T H E J O U R N A L OF I N D U S T R I A L A N D ENGI,\-EERING
844
ILLUMINATING OILS. Sulphur compounds in wick from sulSulphur in lamp phonates and sulcalculated to S. phates calculated Per cent. t o SO+
1 2 2a 3 3a 4 4a
Kerosene original. . . . . . . . . . . . . . . . . Kerosene original. . . . . . . . . . . . . . . . . Kerosene in 25 cc. residue.. Kerosene original. .
0.015 0.035 0.038 0.071 0.135 0 018 0.057
No SO3 Trace SO3 Trace SO8 0.0075 per cent. 0.013 None None
0.035 0.098 0.354 0.345 0.080
None 0.098 per 0.018 per 0.032 per 0.074 per
........
Kerosene original. . . . Kerosene in 25 cc. residue
.......
S.
1
2 3 4 5
Turbine oil..
.
Machinery oil. .................... Heavy gas engine oil
cent. cent. cent. cent.
GALENA-SIGNAL OIL COMPANY, FRANKLIN, PA.
TABLEI.-REL.4TIVE
SOLUBILITY OF METALS AND
MIDVALE STEELCo., PHILADELPHIA.
A NEW ALLOY WITH ACID RESISTING PROPERTIES.' B y S . W. PARR.
While marked advances have been made in the development of alloys with properties which render them resistant t o the corroding influence of the atmosphere, not so much study has been given to the production of alloys which would resist the solvent action of strong chemicals. This latter function of resistance to chemical action has been given over almost wholly t o the noble metals. However, there are certain 1 Paper presented at the Eighth International Congress of Applied Chemistry, Kew York, September, 1912.
ALLOYSIN 25 PER
CENT.
NITRICACID. Percentage dissolved in 24 hours.
B y W. A. KOENIG. Received April 10, 1912.
Nov., 1912
specific requirements such as ordinarily call for the use of gold or platinum where the quantity of metal involved and the excessive cost of the same make its use almost prohibitive. These considerations have led to the studies herein described in which the effort has been. made t o develop a n alloy especially resistant t o nitric and sulphuric acids. A preliminary study was first made of certain of the more common alloys with a view to determining their relative solubility in nitric acid. An arbitrary strength of acid was chosen which was obtained by diluting the ordinary strong acid of 1.42 sp. gr. in the ratio of I of acid to 3 of water, making approximately a 2 5 per cent. or 4 N solution of " 0 , . The alloys employed, together with their order of solubility, is shown in Table I.
CARBOR DIOXIDE ABSORPTION BOTTLE.
Fig. I represents a piece of apparatus that is a great time-saver in making determinations of carbon in steel drillings. It consists of a round bottle having a t mercury trap a t 2 both the inlet and 4 outlet; these make Wa it possible t o weigh the bulb without removing the oxygen. The bottle is filled, as shown, with calcium chloride and dry soda lime ; the traps with a very little freshly d i s t i 1 1e d mercury. When filled, it weighs be tween fifty a n d sixty grams and Cop.ABSORPTION BOTTLE lasts for a t least one hundred determinations where the carbon content is about one per cent. The apparatus is so simple in construction that any fairly good glassblower could make it.
CHEMISTRY.
1 2 3 4
5 6 7
Pure iron 99 .8% pure., . . . . . . . . . . . . . . . . . 100.0 Commercial aluminum. . . . . . . . . . . . . . . . . . . 5 1.4 Monelmet 19.2 Nichrome, .................. 7.9 Copper aluminum, Cu 90, A1 1 0 . . 3.5 Nickel (79), 1.3 Ferro silicon 0.1
.........
The tests in Table I were based on the per cent. dissolved in 24 hours at room temperature. They are of value only as they show relative solubilities. Test pieces were used of approximately the same superficial area. The amounts dissolved expressed as percentages are sufficiently accurate for comparison. The range of solubilities varies widely, being from 100.0to 0.1per cent. The last two items on the list suggest the possibility of carrying the series further. Because of its physic4 characteristics of brittleness, lack of working qualities, etc., the last number, ferrosilicon, was not selected as affording a n encouraging basis for experimentation. The next to the last number however, the nickel chrome compound with a small amount of aluminum, was selected as a suitable type for further study. A series of six mixtures was arranged as in Table I1 wherein i t was sought t o determine the effect of the introduction of copper. Some such modifying element seemed necessary for the reason that the value of No. 6 in Table I was nullified t o a large extent by reason of the difficulty experienced in casting t h a t material free from flaws. The melting point of the mixture was extremely high, approximately I S O O O , and it was thought.that by the introduction of a metal of lower melting point a product would be obtained which would flow more freely and solidify without blow-holes. The series arranged, therefore, was a nickel-copper-chrome combination with decreasing amounts of copper and increasing percentages of chromium as shown in Table 11. Series So. Parts S i . . . . . . . . Parts Cu.,. . . . . Parts Cr.. . . . . . . Soluble in 25 per cent. HNO3--24 hours
1.
65 30
1
5
::%le
TABLE11. 2. 3. 4. 5. 6. 80 80 80 75 70 5 10 5 5 10 20 20 10 15 10 0.023 0.05 0.013 0.02 1.25 per cent. per cent. per cent. per cent. per cent.
