (Fe2O3) | 8.66 | Alumina (Al2O3) | 1.47 | >Feldspar|
|Magnesia (MgO) | 0.36 | Lime (CaO) | 0.25 | Magnesia (MgO) | 0.03 | | 7.34% |
|Carbonic anhydride (CO2) | 43.40 | Magnesia (MgO) | 1.91 | Soda (Na20) | 0.65 |/ |
| | ----- | Soda (Na2O) | 1.00 | | ----- | |
| | 99.92 | Potash (K2O) | 0.45 | | 26.67 | |
| | | Sodium Chloride (NaCl) | 1.86 | | | |
| | | Combined water, organic | | | | |
| | | matter, and loss | 11.36 | | | |
| | | | ------ | | | |
| | | | 100.00 | | | |
+-------------------------+---------+----------------------------+---------+------------------+-------+----------+

Mixing.

Loading the kiln.

These materials are mixed in the proportion of about 3:1 by weight so
that the dried mixture contains approximately 75% of calcium
carbonate, the balance being clay. The mixing may be effected in
several ways. The method once exclusively used consists in mixing the
raw materials with a large quantity of water in a wash mill, a machine
having radial horizontal arms driven from a central vertical spindle
and carrying harrows which stir up and intermix any soft material
placed in the pit in which the apparatus revolves. The raw materials
in the correct proportion are fed into this mill together with a large
quantity of water. The thin watery "slip" or slurry flows into large
settling tanks ("backs") where the solids in suspension are deposited;
the water is drawn off, leaving behind an intimate mixture of chalk
and clay in the form of a wet paste. This is dug out, and after being
dried on floors heated by flues is ready for burning. This process is
now almost obsolete. According to present practice the raw materials
are mixed in a wash mill with so much water that the resulting slurry
contains 40 to 50% of water. The slurry, which is wet enough to flow,
is ground between millstones so as to complete the process of
comminution begun in the wash mill. Thorough grinding and mixing are
of the utmost importance, as otherwise the cement ultimately produced
will be unsound and of inferior quality. The drying of the slurry is
generally effected by the waste heat of the kilns, so that while one
charge is burning another is drying ready for the next loading of the
kilns. The kilns commonly employed are "chamber kilns," circular
structures not unlike an ordinary running lime kiln, but having the
top closed and connected at the side with a wide flue in which the
slurry is exposed to the hot products of combustion from the kiln. The
farther ends of the flues of several such kilns are connected with a
chimney shaft. The slurry, in drying on the floor of the flue, forms a
fairly tough cake which cracks spontaneously in the process of drying
into rough blocks suitable for loading into the kiln. At the bottom of
the kiln is a grate of iron bars, and on this wood and coke are piled
to start the fire. A layer of dried slurry is loaded on this, then a
layer of coke, then a layer of slurry, and so on until the kiln is
filled with coke and slurry evenly distributed. Fresh slurry is run on
to the drying floors, and the kiln is started. The construction of an
ordinary chamber kiln may be gathered from the accompanying diagram
(fig. l). The operation of burning is a slow one. An ordinary kiln,
which will contain about 50 tons of slurry and 12 tons of coke, will
take two days to get fairly alight, and will be another two or three
days in burning out. Therefore, allowing adequate time for loading and
unloading, each kiln will require about one week for a complete run.
The output will be about 30 tons of "clinker" ready to be ground into
cement. The grinding of the hard rock-like masses of clinker is
effected between millstones, or in modern plants in ball-mills,
tube-mills and edge-runners. It is an important part of the
manufacture, because the finished cement should be as fine and
"floury" as possible. The foregoing description represents the
procedure in use in many English factories. There are various
modifications in practice according to local conditions: a few of
these may be described. In all cases, however, the main operations are
the same, viz. intimately mixing the raw materials, drying the
mixture, if necessary, and burning it at a clinkering temperature
(about 1500° C. =2732° F.). Thus when hard limestone is the form of
calcium carbonate locally available, it is ground dry and mixed with
the correct proportion of clay also dried and ground. The mixture is
slightly damped, moulded into rough bricks, dried and burned. A
possible alternative is to burn the limestone first and mix the
resulting lime with clay, the mixture being burned as before. By this
method grinding the hard limestone is avoided, but there is an extra
expenditure of fuel in the double burning.

Other kilns.

