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•

TABLE OF CONTENTS

Page No.

TITLE PAGE............... . • . • . . • • • • • • . . . • • • . . • . . . . . . .• •..•..•..•.. i i

ABSTRACT. • • . • . • • • . • • • • • • • • • • • • • • . • • • . • • • • • • • • • • • • • • • • . • • . • . • • • • • • • • j i i

INTRODUCT ION ••••.•••.••••.•.•......•..•••••....•.••.•••.•..•..••••.

DETAILS OF TEST••••..• - ..••.......••••.•••.•••.•••••••.•••••.••.•

RESULTS AND DiSCUSSiON••.••.•.•••••.•..••.•••.••.•...•••..•.•••..••

REFERENCES •...•.•.•...•.••• '" .•.•..•..•••..•••.••...••..•..••.•.•

APPEND IX A•.•••••..••..•.••. - ••..••...•.•••••.••..••••.•.••••....•.

Tab I es I - X I I ..•.......•..•....•••....•.••••••.....•.•...•......

APPENDIX B•••......•.•...••.•.....•..•...•.••••••..••..••.•.•.•••••

Fi gure•••••..••.••......••..•••..••...••.......................•

DISTRIBUTION LiST•••.••..•••••.••••••••••••••••••••••••••••••••••.•

UNCLASS,FIED

Keport No. CCl #. 12: _copy Number _

DETERGENCY OF THE 12 fO 18 CARBON SATURATED FATTY ACIDS

By

A. Hankowich

14 June 1962

OMS Code No. 5010.11.8420051

Dept of the Army Project No.593-32-006

Coating .nd Chemical LaboratoryAberdeen Proving Ground

Maryland

UNCLASS IFIED

AUTHOR: tI"~llf.",:(A..A. HANKOWICH, ChemistChemical Cleaning &Corrosion Branch

REVIEWED BY~ .<cH. ROSENFELD, Ch efChemical Cleaning &Corrosion Branch

~//7 ~i~--­APPROVED BY: UfV~/V

C. F· PICKETT, DirectorCoating. Chemical Laboratory

.,

ABSTRACT

Systems of one surfactant (two anionic and three nonionic types were studied)with an homologous fami Iy of soi Is (the 12, 14, 16 and 18 carbon saturated fattyacids) were explored to determine the relationship of the detergencies of suchsystems to the physico-chemical nature (HLB, hydrophile-lipophile balance) ofthe soils. A series of systems of ethylene oxide homologs of nonyl ph~nol withthe same soils was also investigated.

Neither surfactant HLB nor adsorptive energy of the surfactant polar group,alone, is responsible for the detergency of the 12 to 18 carbon fatty acids.

Two semi-Iogarithmi~ relationships were derived for th~ nonyl phenolpoly.;!thenoxyether-fatty acid systems; namely, I il1c.ari ty of the R (ethylene oxidemole ratio)-Iog M/eMC and su~factant HLB-Iog MfcMC fu~ctjor.s (M a surfactantconcentration giving ca 100% removal of 16 and 18 carbon fatty acids, and CHC =critical micelle concentration).

Fatty acid soaps are poor detergent:; of the fatty acid :;olls. It issugges ted tha tin such sys tems the ch ief ac t ion is van der Waa Is adsorp t Ionbetween hydrocarbon chains of the surfactant and soil, with adsorption Increasingwith increasing chain length of the former and concentration of the latter.Anionic sodium dodecyl benzene sulphonate is a good detergent of the fatty acids,soil removal being independent of soil chain length.

Polyoxyeth,1enP. (2i sorbitan monolaurate and the 12 and 15 ethylene oxidemole ratio adducts of tridecyl alcohol are poor detergents of the saturated fattyacids.

I I i

I. INTRODUCTION

PrevIous hard surface detergency studies at this laboratory have shown !hatfor several classes of soi I (fatty aCid, fatty alcohol, ester, and amine) a linearrelationship exists between detergency and micellar solubilization beginning atabout 90% soil removal, and that the constants of this functi~n are connected toHLB (hydrophile-lipophile balance) of surfactant, sOil dipole moment and or soilboundary tension (1,2). These studies have covered systems consisting of several(four) surfactant homologs with one soi I, and one surfactant with four classesof soil (2).

Th I S !)aper explor",s sys tems cons 1St I n9 of one sur fac tan t with a homo 1ogousfamily of soi Is, the 12, 14, 16 and 18 carbon saturated fatty acids.

II. DETAILS OF TEST

A. Method

Dynamic procedures were used in determining micel I<li (Orange aT)solubi llzatlon (3) and detergency. Some details of the cietergency testingtechni ,:.Ie (preparation of tc~, panels, cleaning procedure, and measurement ofresidual soil) have already been d~scribed (3). A sl ight change was made in theresidual soil measurement by the substitution of ethyl alcohol for acetone asthe degreasing solvent. Appl ication of the fatty acid soi Is to the steel testpanels was as follows: the molten acid was brushed on one face of the weighedpanel with a small camel's hair brush. The panel was then hung vertically in a105°C oven for a draining period depending upon the acid, as fol lows:

lauric acid I~

myri~tic acid --- 2palmitic acid --- 3stearic acid ---- 3

minutesminutesminutesminutes

The panel was then removed from the oven, cooled to room temperature, andr~w~ighed. The weight of fatty acid per panel WdS 53 - 60 milligrams.

