September 1951
INDUSTRIAL AND ENGINEERING CHEMISTRY
organic, algin derivative, propylene glycol alginate, has been successfully commercialized. This algin derivative, Kelcoloi.l, wit,h built-ill emulsifying properties has extended the range of usrfulness of the algin family to acidic solutions. LITERATURE CITED
(1) Barry, V. C., Dillon, T., and O'Muineachain, P., Sei. Proc. flo!/. D u b l i n Soc., 21, 289-96 (1936). (2) Burgess, L. L. (to Plastic, Iiic.), U. S. Patent 1,729,993 (1929). ( 8 ) Carson, J. F., and Maclay, W. D., J . Am. Chem. SOC., 68, I015 (1946). (4) Chamberlain, K. H., Cunningham, G. E., and Speakman, J. U . , N a t u r e , 158, 553 (1946). (5) Cunningham, G. E., Chamherlain, N. H., and Speakman, ,J. 13. (to Cefoil, Ltd.), U. S. Pat,ent 2,403,707 (1946). (6) Detoeuf, A . , Bull. SOC. c h i m . NrZges, 31, 169 (1922). !7) Findley, T. M.,Sweiii, I),, and Scaiilan, J. T., J . Ani. C ' h c m Soc., 67, 412 (1945). (8) Gohda, T., Fr. Patent 707,870 (1034). (9) Ihid., 767,877 (1934). 110) Hirst, E. L., Jones, J. K . X . , and .Jones. Winifred, J . C'heni. SOC., 1939, 1880-5. (11) Janscn, E. F., and J a n g , R., J . Am. Chem. SOC.,68, 1475-7 (1946). (12) Lespieau, R., Bull. soc. chirn., 7 , 254 (1940). (1:i) Lucss, 11. J., and Pressman, I),, principle^ and Practice i n
ct of
207 7
Organic Chemisti,y," pp. 221, 265, New l - o i k , Joliri PViley d Sons, 1949. (14) Lucas, H. J . , and Stewart, \\.. T., J . Am. Chcm. SOC.,62, 1070 (,-~--,. 1 wn) (15) Nelson, Mi. L., and Cretchei, L. H., Ibid., 51, 1914 (1929) (16)'Ouer, R.A., Ann. AlZeig11. 7, 681-2 (1949). (17) Ouer, R. A., private communication. (18) Snyder, E. G. (to Wyeth. Inr.), I?, 6. Patent 2,508,433 (XIay 23, 1950). (19) Sorenson, C.
W.,Seifter, ,J., aud Wright, I. S . . H d l . X. j. Acad. Med., 25,448 (July 1949). (20) Stanford, E. C. C., Brit. Patent 142 (.July 1881). 254-5 (1883). (21) Stanford, E. C. C., Chem. ~VWS, (22) Steiner, A. B. (to Kelco Co.), U. S.Patent 2,426,125 (Aria. l ! l . 1947).
( 2 3 ) Steiner, A. B., and McNeely, \V. II. (to Kelco Co.), I / ! ; ( / . , 2,463,824 (March 8, 1949). (24) Ibid., 2,494,911 (Jan. 17, 1950). (25) Ibid., 2,494,912 (Jan. 17, 1950). (26) Wallerstein, J. S.,Schade, A . L.,and Levy, H. 13. (to \ F - a l l ~ stein Co., Inc.), Ibid., 2,478,988 (Aug. 16, 1949). (37) Wasserman, A , , J . Ciiein. SOC., 1948, 197. (28) Ibid., A-ature, 158, 271 (1946).
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RADCLIFFE F. ROBINSON ANI) CHESTER R. AUSTINi Battelle ,Memorird Znstiticte, Columbus, Ohio T h e investigation was undertaken to determine if an economical antiseptic concrete could be prepared by the addition of copper o r copper compounds to portlarid cement. More than 20 additibes were tested, including radioactiwe copper. Concrete containing 10% of copper acetoarsenite was very effective in inhibiting the growth of both pathogenic and common molds. It was about four times as effective as oxychloritle cement containing copper, eben after extensive leaching of the specimens. The copper additives lowered the strength of the resultant concrete, but not sufficiently to liniit its use as a finishing layer o v e r a base of ordinary concrete. h copper-portland cement concrete could be used practically as a flooring material in locker rooms or showers, around swimming pools, in industrial kitchens, or wherever a sanitary environment is important. The cost of such a concrete would be low and would be further reduced by using a topping layer of the mixture. The color of the additive would add to its value and would eliminate the necessity of frequent painting.