Many different forms of kiln are used for burning Portland cement.
Besides the chamber kilns which have been described, there are the
old-fashioned bottle kilns, which are similar to the chamber kilns,
but are bottle-shaped and open at the top; they do not dry the slurry
for their next charge. Their use is becoming obsolete. There are also
stage kilns of the Dietzsch type, which consist of two vertical
shafts, one above the other, but not in the same vertical line,
connected by a horizontal channel. At this middle portion and in the
upper part of the lower shaft the burning proper proceeds; the upper
shaft is full of unburnt raw material which is heated by the hot gases
coming from the burning zone, and the lower shaft contains clinker
already burned and hot enough to heat the incoming air which supplies
that necessary for combustion at the clinkering zone. A pair of
Dietzsch kilns, built back to back, are shown in fig. 2. There are
other forms of shaft kiln, such as the Schneider, in which there is a
burning zone, a heating and cooling zone as in the Dietzsch, but no
horizontal stage, the whole shaft being in the same vertical plane.
Another form is the Hoffmann or ring kiln, made up of a number of
compartments arranged in a ring and connected with a central chimney;
in these compartments rough brick-shaped masses of the raw materials
are stacked, and between these bricks fuel is sprinkled. At a given
moment one of these compartments is burning and at its full
temperature; the air for combustion is drawn in through one or more
compartments behind it which have just finished burning, and is
thereby strongly heated; the products of combustion pass away through
one or more compartments in front of it and heat their contents before
they are subjected to actual combustion. It will be seen that the
principle of the ring kiln is similar to that of the stage kiln. In
each case the clinker which has just been burned and is fully hot
serves to heat the air-supply to the compartment where combustion is
actually proceeding; in like manner the raw materials about to be
burned are well heated by the waste gases from the compartment in full
activity before they themselves are burned. (It may be noted that here
and generally in this article "burn" is used in the technical sense;
it is technically correct to speak of cement clinker being "burned",
although it is not a fuel; in accurate terms it is the fuel which is
burned, and it is the heat it generates which raises the clinker to a
high temperature, i.e. technically "burns" it.) By this device a great
part of the heat is regenerated and a saving of fuel is effected.

Rotatory kilns.

The methods of burning cement described above are obsolescent. They
are being replaced by the rotatory process, so called because the
cement is burned in rotating cylinders instead of in fixed kilns.
These cylinders vary from 60 to 150 ft. in length, an ordinary length
in modern practice being 100 to 120 ft.; their diameter
correspondingly varies from 6 ft. to 7 ft. 6 in. The cylinders are
made of steel plate, lined with refractory bricks, are carried on
rollers at a slight angle with the horizontal, and are rotated by
power. At the upper end the raw material is fed in either as a dry
powder or as a slurry; at the lower end is a powerful burner. In the
early days of rotatory kilns producer gas was used as a fuel, but with
little success; about 1895 petroleum was used in the United States
with complete success, but at a relatively heavy cost. At the present
time, finely powdered coal injected by a blast of air is almost
universally employed, petroleum being used only where it is actually
cheaper than coal. In the working of this type of kiln the rotation
and slight inclination of the cylinder cause the raw material to
descend towards the lower end. At the upper end the raw material is
dried and heated moderately. As it descends it reaches a part of the
kiln where the temperature is higher; here the carbonic acid of the
carbonate of lime, and the combined water of the clay are driven off,
and the resulting lime begins to act chemically on the dehydrated
clay. The material is then in a partially burnt and slightly sintered
state, but it is not fully clinkered and would not make Portland
cement. The material continues to descend by the rotation of the kiln
and reaches the lower end nearest the burner where the temperature is
highest, and is there heated so highly that the union of the lime,
silica and alumina is complete, and fully burnt clinker falls out of
the kiln. It is extremely hot, and is cooled usually by being passed
down one or more rotating cylinders, similar to the first, but
smaller, and acting as coolers instead of kilns. On its way down the
cylinders the clinker meets a current of cold air and is cooled, the
air being correspondingly warmed and passing on to aid in the
combustion of the fuel used in heating the kiln. This regenerative
heating is similar in principle and effect to that obtained by means
of the shaft and ring kilns described above. The output of these kilns
varies from 200 to 400 tons per kiln per week according to their size
and the nature of the raw materials burned, as against 30 tons per
week for an ordinary chamber kiln. A large saving in labour is also
secured. The rotatory system presents many advantages and is rapidly
replacing the older methods of cement making. Fig. 3 represents
diagrammatically a rotatory cement plant on the Hurry & Seaman system,
which was one of the first to make cement by the rotatory process
successfully on a large scale, using powdered coal as fuel. Rotatory
kilns of various other makes are now in use, but the same principles
are embodied, namely, the employment of a rotating inclined cylinder
for burning the raw materials, a burner fed with powdered coal and a
blast of air, and some device such as a cooling cylinder or cooling
tower by which the clinker may be cooled and the air correspondingly
heated on its way to the burner.