B. Soi Is

The soi Is were reagent grade fatt, acids with melting points asfollows:

lauric acid ----- 42 - 43°Cmyristic acid --- 52 - 53°Cpalmi tic acid --- 61 - 62°Cstearic acid ---- 68 - 69·5°C

C. SOJrfactants

The surfactants in~luded the following commercial ethylene oxide~dducts of nonyl phenol:

Surfactant

nonyl phenyl pentadecaethylene glycol ethernonyl phenyl eicosaethylene glycol ethernonyl phenyl triacontaethylene glycol ethernonyl phenyl tetracontaethylene glycol ethernonyl rnenyl pentacontaethylene glycol ethernonyl phenyl decacontaethylene glycol ether

Symbol

NPPGENPEGENPTGENPTTGENP50ENPIOOE

Ethylene OxideHole Rat io

1520304050

100

Also studied were two polyethenoxyethers of tridecyl alcohol, a polyoxyethylenesorbitan monolaurate, an alkyl aryl sulphonate, and two soaps, as fol lows:

tridecyldodecaethylene glycol ether --.--------------- .. -- TDDGEtridecylpentadecaethylene glycol ether ----.------------- TDPGEpolycxyethylene (23) sorbitan monolaurate --------------- PSHlsodium dexiecyJ benzene sulphonate ----------------------- SOBSsodium oleatepotassium laurate

The CHC (critical micelle concentration) values of these surfactants are givenin a previous paper (4).

III. RESULTS AND DISCUSSION

A. Fatty Acid Soaps

Tables XI and XII Indicate that aqueous solutions of fatty acid soapsare poor detergents of solid fatty acid soils. The detergency isotherms of the12, 14, 16, and 18 carbon aCid soils with both soaps (excepting the potassiumlaurate - lauric acid system) att.:'!in a low maximum and then fall to "negative"detergency (residual soli) original soli). At the same soap concentration,detergency decr~ase~ with Increasing number or ~~rbons in the soil. A probableexplanation of these iesult5 's the following, a theor.,previously advanced byother workers in the field: the binding energy of the fatty acid to ,he steelsubstrate consists of the adsorptive energy of its polar carboxyl groups to thesteel plus the van der Waals cohesive forces between the hydrocarbon chains ofits molecules. Thus the greater the chain length, the more strongly the fattyacid is adsorbed, and the more difficult it is to deterge. Since the ~~Iar

g.oups of the soap detergents are also carboxyl, preferential adsorption ofdetergentdllflson the 3ubst:-dte is m:limized. Tile chief action is adsorptIonbetween the hydrocarbon chains of the acid SOl I and the fatty acid soap, andthis increases with in~reasing chai~ length of the former and concentration ofthe latter.

B. Alkyl Aryl Sulphonate (SD~ Detergency

Table X shows that sodium dodecyl benzene sulphonate is a good deter­gent of sol id fatty acids. The detergency isotherms of al I four acids approach100% re~oval > Dtters~ncy is substantially independent of tne length of the hydro­~arbon chain uf the acid. This ;ndicates that the adsorptive energy of the polariulphonate group is conSiderably higher than that of the carboxyl group, and thatrref~rential wetting by the former occurs readily.

2

C. Polyethenoxyethers of Tridecyl Alcohol and Polyoxyethylene SorbitanMonoJaura te

Tables VII, VI II and IX indicate that the 12 and 15 ethylene oxidemole ra:.io adducts of ~ridecyl alcohol and polyoxyethylene (23) sorbitanmonolaurate are poor detergents of the 12, 14, 16 ~nd 18 carbon fatty acids.

T~e behavior noted in sections III-A, III-B and III-C indicatesthat removal of solid saturated fatty acid soils is related in part to theadsorptive energy (preferential adsorbability) of the detergent:· i.ns ofanionic surfactants (or detergent molecules of :'lonionic agents). It isobviously an over-simplification to attribute de~ergency solely to thedetergent jon or molecule. While the polar sulphonate group appears to beresponsible for the excellent fatty acid detergency of sodium dodecyl benzenesulphonate, the same group is entirely ineffective as a sOil remover inwetting agents I ike sodium iSQpropyl naphthalene sulphonate and in hydrotropeslike sodium benzene sulphonat~. These facts seem to point to a possibleconnection between detergency, surfactant HLB and soil HLB. But thisinvestigation has shown that HLB cannot be the only factor involved in deter­gency. Table I reveals good fatty acid soil removal ability for the 100ethylene oxide mole ratio adduct vf ~onyl phenol (HLB • Ig.J5). Sodiumdodecyl benzene sulphonate, also an excellent detergent of the same soil, hasan HLB value of 1'.70.

