Water.............................. 96.6144 -------- 100.0000
An average a.n.a.lysis 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 a.n.a.lysis.......... 0.50 "
----- 100.00
The following figures give the a.n.a.lysis 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 a.n.a.lysis, &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 tra.s.s, 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 circ.u.mference, 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 a.n.a.lysis 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 r.e.t.a.r.ded 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 quant.i.ties, 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.
The neat cement briquette tests showed that those immersed in sea-water attained a high degree of strength at a much quicker rate than those immersed in fresh water, but the 1 to 3 cement and sand briquette tests gave an opposite result. At the end of twelve months, however, practically all the cements set in fresh water showed greater strength than those set in sea- water. When briquettes which have been immersed in fresh water and have thoroughly hardened are broken, the cores are found to be quite dry, and if briquettes immersed in sea-water show a similar dryness there need be no hesitation in using the cement; but if, on the other hand, the briquette shows that the sea-water has permeated to the interior, the cement will lose strength by rotting until it has no cohesion at all. It must be remembered that it is only necessary for the water to penetrate to a depth of 1/2 in on each side of a briquette to render it damp all through, whereas in practical work, if the water only penetrated to the same depth, very little ill-effect would be experienced, although by successive removals of a skin 1/2 in deep the structure might in time be imperilled.
The average strength in pounds per square inch of six different well-known brands of cement tested by Mr. O"Hara was as follows:--
TABLE No. 16.
EFFECT OF SEA WATER ON STRENGTH OF CEMENT.
Neat cement 1 cement to 3 sand set in set in Sea Water Fresh Water Sea Water Fresh Water
7 days 682 548 214 224 28 days 836 643 293 319 2 months 913 668 313 359 3 months 861 667 301 387 6 months 634 654 309 428 9 months 542 687 317 417 12 months 372 706 325 432
Some tests were also made by Messrs. Westinghouse, Church, Kerr, and Co., of New York, to ascertain the effect of sea- water on the tensile strength of cement mortar. Three sets of briquettes were made, having a minimum section of one square inch. The first were mixed with fresh water and kept in fresh water; the second were mixed with fresh water, but kept immersed in pans containing salt water; while the third were mixed with sea-water and kept in sea-water. In the experiments the proportion of cement and sand varied from 1 to 1 to 1 to 6.
The results of the tests on the stronger mixtures are shown in Fig. 32.
The Scandinavian Portland cement manufacturers have in hand tests on cubes of cement mortar and cement concrete, which were started in 1896, and are to extend over a period of twenty years. A report upon the tests of the first ten years was submitted at the end of 1909 to the International a.s.sociation of Testing Materials at Copenhagen, and particulars of them are published in "Cement and Sea-Water," by A. Poulsen (chairman of the committee), J. Jorsen and Co., Copenhagen, 1909, price 3s.
[Ill.u.s.tration: FIG. 32.--Tests of the Tensile Strength of Cement and Sand Briquettes, Showing the Effect of Sea Water.]
Cements from representative firms in different countries were obtained for use in making the blocks, which had coloured gla.s.s beads and coloured crushed gla.s.s incorporated to facilitate identification. Each block of concrete was provided with a number plate and a lifting bolt, and was kept moist for one month before being placed in position. The sand and gravel were obtained from the beach on the west coast of Jutland. The mortar blocks were mixed in the proportion of 1 to 1, 1 to 2, and 1 to 3, and were placed in various positions, some between high and low water, so as to be exposed twice in every twenty- four hours, and others below low water, so as to be always submerged. The blocks were also deposited under these conditions in various localities, the mortar ones being placed at Esbjerb at the south of Denmark, at Vardo in the Arctic Ocean, and at Degerhamm on the Baltic, where the water is only one-seventh as salt as the North Sea, while the concrete blocks were built up in the form of a breakwater or groyne at Thyboron on the west coast of Jutland. At intervals of three, six, and twelve months, and two, four, six, ten, and twenty years, some of the blocks have, or will be, taken up and subjected to chemical tests, the material being also examined to ascertain the effect of exposure upon them. The blocks tested at intervals of less than one year after being placed in position gave very variable results, and the tests were not of much value.
The mortar blocks between high and low water mark of the Arctic Ocean at Vardo suffered the worst, and only those made with the strongest mixture of cement, 1 to 1, withstood the severe frost experienced. The best results were obtained when the mortar was made compact, as such a mixture only allowed diffusion to take place so slowly that its effect was negligible; but when, on the other hand, the mortar was loose, the salts rapidly penetrated to the interior of the ma.s.s, where chemical changes took place, and caused it to disintegrate. The concrete blocks made with 1 to 3 mortar disintegrated in nearly every case, while the stronger ones remained in fairly good condition. The best results were given by concrete containing an excess of very fine sand. Mixing very finely-ground silica, or tra.s.s, with the cement proved an advantage where a weak mixture was employed, but in the other cases no benefit was observed.