Another method of making Portland cement which has been proposed and
tried with some success consists in fusing the raw materials together
in an apparatus of the type of a blast furnace. The high temperature
necessary to fuse cement clinker makes this process difficult to
accomplish commercially, but it has many inherent merits and may be
the process of the future, displacing the rotatory method.

Cement clinker.

Portland cement clinker, however produced, is a hard, rock-like
substance of semi-vitrified appearance and very dark colour. The
product from a well-run rotatory kiln is all evenly burnt and properly
vitrified; that from an ordinary fixed kiln of whatever type is apt to
contain a certain amount (5 to 15%) of underburnt material, which is
yellowish and friable and is not properly clinkered. This material
must be picked out, as such underburnt stuff contains free lime or
unsaturated lime compounds. These may slake slowly in the finished
cement and cause such expansion as may destroy the work of which it
forms part. Well-burnt, well-picked clinker when ground yields good
Portland cement. Nothing is added during or after grinding save a
small amount (1 to 2%) of calcium sulphate in the form either of
gypsum or of plaster of Paris, which is sometimes needed to make the
cement slower-setting. For the same purpose a small quantity of water
(up to 2%) may be added either by moistening the clinker or by blowing
steam into the mills in which the clinker is ground. This small
addition for this specified purpose is recognized as legitimate, but
the employment of various cheap materials such as ragstone and
blast-furnace slag, sometimes added as diluents or make-weights, is
adulteration and therefore fraudulent.

Composition.

The composition of Portland cement varies within comparatively narrow
limits, and for given raw materials the variations are tending to
become smaller as regularity and skill in manufacture increase. The
following analysis may be taken as typical of cements made from chalk
and clay on the Thames and Medway:--

Per cent.
Silica (SiO2) 22.0
Insoluble residue 1.0
Alumina (Al2O3) 7.5
Ferric oxide (Fe2O3) 3.5
Lime (CaO) 62.0
Magnesia (MgO) 1.0
Sulphuric anhydride (SO3) 1.5
Carbonic anhydride (CO2) 0.5
Water (H2O) 0.5
Alkalis 0.5
-----
100.0

There may be variations from this composition according to the nature
of the raw materials employed. Thus the silica may range from 19 to
27%, the alumina and ferric oxide jointly from 7 to 14%, the lime from
60 to 67%. All such variations are permissible provided that the
quantity of silica and alumina is sufficient to saturate the whole of
the lime and to leave none of it in a "free" condition, likely to
cause the cement to expand after setting. Other things being equal,
the higher the percentage of lime within the limits indicated above
the stronger is the cement, but such highly limed cement is less easy
to burn than cement containing about 62% of lime; and unless the
burning is thorough and the raw materials are intimately mixed, the
cement is apt to be unsound. Although the ultimate composition of
cement, that is, the percentage of each base and acid present, can be
accurately determined by analysis, its proximate composition, i.e. the
nature and amount of the compounds formed from these acids and bases,
can only be ascertained indirectly and with difficulty. The
foundations of our knowledge on this subject were laid by H. le
Chatelier, whose work has since been supplemented by that of Spenser
B. Newberry, W.B. Newberry and Clifford Richardson. As the outcome of
these inquiries it has been established that tricalcium silicate
3CaO·SiO2 is the essential constituent of Portland cement. The
constituent of next importance is an aluminate, but whether this is
dicalcium aluminate, 2CaO·Al2O3, or tricalcium aluminate, 3CaO·Al2O3,
is still in doubt. In the following description it is assumed to be
the tricalcium aluminate. The remaining silicates and aluminates
present, and ferric oxide and magnesia, if existing in the moderate
quantities which are usual in Portland cement of good quality, are of
minor importance and may be regarded as little more than impurities.
The silicates and aluminates of which Portland cement is composed are
believed to exist not as individual units but as solid solutions of
each other, these solid solutions taking the form of minerals
recognizable as individuals. The two principal minerals are termed
alite and celite; according to the best opinion, alite consists of a
solid solution of tricalcium aluminate in tricalcium silicate, and
celite of a solid solution of dicalcium aluminate in dicalcium
silicate. Celite is little affected by water, and has but small
influence on the setting; alite is decomposed and hydrated, this
action constituting the main part of the setting of Portland cement.
Both the components of alite react, and for simplicity their reactions
may be stated in separate equations, thus:--

(1) 2(3CaO·SiO2) + 9H2O = 2(CaO·SiO2)·5H2O + 4Ca(OH)2
Tricalcium silicate. Hydrated mono- Calcium
calcium silicate. hydroxide.