D. Behavior of Ethylene Oxide Adducts of Nonyl Phenol

Tables I to VI, inclusive, give fatty acid soil removal data ofethylene oxide adducts of nonyl phenol. The following generalities areestabl ished:

(1) The 15R (15 mole ratio) adduct is a poor remOver of 12 - 18 carbonsaturated fatty acids, particularly at normal detergent concentrations (onlyca 6% removal at 30.CHe or 0 29%). At 360.CHC, removal is 73 - 81%; and at480.CHC (4.65%), lauric acid removal is 91%.

(2) The 20R adduct (NPEGE) is also a poor detergent of 12 - 18 carbonsaturated fatty aCids, 74% removal of stearic acid being the best value atconcentrations up to 150.CHC or 2.57%. At 168.CMC, removal of palmitic andstearic acids becomes good, 92 - 95%.

(3) At normal detergent concentrations (to 24.CMC, or 1.02%), the 30Radduct is a poor detergent of saturated fatty acids. Good detergency of the18, 16 and 14 carbon acids is ohtained approximately at 48.CMC, 64.CHC, and80.CHC, respectively.

(~~ Detergency increases with increasing chain length of the 14, 16 and18 carbcn acid soils at the same concentration of 30, 40, 50 and 100 mole rationonyl phenol adducts. Removal of 12 carbon acid by the latter three addlJcts isconsldt,ab!y better than 14 carbon acid soil removal, and is substantiallyequlYal~nt to the good detergency of stearic acid by these surfactants.

(5) Table XIII, a compilation of nonyl phenol -dduct data at a practicaldetergency level (at concentrations providing ca 100% soi I removal for mostof the surfactants), emphasizes the following points: (a) the abnormally

3

high surfactant concenrrations (2.7 - 3.8%) required to give good sol id fattyacid 50:1 re~oval; (b) the sharp decrease in the HfCHC ratio with increasingethylene oXide mole ratio, R (where H = surfa~!ant concentration giving ca100%. 16 and 18 carbon fatty acid removai); for values of R between 15 and 50,t~0 R-Iog (H,'CMt) function is linear (Figure I); and the surfactant HLB-Iog(M/CHC) funct:on is linear for values of R between 20 and 100 (Figure I); thev~lid!ty of these 5em:-'ogarith~,c func' ;0~5 :5 conf,rmed because they indicatelinearity betw~e" R and 5~rfa~~ant HLB, a r~lationshlp previously reported forethylene oxide addu.:.t5 of l10nyl phenol 0); (d poor dete:-gency of the 15mole ratio addu~t.

IV. REFi:.RENCE5

I. Hankow ct>., A. J11 ; . Ar-. 0: I \~heJT;iS~.,' 50-: . II 39 206( 1962)J

20 Hankow .~ .../ A. J ~Odt .'1g a'1d r"'elT):cal Labo.-arory ..epor t # (;";l ! 19, 10 Hay 1962.3, Mankow ' '"I, P••• 11 '.'. A,... 0, , ;~e"':st,>' Soc." 38,589 (1961 )4. Hank.:-·· ,.h. A. ::oa:: "':j and :."e~ . '.' a i Labo... a to.y Report u ,.... .'~. 103, 17 M.:trch 1961.ff \"o\"&"

4

APPENDIX A

Tab les

5

TABLE I

NPIOOE DETE~GENCY ----% Soi I RetTIova I

Surfactant Laur ic Myristic Palmitic StearicMolar i ty Acid Ac:d Acid Acid

.00100 - CMC 98.8 40.0 24. J 62.8

.00200 98·5 31.3 89·3

.00300 37. J 49.2 96.4

.00600 80.8 99·3 99·6

.00800 99.4

6

TABLE III

NPTTGE DETERGENCY

% Soi I RemovalSurfactant Laur ic Myristic Palmitic StearicMolar i ty ACid Acid Acid Acid

.000450 - CMC 10.6 17·4

.::>0264 17·4

.00528 62.4 33·3 27·2 43·3

.00792 90·9 43·4 65·4

.0106 95·7 29·3 57·5 94·9

.0158 93·2 49·2 99.4 ca 100.

TABLE IV

NPTGE DETERGENCY

% Soi I RemovalSurfactant Laur ic Myr; s t; c Palmitic StearicMolar i ty Acid Acid Acid Acid

.000275 - CMC 10·5 6.5 18.9

.00110 10·5

.00440 16.6

.00660 64 I 208 48.9

.0132 89·7 29·5 61.8 98.4

.0176 69·3 68.2 99 7 ca 100.

.0220 98.2

7

TABLE V

NPEGE DETt:Kli~NCY

% Soi I RemovalSur f:tc tan t Laur ic Hyr i 5 tic "'P:iimitic StearicMolar i ty Acid Acid Acid Acid

.000155 - CHC 5.0 3·7 18

.00582 7·6

.0116 13·5

.0232 20·9 73· 5

,0261 (~ ·9 27·1 92.2 94 9

.0290 98·7

,0349 80 6 80.6 ca 100 98·9

TABLE VI

NPPGE DETERGENCY

% Soi I RemovalSurfactant Laur ic Hyr is tic Palmitic S~aaric

Molar i ty Acid Acid Acid Acid

000110 - CHC 3·0 4.2 1.8

• JOIIO 6·5 9·2

.00330 5·7

.0132 11.2 22·7

.0264 47·7 19·2 29·2 35.6

.0396 78. I 73.4 77·0 81.1

.0528 91.0

8

TABLE VII

TDDGE DETERGENCY

% Soi I RemovalSurfactant Laur i c Myristic Palmitic StearicMo lar i ty Acid Acid Acid Acid

