I-VDUSTRIAL A N D ENGINEERIXG CHEMISTRY
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tling in a 14-inch cylinder would correspond to 2 hours' settling in a 10-foot (3-meter)tank the temperature of which would approximate 30" C. We should now be able to pour off more than 800 cc. of clear solution and should, therefore, leave 200 cc. of sludge and solution. If we now add 30 grams of hydrate and again bring up the solution to 1000 cc. and a temperature of 20" C., we can add somewhere between 24 and 27 grams of chlorine without overchlorination. Assuming that we add 24 grams of chlorine, meaning a temperature rise of 8 degrees, we can again repeat our settling test and again draw off 200 cc. of clear solution, which can be added to the first lot and again make up our solution by the addition of another 30 grams of hydrate. This will give a third batch and into this third batch we can pass chlorine to the point where there is only a slight excess of lime, being careful not to overchlorinate. If we again allow this to settle and note the amount of sludge a t the end of 14 minutes, we will have, if the operation has been properly carried out, sufficient data to valuate the hydrate fairly. We will have used 100 grams of hydrate and this should have absorbed a total of about 85 grams of chlorine: hence the added temperature rise should have amounted to about a total of 28 degrees. Anything more than 85 grams of chlorine absorbed would indicate an exceptionally good lime. The most important characteristic, however, would be the amount of sludge a t this time. A very good lime would give about 20 per cent of actual sludge where 85 grams of chlorine have been passed into 100 grams of hydrate and theconcentration kept between 30 and 40 grams of chlorine per liter. This will clearly point to the fact that four or more batches can be operated before the sludge is washed. On the other hand, if the amount of sludge so obtained is 40 per cent, we can hardly operate more than two batches without washing the sludge and then the loss would be a little above normal. The character of a bleach solution so prepared should be noted by determining the total and available chlorine in the solution; further than that, the solution should be set aside and, particularly the last run, allowed to stand on the sludge for a period of 24 hours to note whether there are any characteristics in the lime which tend to cause undue decomposition of the solution. The de-
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velopment of a pink color in these solutions due to traces of manganese does not of itself offer any objections. While this method of testing the lime may be a little laborious, it is more enlightening than any other method that the writer has tried. I n addition to the qualities adherent in the lime itself, there is a material difference in the density of the hydrate produced according to the way the lime i i hydrated. As the method of hydration, however, depends so largely on the mechanical means used in hydrating it, there is only one statement that can be made-aim for the densest possible hydrate with a given quality of lime. The peculiar physical qualities in the limestone itself and in the burned lime which tend to make the ultimate impuritiei, including magnesia, settle well or poorly do not seem to come out in an ordinary chemical analysis, but are of utmost importance in the washing of sludges, and where a paper mill is pushed to capacity in producing bleach solutions a suitable lime is of utmost importance. It must be remembered that an excess of lime is always used and the more batche5 that can be run before throwing away this excess, the lower the lime-chlorine ratio will be kept. It should also be borne in mind that the chlorine used costs a t least four times as much as the lime and that every sludge loss caused by lime is magnified by the value of the chlorine. A lime of moderate purity which absorbs a considerable amount of chlorine might be used in a plant that had much more than ample settling capacity and a long period of time for washing and give a fairly low lime-chlorine ratio without serious loss. The same lime could not be compared in value with a denser lime that absorbed slightly less chlorine for use in a plant working t o capacity.
The Re-Use of Plaster of Paris Molds' By Marie Farnsworth2 NONMETALLIC MINERALS EXPERIMENT STATION, BUREAU O F MINES, N E W BRUNSWICK, N. J.