(2) 3CaO·Al2O3 + 12H2O = 3CaO·Al2O3·12H2O
Tricalcium aluminate. Hydrated tricalcium
aluminate.

Since alite is a solid solution and, although an individual mineral,
is not a chemical unit, the proportion of tricalcium silicate to
tricalcium aluminate in a given specimen of alite will vary; but,
whatever the proportions, each of these substances will react in its
characteristic manner according to the equations given above.

The precise mechanism of the process of setting of Portland cement is
not known with certainty, but it is probably analogous to that of the
setting of plaster of Paris, consisting in the dissolution of the
compounds produced by hydration while they are in a more soluble form,
their transition to a less soluble form, the consequent
supersaturation of the solution, and the deposition of the surplus of
the dissolved substance in crystals which interlock and form a
coherent mass. This theory being accepted, it is evident that a small
quantity of water, by successive dissolution and deposition of a
substance capable of existing in a more soluble and in a less soluble
form, is able to bring about the crystallization of an indefinitely
large quantity of material. It is not necessary that there should be
present sufficient water to dissolve the whole of the reacting
substance at any one time; it is sufficient if there is enough for
hydration and a small surplus for the crystallization by successive
stages as above described. It is generally admitted that the aluminate
is the chief agent in the first setting of the cement, and that its
ultimate hardening and attainment of strength are due to the
tricalcium silicate.

As mentioned above, the constituents other than the tricalcium
silicate and tricalcium aluminate of which alite is composed, are of
minor importance. The function of the ferric oxide present in ordinary
cement is little more than that of a flux to aid the union of silica,
alumina and lime in the clinker; its role in the setting of the cement
is altogether secondary. In fact, excellent Portland cement can be
prepared from materials free from iron. Such cement, if free also from
manganese, is white, and its manufacture has been proposed for
exterior decorative use. Magnesia, if present in Portland cement in
quantity not exceeding 5%, appears to be inert, but there is evidence
that in larger proportion, e.g. 10-15%, it may hydrate and set after
the general setting of the cement, and may give rise to disruptive
strains causing the cement to "blow" and fail. In so-called natural
cement which is comparatively lightly burnt, the magnesia appears to
be inert, and as much as 20 to 30% may be present. Another constituent
of Portland cement which influences its setting time is calcium
sulphate, naturally formed from the sulphur in the raw materials or
fuel, or intentionally added to the finished cement as gypsum or
plaster of Paris. It has a remarkable retarding effect on the
hydration of the calcium aluminate, and consequently on the setting of
the cement; thus it is that a little gypsum is often added to convert
a naturally quick-setting cement into one which sets slowly. It will
be observed that in the hydration of tricalcium silicate, the main
constituent of Portland cement, a large portion of the lime appears as
calcium hydroxide, i.e. slaked lime. It is evident that this will form
a pozzuolanic cement if a suitable silicious material such as trass is
added to the cement. The ultimate product when set may be regarded as
a mixed Portland and pozzuolanic cement. The use of trass in this
manner as an adjunct to Portland cement has been advocated by W.
Michaelis, and undoubtedly increases the strength of the material, but
it has not become general.

Testing.