.000148 - CMC 4. I 17·3 Zero

.001l1 3·6 rt:!s idua J 50i ,) 4.2 4.1original soi I

.0213 3·8 residual soi I.) 8·3 12.4original soi I

.0426 13·7 8 2 9·4

TABLE VIII

TDPGE DETERGENCY

% Soi I RemovalSurfactant Laur I c Myr i s tic Palmi tic StearicMolar i ty Acid Acid Acid Acid

.000165 - CMC 5· I 16.0 Zero

.00528 3·8

.0211 14 9 8·5 16·7 21.6

.0422 40.8 56.6 66.6 72. I

TABLE IX

PSHL DETERGENCY

SurfactantMolar i ty

Laur j cAcid

% So i' Remova I -:-..,.... --,__,.--__Myristic Palmitic StearicAcid ACid Acid

.000106 - CMC

.00106

.0106

.0212

.Q318

37·9

76·7

5.2

11.2

22·7

32.0

45. ,

9

45.3

Zero

42. L,

58.8

TABLE X

SOBS DETERGENCY

% Soi I RemovalSurfactant Laurlc Myr i s tic Palmitic StearicMolar i ty Acid Acid Acid Acid

.00150 - CMC 13.4 18.2

00300 23 3 20.4 22.4

.00600 93 0 84·3 81.5 71.2

.00750 96.8 95·3 99·0

.00900 99·7 98·7

.0120 99·3

TABLE XI

SOD IUH OLEATE DETERGENCY

% SO! I R~moval

Surfactant Laur i c Hyr i s tic Palmitic Stear IcHolar i ty ACid Acid Add Acid

.00110 - CHC 10.4 16·9 10.4

.0132 15·4 22.2

.0264 55.0 58.4 48.5 Zero

.0792 ;,.q.O 49.5 residual soi I) residual soi I)original soi I original soi 1

.1056 42.0 3·7 residual soi I)or i gi na I soi 1

10

TABLE XII

POTASS tuM LAtJRATE DETERGENCY

SurfactantMol ar i ty

.0140G-.

.0233 - CMC

.0466

.0932

lauricAcid

37.8

98.1

98·3

56. J

77·5

sa.6

residual soil)original soi I

419

residual soil>original soi I

StearicAcid

residual soil>or i gina I so i I

res idua I soi 1 )original soil

res idua I so i I ).original soi I

TABLE XIII

PRACTICAL DETERGENCY OF NONYL PHENOL ADDUCTSMoleRatio Concentrat ion % Soi I Removal "i'~t(

Surfactant R HLB H ,': HiCMC 12C 14C 16c i8c

NPPGE 15 15.00 .0396 360 78.1 73·4 77·0 81.1

NPEGE 20 16.00 .0349 225 80.6 80.6 ca 100 98.9

NPTGE 30 '7.20 .0176 64 69·3 68.2 99·7 ca 100

NPTTGE 40 17·78 .0158 35 93·2 49·2 99.4 ca fOO

NP50E 50 18.18 . OJ 26 16 72.6 99·5 ca 100

NP100E 100 19.05 .00600 6 8i).8 99·3 99.6

..:: - molarity giving ca J00% remova I of 16 and 18 carbon saturated acidsi':"'.': - soi J = saturated fatty acids.

i I

APPENDIX B

Figure

12

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.t ,';',.,' ITI'" 1'1'1, !::: : !: 'I f: :, : I ! i ' : I ::: . 1 1 I:I'~.I! ,; i I ri -j i ') I' .., I' ,,: I:,; '" .. , II'!';,,;:ii [ii: :ii;l: :~::,: :: ::!,:: i:!I;~~! iii f~~i /,:1 !,, ! :: I;:! :':: ::;: : " " I, :" ~ ! .... :.: I; I I ,:: i I::: .: ! IItt i .., t I' I' • , I' ,~ "" 'I" I .: , .•. ~ • . ,. I ! I, i" r ' I I 1ft

: ' :, :: i: ; I I: .': I: :I .:: I , ' ; '. ..' " . 'i" ,'! i ! i ; :)': : I i

.1,. ,I·' .," , ... ' .. , ""I' ' I 'I I'>:)':;; Ii:: :;/11 1 ; i i:\.:: !::: ii:il::ij::':::;'I" !":~'I:'::I':::I :.:,!!!,I",':::::,· :,:,/: ;1:. 11'"""'11 ... t.;,; , 'I,,' ,:,/. ,. " ",'

IQ 1'./' 1/'1' ; i ;i -;- i j Ii ill: 1'.1 i i; l:-! : I ! I' i : ; I " I.' j i ' ' i ' '.' l'jl., f17.'t·l-rr.'-fj'fTf',I , ' , I, ' . rd. (,-\ ' I' " I I "r' I", f ", 111· '11 !l• .fi jI; I iii iII . '1 iii i .1-1 diJ1.i '.1. I: I iii; I: I .•. 1/1 1., l!.fl,. ifl l 1'1-1