Plaster of Paris molds deteriorate very rapidly on reW h i l e n o means has beell use, the tensile strength becoming much less on each found for restoring used molds mined in the United States is c a l c i n e d successive recalcination. X-ray photographs of the to t h e i r o r i g i n a l t e n s i l e molds show that the gypsum Particles grow larger as strength, a method has been and sold as plaster of Paris. t h e tensile strength becomes less. The addition of found for greatly increasing The larger part of this calabout '/4 Per cent a l u m i n u m oxide is found t o increase the tensile strength over that tined m a t e r i a l is used in the tensile strength markedly and decrease the particle of the untreated material. building as wall plaster, wall size. This has a possible application in die-casting boards, gypsum blocks, etc., Effect of Repeated Recalcifactories, etc., where molds c a n only be used Once a n d where its use is permanent nations on Plaster and there is no need to rethenthrownaway. use it. H o w e v e r , c e r t a i n industries use large quantities of plaster for die-casting metals. .7 The chemical process underlying the making of plaster When the hot metal is poured into the molds, water is molds is driven off and the molds are pitted so as to be unfit for CaS04.2HzO heat--+CaS04.'/2H20 water + further use. The anhydrite formed by the action of the Gypsum Plaster of Paris heat can be rehydrated to gypsum3 and calcined again to CaS04.2H20 Gypsum or plaster of Paris molds plaster, but the plaster resulting from a second calcination is found to be unfit for further Owing to a large decrease On recalcination the same process repeats itself, so there is in tensile strength. SO far no method for utilizing these no reason from a chemical standpoint why the tensile strength old molds has been found and in addition to buying new should decrease so markedly. order to find out just plaster the company must pay to have the Old what happens on recalcination, the water of crystallization of away. The desirability of eliminating this industrial waste both plaster and the water-carryng capacity of led to a study of the possibility of utilizing old Plaster molds. the plaster (the amount of water necessary to make 100 grams 1 Received November 17, 1926. Published by permission of the of plaster of the right consistency), the setting time, and the Director, U. S. Bureau of Mines. tensile strength were tested for a series of five recalcinations. 2 Present address, Washington Square College, New York University, The plaster employed was a sample from Virginia which was New York, N. Y. taken from the ordinary commercial run before a retarder 3 Farnsworth, THISJ O U R N A L , 17, 967 (1925).
M
OST of the gypsum
+
+
June, 1927
I N D U S T R l A L A N D ENGINEERING CHElMISTRY
was added. The methods of testing were all the standard methods of the American Society for Testing Materials. Methods of Testing
COMBIXED IVATER-The combined water was tested by first drying the sample in an oven a t 45" C. for 2 hours to drive off absorbed moisture. About one gram of the sample was then placed in a platinum crucible and dried a t 215230" C. to constant weight. The loss in weight divided by the weight of the sample gave the water of crystallization. CoxSISTEhTY-For testing samples of different plasters, it was necessary that all be first brought to the same consistency, by the addition of the proper amount of water. This was done by means of a Southard viscometer. The apparatus consisted of a brass cylinder of 2-inch (5-cm.) bore with a circular disk flange flush with its upper end. The screw actuating the piston was 5/8 inch (16 mm.) in outside diame(6 mm.) inch pitch, right-hand square threads ' / I 6 ter, (1.6 mm.) inch deep. The top of the brass disk flange was etched with concentric circles which varied in diameter from 6 cm. up to 28 cm. by increments of 2 cm. When in position for use the brass flange was maintained in a true horizontal position. I n using, the piston, cylinder walls, and top of the plate of the viscometer were carefully cleaned. Then by turning the crank the top of the piston was brought exactly flush with the top of the plate. The piston was then depressed by turning the crank ten times in the reverse direction. A mixture of a t least 300 grams total of dry calcined gypsum and water mas made by shaking the calcined gypsum into the Jvater through a Yo. 8 mesh sieve and allowing it to soak 2 minutes. It was then stirred to a n even fluidity for a time not exceeding 30 seconds. This mixture was immediately poured into the well in the center of the plate of the viscometer, filling the n-ell just flush with the top of the plate. The crank a t the bottom of the viscometer was then immediately turned ten turns a t the rate of one turn per second. The upward motion of the piston caused the mixture to overflow into a circular pat and the average of the quadrant readings of the concentric lines on the top of the plate could be taken. A neat mortar mixture was of testing consistency, if, with this operation, it gave a circular pat averaging 9.7 cm. in diameter, and i s expressed as the number of cubic centimeters of water required to be added to 100 gramris of plaster. This is called the mater-carrying capacity. T I h l E OF SETTING-TWOhundred grams of the Gample were mixed with enqugh water to make a paste of testing consistency. A rubber mold such as is used with a Vicat needle was filled with $he paste and the time of set was determined by means,of a Yicat needle. The needle was allowed to sink into the paste at frequent intervals. After each penetration the needle xhw wiped clean, and the paste moved slightly so that the needle did not strike the same spot twice. The set was determined complete when the needle no longer penetrated to the bottom of the paste. The minutes elapsed from the time when the sample was first added to the water to the time when the set was complete, was recorded as the time of set of the sample. I n this, as in all the other tests, all dishes and utensils were absolutely clean, especially free from all traces of set gypsum which has a marked effect on time of set and other properties of plaster. Also, distilled water was used throughout as small traces of salts markedly affect the properties of plaster. TENSILESTRESGTH-Five hundred grams Of plaster were mixed to testing consistency and cast into a five-gang briquet mold of the shape and size used for testing portland cement. The briquet where broken had a cross section of 6.5 sq. cm. (1 sq.in.). Each briquet was not cast successively,
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but the containing vessel was moved back and forth over the molds while pouring continuously. The briquet was worked slightly with the point of a trowel to remove air bubbles and level off the briquets. When sufficiently hard, they were removed and stored a t room temperature for at least 7 days. When the weight had become constant to within 0.1 per cent, the specimens were tested in a standard machine used for the determination of tensile strength. The tensile strength was determined as pounds per square inch. A tabulation of the results is given in Table I. Table I-Plaster
TIMES CALCINED
MOISTURE
:
WATBR-
Before After calcination calcination
Per cent 1 2 3
Tests
18:33 18.08 18,lj 17.58
Per cent 5.s2 550 5.54 3.50 5,50
Cc. H20/100 g.