The quality of Portland cement is ascertained by its analysis and by
determining its specific gravity, fineness, mechanical strength and
soundness. A good sample will usually have a composition within the
limits cited above and approximating to the typical figures given
above. It will be ground so finely that not more than 3% will be left
on a sieve of 76 × 76 meshes per sq. in., the wires of the sieve being
0.005 in. in diameter. It will have, when freshly burned, a specific
gravity not lower than 3.15, and briquettes made from it and kept in
water will possess a tensile strength of 400-500 lb. per sq. in. seven
days after they are made, while briquettes made from a mixture of 3
parts by weight of sand and 1 of cement will give about 225 lb. per sq.
in. at twenty-eight days. Formerly the soundness of cement was
determined by keeping thin pats of the cement in cold water for
twenty-eight days, or in warm water (110°-120° F.) for twenty-four
hours, and examining for cracks or other signs of expansion. Modern
practice is to measure the expansion of a test piece of cement kept in
water at a temperature of 212° F. The simplest and most generally used
method is due to H.L. le Châtelier, and consists in measuring the
increase in circumference of a cylinder of cement 30 mm. in diameter
by means of a split ring encircling the cylinder, the motion of which
is magnified by two light rods extending radially. Another
quantitative test for soundness is that formulated by L. Deval, who
has shown that briquettes of 3 of sand and 1 of cement kept in water
for two days at 80° C. = 176° F. attain approximately the same
strength as similar briquettes attain at seven days in water at the
ordinary temperature. In like manner briquettes kept at 176° F. for
seven days are approximately equal in strength to those kept at the
ordinary temperature for twenty-eight days. A cement not perfectly
sound will give low results in the hot test, and a cement of
indifferent soundness will crack and go to pieces. The test is
admittedly severe, but can be passed without difficulty by cement made
with proper care and skill. There are many modifications and
elaborations of all the tests which have been mentioned. Cement for
all important work is submitted to a rigorous system of testing and
analysis before it is accepted and used.

_Hydraulic Lime_ is a cement of the Portland as distinct from the pozzuolanic class. The most typical hydraulic lime is that known as Chaux du Theil, made from a limestone found at Ardèche in France. This limestone consists of calcium carbonate most intimately intermixed with very finely divided silica. It contains but little alumina and oxide of iron, which are the constituents generally necessary to bring about the union of silica and lime to form a cement, but in spite of this the silica is so finely divided and so well distributed that it unites readily with the lime when the limestone is burned at a sufficiently high temperature. English hydraulic limes are of a different class; they contain a good deal of alumina and ferric oxide, and in composition resemble somewhat irregular Portland cement.

Analyses of the two classes of hydraulic lime are as follows:--

Chaux de Theil. Blue Lias.
Per cent. Per cent.

Insoluble silicious matter 0.3 2.39
Silica (SiO2) 21.7 14.17
Alumina (Al2O3) 1.8 6.79
Ferric oxide (Fe2O3) 0.6 2.34
Lime (CaO) 74.0 63.43
Magnesia (MgO) 0.7 1.54
Sulphuric anhydride (SO3) 0.3 1.63
Carbonic anhydride (CO2) \ 0.6 / 3.64
Water (H20) / \ 2.69
Alkalis and loss · · 1.38
----- ------
100.0 100.00

Hydraulic lime contains a good deal of uncombined lime, and has to be
slaked before it is used as a cement. In France this slaking is
conducted systematically by the makers, the freshly burned lime being
sprinkled with water and stored in large bins where slaking proceeds
slowly and regularly until the whole of the surplus uncombined lime
is slaked and rendered harmless, while the cementitious compounds,
notably tricalcium silicate, remain untouched. In English practice
hydraulic lime is slaked by the user. Seeing that regular and perfect
slaking is more easily attained when working systematically on a large
scale and by storing the material for a long period, the French method
is the better and more rational. The product may then be regarded as a
cement of the Portland class mixed with slaked lime. When gauged with
water and made into a mortar it sets slowly, but ultimately becomes
almost as strong as Portland cement. Its slow setting is an advantage
for some purposes, e.g. for foundations and abutments where
settlements may occur. The structure is free to take its permanent
position before the lime sets, and cracks are thus avoided. A case in
point is the employment of hydraulic lime in place of Portland cement
as grouting outside the cast-iron tubes used for lining tunnels made
by the shield system.

_Roman Cement_ is another cement of the Portland class which came into use shortly before the manufacture of artificial Portland cement was attempted. It is still in use, though only for special purposes where a quick-setting material is required. It is made from septaria nodules which are dredged up on the Kent and Essex coasts and consist of about 60% of calcium carbonate mixed with clay, the mass being sufficiently indurated to remain coherent under water. The nodules are not prepared in any way, but simply burned at a moderate red heat.