1j 1,1 IJ ! i II !i j ! . r i I! j; j /1 i )!,;):f ni, i I!1,;!111 ;, iIll! jill

'lti-!ltml,J .:111\ I [1; 1,:-jf!II!Wit ;!:.;! 1'-il!Jililit-:1:jJ1I'il!jiITll-i l!,I,!~jL

II, j'H jl'/·' 4!f> /'" ", l[i1l!' jl·t ' j! 'f'" ~-r! : I ""j - j ;11 ·!·'I··:: :": :'1':,i; rr!~'!I'-1 "I fif·j! :,:' .". ,. L .. :_I !, I.'-I.:.__: ....._~,~~,'-, ..I~" 1, ,_.,:"': ·~_;,.,_U_:...~L .,1...:(,.

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t--- <

AD NO Accession No I UnclassifiedCoating & Chemical Laboratory, Aberdeen IProving Ground, Md., CCl # 123 - DETER- I

GEHCY OF THE 12 TO 18 CARBO:; SATURATED !FATTY ACIDS - A. Hankowich, R;Jt No. 123, l

i4 June 1962, 20 pgs, OMS 5010.11.84200511DA Proj No. 593-32-00E '

Systems of one surfactant (two anionicand three nonionic typ~s wer~ st:Jdled)with an homologous family of soils (the12, 14, 16 and 13 carbon saturated fattyacids) were explored to determine the re­lationship of the deterse~cie~ of suchsystems to the Ilhysico-c!.emical nature(HlB, hydrophi Ie-I i.~(\.,,,i Ie Jal,nce) ofthe soils. A series of systems of ethy­lene oxide homologs of nonyl .llenol wi th

AD NO Accession No I UnclassifiedCoating & Chemical laboratory, Aberdeen--Proving Ground, Md., eCl # 123 - JETER-GENCY OF THE 12 TO 13 CARBOI! SATURATEDFATTY ACIDS - A. Hank0'·!ich, R;1t No. 123,14 June 1962, 20 pgs, OMS 5010.11.8420051DA Proj No. 593-32-COc

Systems of one surfactant (two anionic~nd three non ionic t~,es ~ere studied)~ith an homologous family of soi;s (th~

12, 14, 16 and 18 careon saturat~d fatty~cids) were explored to aetermi~e the re­lltionship of the detergencies of such~ystems to the physico-chemical :.ature(HlB, hydrophi Ie-I iPOFtd Ie :)alallce) of

fhe soils. A series of systems of ethy­ene oxide homoloas of nonvl ,henol with

AD NO Acces:::--;: 1 Unc;:ss i f iedCoating & Chemical Laboratory, AberdeenProving Ground, Md., Cel # 123 - DETER-GENCY OF THE 12 TO 18 CARBON SATURATEDFATTY ACIDS - A. Hankowich, Rpt No. 123,14 June 1962, 20 pgs, ~S 5010.11.8420051DA Proj No. 593-32-006

i Systems of one surfactant (two anionic

land three nonionic types were studied)with an homologous family of soils (the

112, 14, 16 and 18 carbon saturated fattyacids) were explored to determine the re­

i lationship of the detergencies of such!systems to the physico-chemical nature ii (HLB, hydrophile-lipophi Ie balance) of i,the soils. A series of systems of ethy- I

Ilenc 9*i de hQDgIgQS of ogPV' phenolw~ iAD NO Accessio~, i~o ,Ur-classifiedCoat i;;g &. Chemi ca I laboratory, Aberde;~

jProving Ground, Md., CCl # 123 - DETER- 'iGENCY OF THE 12 TO 18 CARBON SATURATED

FATTY ACIDS - A. Hankowich, Rpt No. 123,114 June 1962, 20 pgs, OMS 5010.11.8420051iDA Proj No. 593-32-006

'I SYitems of one surfactant (t\.,: a!"lionic.and three nonionic types were studied)~with an homologous family of soi Is (thej12, 14, 16 and 18 carbon saturated fatty!acids) were explored to deter~ine the re­ilationship of the detergencies of such!systems to the ;li,ysico-chemical natureI(HlB, hydrc~hile-lipophjle belance) ofIthe soils. A series of systems of ethy~ ,~~ oxide ;,omoloQS of nonXI phenol wjID_.... ...-:

Unclassified

the same soi Is was also investigatedNeither ~urfacta~t HLB nor adsor?tive energy of the sur­

factant .c:ar gro;J', alone, is res"onsible for the Ceter­gency of ti:e 12 t-:J I ~ carbon fa t ty ac i ds

T","o sC'1i-l:)sarit:.,,~;c reJationshi:)s were derived for t,lenonyl ~.he"lol 01~'elh2:10.yet;,er·fattyacid systems; namely,l;n~~rity of the R (:~thylene o::ide mole ratio)-log M CMCand surfactant HLa-log M CMC functions (~ = surfactant con­centratio~1 <;;vinS ca 1:)0/; removal of 16 and 18 car00n fattyacids, and CMe = critical mice! Ie concentration).

