Sodium chloride……………….. 2.6439 per cent.
Magnesium chloride…………….. 0.3150 " "
Magnesium sulphate…………….. 0.2066 " "
Calcium sulphate………………. 0.1331 " "
Potassium chloride…………….. 0.0746 " "
Magnesium bromide……………… 0.0070 " "
Calcium carbonate……………… 0.0047 " "
Iron carbonate………………… 0.0005 " "
Magnesium nitrate……………… 0.0002 " "
Lithium chloride………………. Traces.
Ammonium chloride……………… Traces.
Silica chloride……………….. Traces.
Water………………………… 96.6144
————
100.0000
An average analysis of a Thames cement may be taken to be as follows:—
Silica………………………….. 23.54 per cent. Insoluble residue (sand, clay, etc.)………………………. 0.40 " Alumina and ferric oxide…………… 9.86 " Lime……………………………. 62.08 " Magnesia…………………………. 1.20 " Sulphuric anhydride……………….. 1.08 " Carbonic anhydride and water……….. 1.34 " Alkalies and loss on analysis………. 0.50 " ——- 100.00
The following figures give the analysis of a sample of cement expressed in terms of the complex compounds that are found:—
Sodium silicate (Na2SiO3)…….. 3.43 per cent.
Calcium sulphate (CaSO4)……… 2.45 "
Dicalcium silicate (Ca2SiO4)…. 61.89 "
Dicalcium aluminate (Ca2Al2O5).. 12.14 "
Dicalcium ferrate (Ca2Fe2O5)….. 4.35 "
Magnesium oxide (MgO)………… 0.97 "
Calcium oxide (CaO)…………. 14.22 "
Loss on analysis, &c…………. 0.55 "
——-
100.00
Dr. W. Michaelis, the German cement specialist, gave much consideration to this matter in 1906, and formed the opinion that the free lime in the Portland cement, or the lime freed in hardening, combines with the sulphuric acid of the sea-water, which causes the mortar or cement to expand, resulting in its destruction. He proposed to neutralise this action by adding to the mortar materials rich in silica, such as trass, which would combine with the lime.
Mr. J. M. O'Hara, of the Southern Pacific Laboratory, San Francisco, Cal., made a series of tests with sets of pats 4 in diameter and 1/2 in thick at the centre, tapering to a thin edge on the circumference, and also with briquettes for ascertaining the tensile strength, all of which were placed in water twenty-four hours after mixing. At first some of the pats were immersed in a "five-strength solution" of sea-water having a chemical analysis as follows:—
Sodium chloride……………….. 11.5 per cent.
Magnesium chloride…………….. 1.4 " "
Magnesium sulphate…………….. 0.9 " "
Calcium sulphate………………. 0.6 " "
Water………………………… 85.6 " "
100.0
This strong solution was employed in order that the probable effect of immersing the cement in sea-water might be ascertained very much quicker than could be done by observing samples actually placed in ordinary sea-water, and it is worthy of note that the various mixtures which failed in this accelerated test also subsequently failed in ordinary sea-water within a period of twelve months.
Strong solutions were next made of the individual salts contained in sea-water, and pats were immersed as before, when it was found that the magnesium sulphate present in the water acted upon the calcium hydrate in the cement, forming calcium sulphate, and leaving the magnesium hydrate free. The calcium sulphate combines with the alumina of the cement, forming calcium sulpho-aluminate, which causes swelling and cracking of the concrete, and in cements containing a high proportion of alumina, leads to total destruction of all cohesion. The magnesium hydrate has a tendency to fill the pores of the concrete so as to make it more impervious to the destructive action of the sea-water, and disintegration may be retarded or checked. A high proportion of magnesia has been found in samples of cement which have failed under the action of sea water, but the disastrous result cannot be attributed to this substance having been in excess in the original cement, as it was probably due to the deposition of the magnesia salts from the sea-water; although, if magnesia were present in the cement in large quantities, it would cause it to expand and crack, still with the small proportion in which it occurs in ordinary cements it is probably inert. The setting of cement under the action of water always frees a portion of the lime which was combined, but over twice as much is freed when the cement sets in sea-water as in fresh water. The setting qualities of cement are due to the iron and alumina combined with calcium, so that for sea-coast work it is desirable for the alumina to be replaced by iron as far as possible. The final hardening and strength of cement is due in a great degree to the tri-calcium silicate (3CaO, SiO2) which is soluble by the sodium chloride found in sea-water, so that the resultant effect of the action of these two compounds is to enable the sea-water to gradually penetrate the mortar and rot the concrete. The concrete is softened, when there is an abnormal amount of sulphuric acid present, as a result of the reaction of the sulphuric acid of the salt dissolved by the water upon a part of the lime in the cement. The ferric oxide of the cement is unaffected by sea- water.