I
NVGYTIGATIONS have 1)t:cn inntic: previously t o dcteriiiiiic: the effect of various kinds of cc:nit.nt or concrete on the growth of microorganisms. These studies by Farrell and \Yoiff ( 6 ) , intlicttted that magnesium osychloridt: cement containing coppcr h i d u marked inhibitory effect on mold cultures. The tosit eiTc.cat o f this cement was attributed t,o t.he finely divided coppc'r whirl1 is iiicorporated iu the c:~incnt. The known fungicidal propc:rties of v:trious copper compounds suggosted that these materiitls might be added to regulrti. pr)rtlarld cement to develop n c.oncrtxt.c3
*
Present address, Koppera Co., P i t t s b u r g h , P a
having inhibitory o r destructive pokvers against certain s p w i c of ~ microorganisms. This study wts undertaken t o detei,minr the effect of coppei.bearing concrete on various typcis of molds, and seeorid:lril>-,tlit, effect of the coppc~radditions oil the physical propprtiw of tl>c* concrete. A concrete h2iviiig :L tl(lstruct,ive or inhiliitoi,y vti'rc,t upon molds would h v c : it variclty o f pr:icticnl uses-fo? i ~ x m i p l ~ ~ . as a floor-surfacing mutei~ixliri locker rooms 01' showers, awuiid swimming pools, in industri:tI kitchrlns, or whcrrvcr R saiiitnry nivironment is importitiit. EXPER131 E:Y'I'A L I'KOCEDCRE
blolds of the genus Gpidermoph!lton have brcn shown to 1w among those causing the di ~ I I O M as . ~ "rtthlete's foot." TIN. species Epidermophyton i n t r d i g i t a l r its chosen for this project. The mold was grown on it modiiic*ationof Saboursud's d~1str0w agar, composed of 15.3% o f I3acto-ircopcptonc, 61.5% of (Itbstrosr.,and 23.2% of itgar i i i 1 litci, ui'watcr. Little information was av:iilati>le on the growth of ~ : O I ~ I I I I O I I molds on concrete. Preliminary investigations were c o i i d u ( ~ t t ~ d , therefore, to determi~~r. which ro111mon mold could bc foulltl living on the surf:ice of phiin conorc~ti~--i.c?., concrete surf:wcss \I hicdi had not been p i i t i t d , whitc.\wshc4, or o t h e p h treatcd. \':ii,ious plttces having :t mit:tl)l(l c>nvilmulnent for inoid grov t i 1 u ('nvisited und the riiolcls fouiid ~ V V I Y , for the most p:trt,, mcnilwi~s0 1 t,he gcnera Aspergillus o r P e n i c i U i u m . Siiiiilur t r s t s by 1':i I t,arisky and hIcPhi,rson ( 7 ) o f t h t b iiiolds groniiig on p : h t l i l i i l b sholvcd these gener;l to I)(:tht. iiiost rommon typc's r e p i ~ w n t c ~ l . .4s these molds arr krlowii to t w \yicic>sprc:id and prolxibly til(, most reprcscrltntivc of t h c ( ~ o n i n i o l 1fungi, one spwic.s of c:ii5li t>.l)(' )vas selected for t,hv tcxsts w i t h t l w concrett': :L g r c ~ i i~ I ~ Y X ~0 1 ( Y Penicillium mold and rispcrgi'ilits niger. The nioltls \V(II'(' vkilt u i d o n potato dcstrosv : ~ g : t rI!? 1 1 1 :~ ~ c c ~ p t mc~tliod. c~l
INDUSTRIAL A N D ENGINEERING CHEMISTRY
2018
10% COPPER ACETO-ARSENITE
Vol. 43, No. 9
riais (6). Although this standard method WRS designated speoifioally for the preparation of oomprwsion testspecimens, the procedure was considered to he appropriate for the preparation of small test eahea in general. The concrete upecimcns were stared in s moist condition iit a temperature of 75" F. for 24 hours and then were removsd from the molds. After 24 additional hours o i ~tomgeunrh:r the ~ a m econditions, they w~re c u r d rapidly in a saturated atmmphere by autoelsving for 1 hour at 300 pounds per square inch stcom pressurr. A l l additions to the corromto were bawd on thc wight of portland cement in thc mix md WPTP inrorprated in the dry nratwials prior to the preparation oithe cubes. Preliminary iesta were made Kith orgmisms chosen to determine the inhibiting effect of regular concrete on the growth of the molds, the effect of various media on the growth o f the OTRHILisms, xnd the effect of various methods of inoculation upon the final growth 01 siirvival of the fungus. The informntion obtained from the preliminary testa was used is setting up standardized methods of testing.
C O P E R ARSENITE
Thr fuegieida. @properties of thc roncrete euhea eontaming additions of various copper compound8 were determined by "Ring a modification of the Farrell and Wolff ( 6 ) method. A suitable BXBT ru1-
wits filled until a thin layer oftho medium
21040
Figure 1. Effect of Copper-Rearing Concrete on Gmwth of Epidermoplryton interdigitole Photogrsph. x u c tnkur W h e n ~ u l t u r e swere 10 deis old. Dark siea surrounding mnorcte s w i m e n iroulture medium; rhife erce in culture dish 1s mold
The concrete specimens used in the tests were prepsred &ceoitling to the specificationa given by the Portland Cement Association for basement walls nnd Boors. The specified large;aize ~ g gate was replaced, however, with a smaller aggregate having i t t i equivalent surface ares in order to have smoother specimens. The concrete had the following oomposition: Amount b y Amount v .4 VOl","e.
Portland cement
.