The a.s.sociation of German Portland Cement Manufacturers carried out a series of tests, extending over ten years, at their testing station at Gross Lichterfeld, near Berlin, the results of which were tabulated by Mr. C. Schneider and Professor Gary.
In these tests the mortar blocks were made 3 in cube and the concrete blocks l2 in cube; they were deposited in two tanks, one containing fresh water and the other sea-water, so that the effect under both conditions might be noted. In addition, concrete blocks were made, allowed to remain in moist sand for three months, and were then placed in the form of a groyne in the sea between high and low-water mark. Some of the blocks were allowed to harden for twelve months in sand before being placed, and these gave better results than the others. Two brands of German Portland cement were used in these tests, one, from which the best results were obtained, containing 65.9 per cent. of lime, and the other 62.0 per cent. of lime, together with a high percentage of alumina. In this case, also, the addition of finely-ground silica, or tra.s.s, improved the resisting power of blocks made with poor mortars, but did not have any appreciable effect on the stronger mixtures.
Professor M. Moller, of Brunswick, Germany, reported to the International a.s.sociation for Testing Materials, at the Copenhagen Congress previously referred to, the result of his tests on a small hollow, trapezium shape, reinforced concrete structure, which was erected in the North Sea, the interior being filled with sandy mud, which would be easily removable by flowing water. The sides were 7 cm. thick, formed of cement concrete 1:2 1/2:2, moulded elsewhere, and placed in the structure forty days after they were made, while the top and bottom were 5 cm. thick, and consisted of concrete 1:3:3, moulded _in situ_ and covered by the tide within twenty-four hours of being laid. The concrete moulded _in situ_ hardened a little at first, and then became soft when damp, and friable when dry, and white efflorescence appeared on the surface. In a short time the waves broke this concrete away, and exposed the reinforcement, which rusted and disappeared, with the result that in less than four years holes were made right through the concrete. The sides, which were formed of slabs allowed to harden before being placed in the structure, were unaffected except for a slight roughening of the surface after being exposed alternately to the sea and air for a period, of thirteen years. Professor Moller referred also to several cases which had come under his notice where cement mortar or concrete became soft and showed white efflorescence when it had been brought into contact with sea-water shortly after being made.
In experiments in Atlantic City samples of dry cement in powder form were put with sea-water in a vessel which was rapidly rotated for a short time, after which the cement and the sea- water were a.n.a.lysed, and it was found that the sea-water had taken up the lime from the cement, and the cement had absorbed the magnesia salts from the sea-water.
Some tests were carried out in 1908-9 at the Navy Yard, Charlestown, Ma.s.s., by the Aberthaw Construction Company of Boston, in conjunction with the Navy Department. The cement concrete was placed so that the lower portions of the surfaces of the specimens were always below water, the upper portions were always exposed to the air, and the middle portions were alternately exposed to each. Although the specimens were exposed to several months of winter frost as well as to the heat of the summer, no change was visible in any part of the concrete at the end of six months.
Mons. R. Feret, Chief of the Laboratory of Bridges and Roads, Boulogne-sur-Mer, France, has given expression to the following opinions:--
1. No cement or other hydraulic product has yet been found which presents absolute security against the decomposing action of sea-water.
2. The most injurious compound of sea-water is the acid of the dissolved sulphates, sulphuric acid being the princ.i.p.al agent in the decomposition of cement.
3. Portland cement for sea-water should be low in aluminium and as low as possible in lime.
4. Puzzolanic material is a valuable addition to cement for sea-water construction,
5. As little gypsum as possible should be added for regulating the time of setting to cements which are to be used in sea- water.
6. Sand containing a large proportion of fine grains must never be used in concrete or mortar for sea-water construction.
7. The proportions of the cement and aggregate for sea-water construction must be such as will produce a dense and impervious concrete.
On the whole, sea-water has very little chemical effect on good Portland cements, such as are now easily obtainable, and, provided the proportion of aluminates is not too high, the varying composition of the several well-known commercial cements is of little moment. For this reason tests on blocks immersed in still salt water are of very little use in determining the probable behaviour of concrete when exposed to damage by physical and mechanical means, such as occurs in practical work.
The destruction of concrete works on the sea coast is due to the alternate exposure to air and water, frost, and heat, and takes the form of cracking or scaling, the latter being the most usual when severe frosts are experienced. When concrete blocks are employed in the construction of works, they should be made as long as possible before they are required to be built in the structure, and allowed to harden in moist sand, or, if this is impracticable, the blocks should be kept in the air and thoroughly wetted each day. On placing cement or concrete blocks in sea water a white precipitate is formed on their surfaces, which shows that there is some slight chemical action, but if the mixture is dense this action is restricted to the outside, and does not harm the block.