The resulting cement varies somewhat in composition, but approximates
to the following figures:--

Per cent.
Insoluble silicious matter 5.86
Silica (SiO2) 19.62
Alumina (Al203) 10.30
Ferric oxide (Fe2O3) 7.44
Manganese dioxide (MnO2) 1.57
Lime (CaO) 44.54
Magnesia (MgO) 2.92
Sulphuric anhydride (SO3) 2.61
Carbonic anhydride (CO2) 3.43
Water (H2O) 0.25
Alkalis and loss 1.46
------
100.00

The most characteristic constituent is the oxide of iron, which gives
the cement a reddish colour, and the presence of manganese also
differentiates Roman from Portland cement, which rarely contains
appreciable quantities of that element. The high percentage of alumina
causes the cement to be quick-setting, and it becomes hard in about
five minutes. It resists the action of water, salt or fresh, very
well, and is therefore useful in situations where the work is likely
to be submerged immediately after it has been put in place.

The term _Natural Cements_ is applied to cements made by burning mixtures of clay and carbonate of lime naturally occurring in approximately suitable proportions. They may be regarded as badly-mixed Portland cements, and need no special description. American "natural" cements are of a somewhat different class. They are usually made from a silicious limestone containing magnesia, and are comparatively lightly burned.

The following analysis is typical of a cement of this kind:--

Per cent.
Silica (SiO2) 24.30
Alumina (Al203) 7.22
Ferric oxide (Fe2O3) 5.06
Lime (CaO) 33.70
Magnesia (MgO) 20.94
Water, carbonic anhydride, and loss 8.78
------
100.00

These irregular cements of the Portland class are good building
materials for ordinary purposes, but are not so suitable as good
artificial Portland cement for heavy and important undertakings.

_Passow Cement _is a recent product which is in a class by itself. It is made by granulating blast furnace slag of suitable composition and finely grinding the product, either alone or with an admixture of about 10% of Portland cement clinker. It differs from ordinary slag cement (see above) in that it is not a pozzuolanic cement depending on the interaction of granulated slag and lime. The particular method of granulating slag for Passow cement produces a material which sets _per se_ and attains a strength comparable with that of Portland cement. Passow cement has been successfully made from slag of different compositions in Germany, England and America.

Uses of hydraulic cements.

The chief use of hydraulic cements, whether of the pozzuolanic or Portland class, is to act as an adhesive material in work which is to be exposed to water. No doubt in times of remote antiquity it was found that the jointing of masonry which was to be immersed required the use of a cement indifferent to the action of water. Ordinary mortar failed in such positions; mortar made from lime prepared from limestones or chalks containing a little clay was found to stand; mortar made from lime mixed with trass or similar active silicious material was also found to stand. On this observation rests the whole of the present enormous employment of hydraulic cements. It was a natural transition to utilize these cements not merely for jointing masonry but also for making concrete, and the only reason why hydraulic cements, as distinct from cements which are not hydraulic (e.g. ordinary mortar), are used for the latter purpose is their great mechanical strength. Their use in above-water work is checked by the low price of common brick. Even in such work, where it would be thought that masses of burnt clay would be the cheapest conceivable material, concrete is at least on level terms with its rival. It must be remembered that one of the great advantages of concrete is that five-sixths of its total mass may be provided from local sand and gravel, on which no carriage has to be paid. The cement, on which alone freight is to be reckoned, converts these from loose incoherent material into a solid stone. Thus it comes about that the largest use of cement is for manufacturing concrete for dock and harbour work, and for the making of foundations. It is also employed for the building of light bridges, floors, and pipes constructed of cement mortar disposed round a skeleton of iron rods. Such composite structures take advantage at once of the high tensile strength of iron and of the high compressive strength of cement mortar. (See also CONCRETE.)

Good hydraulic cements are highly permanent materials provided certain conditions be observed. It might be supposed that hydraulic cements from their nature would be indifferent to the action of water, but this is only true if the structures of which they form part are sufficiently compact. In this case the action of the water is checked by the film of carbonate of lime which eventually forms oh the surface of calcareous cement. This, together with the compactness of the mortar, hinders the ingress and egress of water, and prevents the dissolution and ultimate destruction of the cement. But where the concrete or mortar is not well made and is porous, the continual passage of water through it will gradually break up and dissolve away the calcareous constituents of the cement until its strength is utterly destroyed. This destructive action is increased if the water contains sulphates or magnesium salts, both of which act chemically on the calcareous constituents of the cement. As sea-water contains both sulphates and magnesium salts, it is especially necessary in concrete for harbour work to take every care to produce an impervious structure. There are various minor external causes for the failure and ultimate destruction of cement mortar and concrete, but their discussion is a matter for the specialist. Failure from inherent vice in the cement has been already touched on; it can always be traced to want of skill and care in manufacture.