plaster 72.5 87.5 120 150 175
s%pXI%% Minutes 22 12 8.5 8 11
Lbs./sq. i n .
249.5 91.9s
203 1
66.2 52.1
The material did not change much chemically, as shown by the practical constancy of the water of crystallization. Moreover, it has been definitely proved that the presence of anhydrite (Cas04 would be shown by a decrease in mater of crystallization) does not lower the tensile strength unless in such large amount that it hinders the plaster from sticking together. Since the underlying cause does not seem to be chemical, it is natural to seek a physical explanation of the decrease in plasticity, and therefore an x-ray study of the new plaster and gypsum, and of plaster and gypsum after repeated calcinations, was undertaken. X-Ray Methods
Since the difference in the original sample and the recalcined sample was probably one of particle size, the pictures taken were the ordinary monochromatic pinhole pictures. These pictures were taken on a multiple diffraction apparatus in the Research Laboratory of Applied Chemistry of the Massachusetts Institute of T e ~ h n o l o g y . ~The tube employed was the usual Coolidge water-cooled molybdenum anode type operated a t 15 milliamperes and 30,000 volts, R.M.S. The x-rays were restricted by means of two pinholes 1.5 mm. in diameter 4 inches apart in a brass cylinder with a lead end. Flat cassettes in which a calcium tungstate intensifying screen was mounted back of the film were used to record the patterns. Films 31/4X 4 inches (8.25 X 10.16 cm.) were used. The cassettes were automatically held perpendicular to the x-ray beam during exposure by means of easels locked in a T-slot guide a t a distance of 5 em. Two pins which fit into slots in the top of the easel permitted quick adjustment or removal of the cassette. Since the plaster was in powder form i t was enclosed in gelatin capsules such as can be purchased in any drugstore. Since the gypsum was already in the form of a continuous solid it was employed in pieces about inch in thickness. These samples were mounted directly over the pinhole. X-Ray Results
The pattern as thus recorded is circular in form; the diagram depending upon the substance being examined. With amorphous substances the pattern is a general blackening around the darker image of the central beam. With crystals concentric rings appear, diffuse or sharp according to whether the crystals are small or large. If the crystals become still larger, spots appear on the diagram. Pictures taken for Clark B r u g m a n , and Aborn, J Oplical SOC.A m , 12, 379 (1925)
all the five plaster anniplea noted in Table I showed no differences. The five gypsoin samples made from the plaster samples, however, showed a regular gradation in particle size, the crystals growing continuously larger (though not rapidly) wit.h each successive calcination. Figure 1 shows gypsrmi made from the plaster of faris wlrich had heen calcined once and Figure 2 shows gypsuiri made from plaster of Paris which had been calcined five times. In Figure 1 there are a few large crystals (as shown hy the
darker spots on t,lie filnr a i d lighter spots on the positive; the figures are positives) held together hy crystals which are very small (shown by very slight ring formation and thc general blackening of the film). Figure 2 shows less real large crystals (fewer spots) but larger crystals in general, its shown hy the well-funled rings and less general blackening of the film. Since the CaSO,.'/&O pictures showed no appreciable differences, it was assumed t.hat the small amount of uncalcined gypsum iuvariably left in the plaster acted as centers of crystallizai~ionor catalytically to cause the crystals to grow larger and t.hus cause the molds to he less strong. This is verified by t.he fact that the presence of old wpsum in even a very small amount greatly impairs the quality of an othemise excellerit piaster.