The interesting fact developed in this series was the
~
Nov.,
1912
T H E J O L - R S A 4 L OF I L V D C S T R I r l L A N D E N G I N E E R I N G C H E M I S T R Y .
degree of resistance that could be attained with considerable quantities of copper present. Kos. 3 and 6 were substantially of the same resistivity but ?So. 3 was more sluggish in pouring. Very little difference could be detected between Kos. 5 and 6 , hence the latter was taken a.s a basis for further experiments. I t n-as evident from the impossibility of securing perfect cast material from No. 6 t h a t a study must be made of purging agents to clear the bath of oxides and dissolved gases. Aluminum could be used to advantage in this regard while a t the same time the resistance t o the acids was slightly increased. Tungsten was a slight further aid and manganese up to a n amount equaling I per cent. did not appreciably augment the solubility factor. Other deoxidizers and denitrifiers in various forms were used, such as boron, silicon, titanium and vanadium--the effect of the last one, seemingly, t o increase the solubility. The others in fractional percentages were effective both in improving the resistivity and the texture as well. The average range of values employed was approximately as follows: TABLE III.-SHOWINGCOhIPOSITION O F ACID RESISTAST ALLOY. Xi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66.6 . . . . . . . . . . . . . . . . . . 18.0 .................. 8 5 ......................................... 3.3 . . . . . . . . . . . . . . . . . . 2.0 n. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.0 Ti. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.2 B ................................. 0.2 Si . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.2
__
100.0
Not all of the difficulties of casting the material have been eliminated b y any means. I n proportion as the texture and soundness have been improved upon, the difficulties connected with casting the material have increased. The contraction of the metal a t the moment of solidification is very pronounced and shrinkage cracks are very likely to occur. However, these difficulties are chiefly physical and mechanical and in each specific condition they can doubtless be finally overcome. The alloy draws into wire and spins readily and may have numerous interesting applications. As a method for more precisely measuring the acid resistance of the material, test pieces were prepared having a n easily determined superficial area. These pieces were subjected t o 4 N HNO, and in mixtures of nitric and sulphuric acids of similar concentration, for 24 hours a t room temperature. The loss in weight was calculated t o a unit area of I O O sq. cm. per hour. The comparative values are given in Table IV. The various melts differed slightly in composition, the attempt being made t o determine the limits of certain ingredients, especially manganese, copper and aluminum. The best results were obtained with compositions conforming most nearly to the values given in Table 111. The solubility in sulphuric acid was found t o be as a rule no greater than in nitric acid, hence, the solubility tests were made on mixtures of the two instead of upon the sulphuric acid alone. Very few tests on hydrochloric acid were made. As a rule the solubility of this type of alloy is considerably
TABLEIV.-SHOWING Loss
NUMBER OF 23
IS
845
MILLIGRAMS PER 100 SQ. CM. PER HOUR.
4NHNOs. 3iELT. mg. 0.03 0.03 0.50 0.06
4NH2S04 mg.
...
0.79
1 v01. 4NHNOs. 4NHC1. 2 vol. 4NH2SOI. mg. mg. 1.95 1.95 1.98
25 . . . . . . . . . . . . . . . . . 0.19 0.08
0.3
0.0 0.17 1.10 1.30
0.09 0.10 1 .oo
3.70
0.8
60. . . . . . . . . . . . . . . . . 0.2 0.4
1.95 2 .05
4.8 5.2
64 . . . . . . . . . . . . . . . . .
2.70
2.0 1.85
0.3 0.2
greater in hydrochloric acid than in nitric or sulphuric acids.1 Indeed, a study of the various properties of the material up to the present time has been preliminary and largely qualitative. The detailed examination on structure, solubilities, physical and electrolytic properties has been deferred until a practicable or workable alloy could be obtained. This has now been accomplished in a very satisfactory manner and further work as above indicated will be continued. As illustrating the practical value of the alloy a calorimeter bomb was constructed and has already served for heat determinations upon a n extended series consisting of sugar, benzoic acid, ethyl-benzene and coals. The pressures employed have ranged from 2j-50 atmospheres and charges of material up to The results are all that IT/* grams have been used. could be desired. An illustration of the cap or cover t o the bomb was given in my article published in THIS JOURSAL, page 746. The interior surface which comes in coqtact with the corroding gases retains its polish and luster without any evidence of chemical action. The details of the behavior of the alloy in this apparatus were given in a paper entitled "Some Tests on a New Calorimeter Bomb," by Dr. R. H. Jesse, Jr., THIS J O U R N A Lpage , 748. UNIVERSITY O F ILLINOIS, URB.AXA.
MODIFIED BUNSEN VALVE. B y LESLIERUSSELLMILFORD.
Received August 12, 1912.
I n making analyses of total iron, the following scheme has been adopted by the author in working on the Saratoga Mineral Waters. When reducing the ferric compounds to ferrous, by means of nascent hydrogen, a n Erlenmeyer flask with a Bunsen valve attachment has been used. The accompanying cut shows a t a glance the modification which has been satisfactory. A, Erlenmeyer flask. B, Cork. C, Bulb cut from I O cc. pipette. D, Rubber tubing. E,Glass plug. SS', Slits for valve. "Stellite," a cobalt-chrome alloy described by E . Haynes. THIS 2, 397 (1910), shows a solubility under the same conditions of li milligrams per 100 s q . cm. 1
JOURNAL