Cubio Feet 1
weP 24.8
2.75 65.21 F o ndr a e a f p a t s (--6,C 8 meshY 0.44 10.0 Water a ed +Adry rn/x 5.5 ~ S I l O ~ ... The n u r e ste paseed through a standard testing aieve having 36 holes er s w r v e in& but w m rstsined on B atandard testing sieve having 64
Ed,
perilquare mch.
Quartz aggregate and mason's nand (obtained irom Marble Cliff Querries, Columbus, Ohio), and a commercial hrand of portland cement were employed for the prrpaation of the test cubes. The cubes were prepared in the manner prescribed far the p r e p aration of concrete by the Americdn Society for Testing Mate-
covcred the conmete specimen. T h m 1 ml. of an aqueous suspension a i the orpanism under test WBS placed in t.he pi& and distributed over the surinre of the medium. The plates were storcd in B dark room hsvine R constnnt relative humidity of 50% -&d a constant trmpereture of 75' F. Inhibition hy the comer-bearine concrete was shown hv thk'presenee 2 an area free irom grcxth immediately surrounding the cement.. All the testa woro N" in triplieatc and the rrportcd width of the sterile lion^ is the average of the three teak.
The d k t s of various coppcr compounds, organic and inorganic, drtermined. A list of many of tho oo-unds and the p w grentage ~ used in the concrete mixw is rlmm in T d h I. wwe
INHIBITION OI'GROWTH O F EPIDERMOPIIrrON
Tnhle I 1 and Figure 1 show representative rosults of thr inhihitiim of the mold growth by oopper-bearing cemont. Copper acetonrRcnite showed inhibition of the growth of Epidermophyton inlediyitnle in concentrations as low &B 1%. Concrete eonkrining 496 of the same addit,ion inhibited the mold growth witbin B radius o i 0.54 inch after 22 days, while oonorete containing 10% of oqqx:r arrtoarsenitc wa8 surrounded by a stcrile zone of 1.3 inches xft,er 22 days. Oxychloride cement containing eop)x'r check& tho m o l l growth within a distance of 0.25 inch, or wits approximately half &a effectivein this test as tho conorcte coutnining4%of copper metoarsmite. Small additions of copper arsenite were effective d m iri inhibit,ing the growth of the mold. T h e portland cement, pcr s ~ , had DO inhibiting effect OD tbe growtb of the specimens, iis f h o
September 1951
INDUSTRIAL AND E N G I N E E R I N G CHEMISTRY
mold grew up to or over the surieee of the edges of the concrete containing no coppw compound. That the arsenical group was an ltct,ive ingredient i t , the inIri1,itiug mittttrinl \vas evidenced by the results obtniricrl with concrete containing nrsrriious oxide, or lead arsenate (Figures 2:bnd 3). A~ldiiionsoitbL.copperarsellic i ~ loompourds were mort effective, honevw, when added to thc conawte iri siruihr amounts.
2079
\\
I' COPPERIIRSENITE
EFFECT OF COPPER ADDITIVES O\ A9PERGILLUS AND PENICILLIUM
In general, thc conimon molds showed g r c x t , ~resislmce to the eRcet of tlic wpwr-lmwing concrete tlim the pathogenic mold, Epidernmphylon; and the green Penicillium mold was more refiistiriit than Aspigillus niger. An addition oi 5 or 10% of copper acetoarscnitt+ vfirct.ively inhibited the growth oi AsperyCl/t~sniger, while the green Penicillium mold was inhibited only by tile 1070 addition as shown in Table 111. Ti,,, skrile zones pniduccd by these additions w w e small, however, indicating a greater wsiutance of these molds to the inhibitnry property of tho concrete. Additions of coppcr arwnite were BS effectivr. 8 s tqunl smounts oi copper acetoarsenite on the grew Penicillium mold, but wore l e a effective on Aspergillus niyer. Ttic e ~ m r n o nmolds were inhibited by oxychloride cement containing copper; howevrlr, it was not so effective as eoncwte containing 10% of copper aeetoarsenite. The growth of the common molds on the control spocimens occurred in nil cases within 5 days after inoculation. Iittle or no change w m noted, however, Figure 2. EKeot of Arsenioal Group and of Copper Arsenical Compounds on in the efiectiveneus of concrete conGrowth of Epidermophyton interdigitole taining copper acctoarsenite, copper Photographs faken uhsn rultvms were 10 days old msonite, or oi onvchloride cement containing copper over a period of 75 days. Tlri inhibition by the copper-hearing concrete, as meafiurrtl Ily
x x -~
-
x
- _
_ _ x __ -- _x _-
x - x x - x x - x x - x - x x - -
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INDUSTRIAL AND ENGINEERING CHEMISTRY
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Vol. 43, No. 9
used in the USUILI manner. Tests wrw made on thc effect of the addition of c.opprr ncctotwsenite on the normal consistency and setting time of portland m m m t . The cffeets of the addition fwppw acetonrspnitc on the eomprrssivr s t r ~ gnt h a n (1 t,rnai IC strrirgth wcrc determined with 370 qrcimeris of portland rernmt rnnrtw. sp