times was only 52.1 pounds per square inch, hut that of the briquets after the addition of 3 per cent aluminum oxide and an additional calcination rose t.o 126 pounds per square inch. A sufficient. amount of plaster was not available fur additional tests, so tests were started with new samples of p1a.ster. Effect of Varying Percentages of AI,Oa
A iicw sample of plaster of Paris was obtained froiri the same mine in Virginia and additional tests were carried 0x1 with it. Briquets made from this plaster vere found to have a tensile strength of 316, set.ting time 19.5 minutes, and watercarrying capacity 50 cc. water per 100 grams plaster. 4 sufficiently large amount of this plaster was made up into molds, dried, and reground, and then calcined with the addition of varying proportions of aluminum oxide. Unless the oxide was added before ihe calcination, it had very little effect,. These results are t.abulated in Tahle 11.
l'liis table shows t,hat the most advautageous percentage of aluniinuiri oxide is :i6 per cent, and tlierefore this percentage ums used in all uther experiments. There was no apparent reason why this sample should decrease in tensile st,rength so much more on recalcination than the first sample from the same locality. While this sample decreased in tensile strengt,h from 316 to 76 pounds per square inch with one recalcination, with the firfit sample, the decrease in tensile
Prevention of Crystal Growth
From these x-ray resuks it was decided that if crystal growth could be prevent.ed niulds having much greater tensile strength would result. It has heen found by Wyckoff and (,kittendens that potassium aluminate added t.o iron catalysts decreases the size of iron cryst:als and thus better catalysts result. Potassium aluminate made hy heating toget,her 3 parts of aluminum oxide and 1 part of potassium oxide at 350" C. for several hours was added to an old sample of plaster in the proportion of 3 grams of salt to 100 grams of plaster. I t was found, however, that by the above process of making pot,assium aluminate some free akali remained and this made the plaster so quick-setting that any good effect resulting from a prevention of crystal growth was completely masked. .~luminuiooxide was next tried and this was found to work very well. Plaster was made by adding 3 per cent aluminum oxide to gypsum made frum the plast.er calcined five times in Tahle I and calcining a sixth time. As seen by Tahle I, the tensile strength of briquebs made From plaster calcined five 6
J 4 m Chcm 5 0 r . 47, 2800 (1925)
Fisure
2-CaSO1.2H20
Made
from
Calcined Five TImes
C~SOI.'/ZHIO
strength was only from 249.5 to 203.1 pounds per square inch for one calcination, and the tensile strcngth had only decreased to 52.1 after a series of five recalcinations. Because plaster of Paris is so susceptible to small variables, it is difficult t.o draw any far-reaching conclusions. However, the addition of aluminum oxide to various samples caused roughly the same percentage inorease in tensile strength, so i t ought to he possible to re-use an ordinary mold a t least once or twice hv the simule addition of ahout l / 4 uer cent aluminum oxidebefore the second calcination.
ISDL:’iTRI.11, A N D E.WI“VEERIYG CHBMIli?” Y
Junr, 1 w Effect of At20;8on
11
Second Recalcination
’The next test was tu find whether the beneficial action of the tilominuin oxide continued or whether it was necessary to add a n e ~ ssupply each tiiue. The molds to which ‘/*per
Figure
3--CaS01.2HzO Mads from CaSOi.’irllrO Calrined Once (Second Sample)
cent tiluniinurii oxide lind heen added were calcined for the third time, lialf were cakined without the addit.ion of inore oside and half were rnlciried after tlie addition of ‘/a per cent, more oxide. These two samples were compared with two additioiial samples, m e calcined for three times without the addition of anyt,hing and the second calcined with the addition of alumiiiurn oxide OD the third calcination. These Entnples are designated 1, 2, 3, and 4, respectively, niid the results w e given in ‘I’ahle 111. Table
317
plaster causes i t to deteriorate n r y nisrkedly. Traces of many foreigti suhstatices caiise a deterioration of plaster and it i s just as likely that traces of runny substatices would improve it, It has been found t,hat the addition of as small an amount a s I/( per cent, nlumiiruiii oxide will cause the tensile
Piaure
4--TaS0~2&0 M a d e from CaSOl.VzH2O Calcined Twice (Second Sample)
strerigt,h to increase ahout threefold, and n o doubt other suhst,nrires would he just. ns good: or even hetter, hut a search was not made for sue11 substances. X-ray photographs from new plaster and front re-used plaster show that the smaller the tensile strengt,li the larger is the particle size. The addition of aluminum oxide causes a decrease in the particle size and increases the tensile strength. This has a possible application in the m u s e of plaster molds where tlie decrease in tensile strength on reonkination is not, too great.
lll~-EBect of Al:Oz on s Second RecalcinatIOn
s ~ ~ ~ WAirR-CnXnu,Na , . ~ CAPACLTY
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