_Calcium Sulphate Cements._--Under this term are comprehended all cements whose setting properties primarily depend on the hydration of calcium sulphate. They include plaster of Paris, Keene's cement and many variants of these two types. The raw material is gypsum (q.v.). This may be almost chemically pure, when it is generally used for Keene's cement; or it may contain smaller or greater quantities of impurities, in which case it is suitable for the preparation of cements of the plaster of Paris class. The mode of preparation is to calcine the gypsum at temperatures which depend on the class of cement to be produced. If plaster of Paris is to be made, calcination is carried out at about 204° C. (=400° F.); at this temperature, gypsum, CaS04.2H20, loses three-quarters of its combined water and becomes 2CaSO4.H20. If a cement of the Keene's cement class is to be prepared the temperature used is higher, e.g. 500° C. (=932° F.), and the whole of the combined water of the gypsum is expelled, the anhydrous sulphate CaSO4 being obtained.

Plaster of Paris; Keene's cement.

To produce plaster of Paris European practice consists in baking the
mineral in ovens, and in America in heating it in kettles. Both
processes are inferior in economy to calcination in rotatory kilns, a
process which may be regarded as the method of the present and the
immediate future. Keene's cement and its congeners are made in fixed
kilns so constructed that only the gaseous products of combustion come
into contact with the gypsum to be burnt, in order to avoid
contamination with the ash of the fuel.

The setting of plaster of Paris depends on the fact that when
2CaSO4·H2O is treated with water it dissolves, forming a
supersaturated solution of CaSO4·2H2O. The excess held temporarily in
solution is then deposited in crystals of CaSO4·2H2O. In the light of
this knowledge the mode of setting of plaster of Paris becomes clear.
The plaster is mixed with a quantity of water sufficient to make it
into a smooth paste; this quantity of water is quite insufficient to
dissolve the whole of it, but it dissolves a small part, and gives a
supersaturated solution of CaSO4.2H2O. In a few minutes the surplus
hydrated calcium sulphate is deposited from the solution, and the
water is capable again of dissolving 2CaSO4·H2O, which in turn is
fully hydrated and deposited as CaSO4·2H2O. The process goes on until
a relatively small quantity of water has by instalments dissolved and
hydrated the 2CaSO4·H2O, and has deposited CaSO4·2H2O in felted
crystals forming a solid mass well cemented together. The setting is
rapid, occupying only a few minutes, and is accompanied by a
considerable expansion of the mass. There is reason to suppose that
the change described takes place in two stages, the gypsum first
forming orthorhombic crystals and then crystallizing in the
monosymmetric system. Gypsum thus crystallized is in its normal
monosymmetric form, more stable under ordinary conditions than the
orthorhombic form. Correlatively in its process of dehydration to form
plaster of Paris, monosymmetric gypsum is converted into the
orthorhombic form before it begins to be dehydrated.

The principles which govern the preparation and setting of the other
class of calcium sulphate cements, that is, cements of the Keene
class, are not fully understood, but there is a fair amount of
knowledge on the subject, both empirical and scientific. The essential
difference between the setting of Keene's cement and that of plaster
of Paris is that the former takes place much more slowly, occupying
hours instead of minutes, and the considerable heating and expansion
which characterize the setting of plaster of Paris are much less
marked.

It is the practice in Great Britain to burn pure gypsum at a low
temperature so as to convert it into the hydrate 2CaSO4·H2O, to soak
the lumps in a solution of alum or of aluminium sulphate, and to
recalcine them at about 500° C. On grinding they give Keene's cement.
Instead of alum various other salts, e.g. borax, may be used. The
quantity of these materials is so small that analyses of Keene's
cement show it to be almost pure anhydrous calcium sulphate, and make
it difficult to explain what, if any, influence these minute amounts
of alum and the like can exert on the setting of the cement. It seems
probable that the effect of the salts is inconsiderable, and that the
governing condition is the temperature at which the cement has been
burnt. The setting of Keene's cement takes place by the same sort of
process which has been described for the setting of plaster of Paris,
the chief differences being that the substance dissolved is anhydrous
calcium sulphate and that the operation takes a longer time.

All cements having calcium sulphate as their base are suitable only
for indoor work because of the solubility of this substance. They form
excellent decorative plasters on account of their clean white colour
and the sharpness of castings made from them, this latter quantity
being due to their expansion when setting.