Fatty acid s,)aps ,re ;Jocr detergents o~: the fatty acidsoils. It is sussested t~at ;n such systems the chiefactio!') isvan der Waals adsor;:>tlor. betwee'l hydrocarbor. chainof the s~rfac[ant and SOl I, WI th adsorption increasingwith increasi"9 c:-.ain 1ensth of the former and concentratio

Unclassified

the same SOl Is was also inv!st'sated.Neither surfactant hL3 ~or adsorptive energy of the sur·

factant ;Jolar srou:~, alone, is responsible for the deter­gency of the 12 to 13 carbo~ fatty acids.

Two seri-Iosar,tr.r,lic relationships were derived for thenOl"yl ;:-:'e,,01 ~olyetheno: yether-fatty acid systems; namely,linearity of the R (ethylene Q:ide mole ratio)-Iog M CMC

.and surfactar.t ~:t.3-loS M CMC functions (1'1 = surf..cta~lt con­fcentration SivinS ~a 100% removal of 16 and 18 carbon fatty~acids, ana (h( '" critical micelle concentration).

Fatty aCid soa~s are .)oor detergents of the fatty aCidsoi Is. It IS susseste-: tr,at in such systems the chi,~f

actio') is van der ~:aals dcsc,nti,Jn between hydrocarbon cnail~

of ~he 3~rfactant a~d sci I, with adsorption increasinglwith increasi~S c~ai~ :e~(:~ of the fo-ner and concentratio,i __ .._~_~ J _

In:;~::;''i ed 1the same s:Ji IS ;.as also investigated I

Neither surfacta,t HlB nor adsor~tive energy of the sur­factai"1t ;:>olar srou.), alone, is responsible for the deter­sency of the :2 to J8 carbon fatty aCids.

Two semi-I~sarithmic relationships were derived for thenonyl phen:;;1 :1~ether.o::yether·fatty aCid systems; namely,I inearity ~f '_:.~ R (ethylene oxide mole ratio) --log 1'1 CMCand surfacta'.t f;L3-loS M CMC functions (1'1 = surfactant concentratlon (iVI~( ca IJO% removal of 16 and 18 carbor fattaCids, and (r.C :,,-critical micelle concentration).

Fatty aciu soa s are ?oor detergents of the fatty acidsoils. It:s suss~st~d that in such systems the chiefact on ,svan der Waals adsorption between hydrocarbon ci.amof the surfa~:a:t and 501 I, with adsorption increasingwith ir.cre.:::.'.s cr.alrl iength of the former and concentration

Unc lass i f I,~d

the same soils "cs also investigated.Neither surfscta~t HLB nor adsorptive energy of the sur­

factant ,oo!ar ~r;)u.:., alone, ,s responsible for the deter­gency of t:'~ 12 to 13 carbon fatty acids.

Two se;ni-l.:)~2ritl',mic relationships ....ere de-rived for t:~e

nonyl ,:Jhe;.0! ::,o::'etl-.a:;o: yether-fatty acid systems; nar.Jely,linearity of L:·~;. (etr,ylene oxide mole ratio)-Iog M CMCand surfacLa~t r L3-loS M CMC functions (1'1 = surfactant concentratioi"1 ~IV:-< ca iOO% removal of 16 and 18 carbon fattacids, an':· C,;::" critical micelle concentration).

Fatty acie ,;;:a.5 are poor detergents of the fatty acidsoils. It is s';:o:;~sted that in such systems the chiefaction isvan der ',!-3"ls adsorption between hydrocarbonchaLof the sur;ac:z~: znd soi 1, with adsorption increaSingwith hcrecsii~~ c:,a:;) length of the former and con':entratio

---_. _..---------------_.

-- .p.....-......- i

Unclassified

of the latter. Anionic sodium dQdec"y'I benzene sulpho,ate ISa good detergent of t1'e fatt)' ,~':ids, soil rell'oval beingindependent of soi 1 -:hain lerlgth.

Po Iyoxye th~ IHe ('~3) sor::> i tan mC10 Iaura ,e and the 12 and15 ethylene oxi&,~ole ratio addUCeS o· tridp.cyl alcohol arepoor detergents of the saturated fatty ac:ds.

Unclassified

of the atter. Anionic sodium dodec~l benzene sulphonate isa ;ooC jetergent of the fatty ae Ids, "oil rer.Joval beingindep~rdent of SO! 1 chain length.

Polyo; yethylene (23) sorbl tan monoldruate and the 12 and15 ethylene oXide mole ratio adducts of uldecyl al::ohol3repoor detergents of the saturated fatty aCids.

------ .. ,.-~--.-- ...---~- I ---,_.'-"._-" ..- ........--..--IJnc !dSS if ied

of the latter. Anion.c soc;:.;,', dfJd€·~yl benzene 5ul;:>hemate isa sood dete:::-gent of rhe fat Li "'~ '(1), sal I re-r-:o·,a I beingIndependent of soil chain ler;:h.

Polyru:yethylpne (23) sor0itan nonolaurate and the 12 and15 ethylene oxide mole rat:o adducts of tridecyl alCOhol arepoor detergents of the ~atura:ed fatty acids.

1~~'

Unclassified

of the I~tter, An.onl~ ~odium dt~ecyl benzene sulphonatea Sood ~tergent of the fatty aCids, soi I removal beingIndeperjent of SOl I chain length.

Polyo:yethylene (23) sorbitan monolaurate and the 12 and15 ethylene oxide mole ratIo adducts of tridecyl alcohol arepoor detergents of the saturated fatty acids.

•

tAD NO A~~~n No i Unclassified AD NO Acces~:~-;; I :~c'7:ssified

ICoating & Chemical LaDora.tor y, Aberdeen I Coating & Chemical Laboratory, AberdeenProving Ground, Md., CCl # 123 - DETER- ; Proving Ground, Md., Cel # 123 - DETER-GENCY OF THE 12 TO 13 CAR30:; SATURATED GENCY OF THE 12 TO 18 CARBON SATURATEDFATTY ,dCIDS - A. Mapkowich, R,)t No. 123, ' IFATTY ACIDS - A. MaOlkOo'lich, Rpt tlo. 123,14 June 1962, 20 ~~:,;, OMS 50lQ.II.8420051 14 June 1962, 20 pg~, OMS 5010.11.8420051DA Proj No. 593-32-'OE DA Proj No. 593-32-006

_V'ti1Jijr

Systems of one surfactant (two anionicand three nonionic typas wer~ ~t~died)

with ar homoiogou5 f~mi Iy of soils (the12, 14, 16 and 13 ceorl;on saturated fattyaci<1s) wer~ explored to tietermi:1e the re­i'lt,onsh;~- "f the d(,terse;~cie:; of suchSIS ~ms t· :he r>hys ' co-chefTlical nature(hL2, hyc.; :>~.li Ie-I ii-v,':,i I~ Jal<: l!:e) oft~~ s~ils A serie~ of systems of ethy­~,~:~')~"i~_~-S1.~Y.l .!,enol wi thAD NO Access ion 140 1 Unc Iass i f iedCoating & Chemical laooratory, AberdeenProving Ground, Md., CCL # 123 - JETER-GENCY OF THE 12 TO 18 CARao:! SATURATEDFATTY ACIDS - A. HankO\·!icr., R:Jt i'lo. 123,14 June 1962, 20 ~ss, OMS 501a. 11.8420051DA Proj No. 593-32-COc

Systems of one s:Jrfaclar:t (t~;o a:lionic~nd three nonionic ty~es ~er~ studied)~ith an homologous family of soi Is (the12, 14, 16 and 18 carbon sai::.Jrated fattyacids) were e~~lored to aetermi~e the re­1.tionship of the detersencies of suchsystems to the physico-chemical ~ature

(HlB, hydrophi Ie-I iporhi Ie Jala!lce) of

fhe soils. A series of systems of ethy­ene oxide homologs of ~onyl -henol with

: Systems of one surfa~tant (two aniOOlic',and three nonionic ty .l.S were studioed),with an homologous fami Iy of soils (thei 12, 14, 16 and 18 carbon saturated fattyacids) were explored to determine the re­

: lationship of the detergencies of suet,:systems to the physico-chemical r.atur~ I

I (HlB, hydrophi le-I ipo;>hi Ie balance) (f ithe soi Is. A series of ststems of elr l - ~

lene 9'ijde hqpolggS gf P9P'!'! Rb.eO~..i.A L -9AD NO Accession Ik ~ Lr.cJ.Js_ iedCoating & Chemical laboratory, Aberdr~n I

:Prov i ng Ground, Md., CCl # 123 - DETER- ; I:GENCY OF THE 12 TO 18 CARBON SATURATED I'FATTY ACltS - A. Hankowich, Rpt No. 123,114 June IS62, 2u pgs, OMS 5010.11.8420051 , IIDA Proj No. 593-32-006

Systems of one surfactant (~~ a~ionic

and three nonionic types were ~tudied)

with an homologous fami Iy of soi Is (the112, 14, 16 and 18 carbon saturated fatty'acids) were explored to determine the re­: lationship of the detergencies of suchsystems to the ::r,ysic.o-chemical nature

:(HLB, hydro;:hile-lipophile balance) of·the soi Is. A series of systems of ethy­. Iel1e ox ide homo Ioas of non\ll ~heno I with

--------------,Unclassified

the sam~ s~i Is was also investigatedNeithzr ~urfacta,~t HLB nor adsor;Jtive energy of the sur­

factant c,ar gr0;.1, alor.e, is resl·onsible for the ceter­gencvof t,:e 12 t'J I ~ carbon fatty acids

Two Sem i -l oc:;ar it:,;: c re 1a t i onsh i :)S were der i ved for thenonyl r,he,',ed ol~'el,-,~,.o/y~tLer-fatty acid systems; namel"line~rity of the R (ethylene o;:ide mole ratio)-Iog M CMCand surfactant HLB-log M CMC functions (M = surfactant con­centration S;vinS ca I~O% removal of 16 and IE car~on fattyacids, and tHC = critical micel Ie concentration).

Fatty acid soaps are ?ocr detergents of the fatty acidsoils. It is su<;gest~d that in such systems the chiefac t i on I:' van d,Jr waa Is od _Jr? t vn c.e t\'leen hyd roca rbur, ::ha i 11

of the surfaceant and so, I, with adsorption increasingwit, ir.creasiOlg c:-,ain lensth of the former and concentratlo

-' .. _-.L,..," ..

Unclassified

the !,ijme ;Ji Ie ·..as also i:westigated.Neither surfacta~t HLB nor adsorptive e-ergy of the sur­

factant :Jolar srou.J, alone, is responsibl~ for the deter­gency of th~ :2 t'J I.g carbo,) fatty aCids.

Two semi-I~~aritnmIC relationships were derived for thenonyl phen~1 :I~ethen~:yether-fattyaCid systems; namely,Iinearlty::f ~:,~ R (ethylene oxide mole ratio) log H CHCand surfac:a·.t f:L3-10S M CMC functions (1'1 = surfactant concentratlon (iVI~(" ca 100% removal of 16 and 18 carbo" fattaCids, and ~~C ~-critical micelle concentration).

Fatty acid S02 s are ~oor detergents of the fatty acidSails. It IS suss':?sted that i" such systems the chiefaction IS 'Ian der waals adsorption between hydrocarbon d,a,"of the surfac:a ,t and sOil, with adsorption increasingwith ir.cre.:::: ... s, daln length of the former and concentration

--.-------.-- _._~ . ---1-----Unclassified Unclassified

the same sOils \';a~ also inv~stlsated. the same soi Is. as also investigated.Neither s~rfactant hLB ~or adsorptive energy of the sur' Neither surfacta~t HLB nor adsorptive energy of the sur-

factant ?olar srl1u::-, alone, is responsible for the deter- factant ;Jolar ~r,)L:.;, alone, IS responsible for the deter-gency of th~ 12 tJ 13 carbo~ fatty acids. gency of t~~ 12 to 13 carbon fatty acids.

Two se,ci-10sarltr.mic relatlonshi;>s WE.re derived for the Two se,ni-lo<:2ritLmic relationships were derived for t:-enonyl ~;·.z!1;)I)Qlyetheno:·yether-fattyacid systems; namely, nonyl ?he;,o! ·,u:':ztr,eno; yether-fatty acid systems; namely,

.Iinearity of tr.e R (ethylene o:dde mole ratio)-Iog M CMC linear:ty of I::'~ ;. (ethylene oxide mole ratio)-Iog M CMCtand surfac!a~t HLB-log H CHC functions (M = surfactant con- and surfacl:a~1: ~ L3-1oS M CMe functions (H = surfactant con[centration SivinS ca 100% r~moval of 16 and 18 carbon fatty centration flv:·.: ca 100% removal of 16 and 18 carbon fattacids, and Ci-C :: critical micelle concentration). acids, ar.c' Cr',C :: critical micelle concentration).

Fatt)' aCid sva~s are .Joor detergents of the fatty aCid Fatty aciC :2a.5 ar.= poor detergents of the fatty aCIdsoils. It,s sussestec troat in such systems the ch;ef soils. It is s'.::S:lstad that in sue:, systems the chiefactio., is van der ~!aals aCs.:lr;:>tion between hydrocarbon chair. action isvan der '.:0<.>15 adsorption between hydrocarbon chaioi the s~rfactant a~c soi I, with adsorption increasing of the sur7acta~t 2nd soil, with idsorption increaSing~with ir.c;zosi.~<; cr.;)i,) ler,s:r of the former and concentration with l'1craa5i,.~ c:,ain length of t,'e former and concentratlo: ~--"'_._" - .. __.........

I ._-._-. i

Unclassified

of the latter. Anionic sodium dodecyl benzene sulphonate isa good detergent of the fatty acids, soil rem0~al beingi nd'~pendent of so i 1 cha in length.

Polyoxyethylene (23) sorbitan monolaurate and the 12 and15 ethylene oxidemole ratio adducts of tridecyl alcohol arepO<Jr detergents of the saturated fatty ac ids.

Unclassified

of the latter. Anionic sodium dodecyl benzene sulphonate isa good detergent of the fatty aCids, ~oil removal beingindependent of soi I chain length.Poly~;yethylene (23) sorbitan monolaruate and the 12 and

15 ethylene oXide mole ratio adducts of trldecyl alcohol arepoor detergents of the saturated f~tty acids.

.,~

I _.- I --.--.---------Unclassified

of the latter. Anionic sodium dodecyl benzene sulphonate isa good detergent of the fatty acids, soil removal beingindependent of soil chain length.

Polyoxyethylene (23) sorbitan monolaurate and the 12 and15 ethylene oxide mole ratio adducts of tridecyl alcohol arepoor detergents of the saturated fatty acids.

Unclassified

of the latter. Anionic <;odium dodecyl benzl~ne sulphonatea good detergel"it of the fatty a::ids, soil r,~rr.oval being~ndependent of soi I chain le~gth.

Polyoxyethylene (23) sorbitan monolaurate and the 12 and15 ethylene oxide mole ratio adducts of tridecyl alcohol arepoor detergents of the saturated fatty acids.

UNCLA§SIfIED

lIJNt lLA §§K FKlE JI)