'1 “LUBRICATION OIL EMULSIONS” BY DOUGLAS IRVING MAXWELL THESIS FOR THE DEGREE OF BACHELOR OF SCIENCE IN , I CHEMICAL ENGINEERING COLLEGE OF LIBERAL ARTS AND SCIENCES UNIVERSITY OF ILLINois 1922 Digitized by the Internet Archive in 2015 https://archive.org/details/lubricationoilemOOmaxw 5C0274 li .-w< MVMi iiiii-^-iit.- V 8io>!Tjji YTieMavim ' ;iv 'i - ..•w YQ ’40ier/jmu£ YK ynn/u sisaijt aiinfAJi r r>ing3 ot ai aI§P ■»• ■ ■- .y^ _ . <0^ >, . . 'j;' ^r '■Vi -V ^ » A, r... . • » •«» » ♦ « ' ' ’''4 , •. V-J \ ni K^t'.*n}’f!i «V»Jb;?5^?.. .N-'-SC".- J- f '' — "j ? »■* ’ *»!►•••- ^ ■ . T'P ■ -V..V •.* . f >. k h ,-J*<.l , * ^ J ‘ •> ^ .J.,‘ « F »• ’’..t • ■^-’.‘11 fe*- ^•' ;' /• ^ i»-& ^sMk • J. '. f 1 .r55?aHi£Er. ‘iv/ ic> cjai^A / .' . ‘ ■ ^ 1 . jr 4 Ta'blt? of lontentf! Xiitro duction Page 1 Theo r-gti cal Page 2 .^xp(irimental Page 9 iJiacossion arid conolusiojn Page :*.3 34131 iograpi'^y Page 15 • > . <’''r| iiW'' ^ •'■^n ■ ..”T A^.'l '.• «’ ,A iiviyii‘'l . 'i , “> ■: ^.l| liJi^*r ■ • ■ .11 ■ v^ c' .'• ' ■ ■■». »' I p a, 1 L'» ^ ;K; 't |! '0&y t.:’i ’ i ' f I? J « Ui» . tV ^' • : '’’ V ■; . »•<■ '.r ; • ^ ' •. .'V j*.'**i ’ ' ^ V*i& 4 r-: . i i • * .. ./ t 1 1 a . . •. * '• Lil: i / • .* • ■ 4 i_ ft' ,a 1 ! ?*»>■ C V i L ’■ ^^*.- • '■' ;.i} '''*L ' ' ■ vr ' ," V‘ if- ••i-’^V ■ . ■• _Vr* 'fi" '^rf- 1 ^, ' ■. ^ ' ^ , ^•'^'''*[' "' 1 .' ' '?■ ^ • - i %1 ■ r- r (T a-'V „ '.'. ,„V»i : 1 ... ’*, •'. >,■.'. . ■ ■.•;'-■•■ ■ •■ to. I *'Tmr * i"^r~ ' ft. *^ca •' ;<,'. m -- 2?v*»PSBi , . >'V . V m ti- '* ' - '• St ‘ ■■' '■\VhS^'Ws%i -i' t a -t- !>■' i\^‘ /"JljSuki '^.''itSiD " '( ’’/* r -''■' ’A - ? l' I ' * ■ ■'' ■ w|! .V , ' “ ■ . - ' . . ' ^ ^ i a".' . Wr .''S'( i^^f’’^i t rffifiiit— j^Slr . ! r. j''^- ‘' '. LU}iRICATION OIL EMULSIONS The subject of e^^riulsions has been one of interest to the chemist for the past twenty years. Hany theories have been advanced as to the cause of the phenomena of emulsification, but thej' were specific and not general in their application. A great deal of work has been done on the subject, each -worker dealing with some particular phase of the subject tnat inter- ested him iiiost. ^ As result a moss of arbitrary data has ac- V cujiaulated which has a bearing upon almost ony question that rai^^ht arise. In the petroleum industry the handling of e-iulsions and their subsequent breaking up is ofte?i a troublesome and expensive operation, often the crude oil appears at the sur- face as an emulsion, Wi^.iie in refinery practice the care and means taken to prevent its forjuation and tne equipment for handling emulsions form quite an iteui in plant expense. Recognizing two types of emulsions with which the pe- troleum chemist has to deal, (l) crude oil emulsions, and (2) refined oil emulsions, this work was undertaken in an attempt to try and find out some of the oharact eristics of lubricating oils when emulsified, the cause, and if possible, a means by which an emulsion of lubricating oil with -water could be pre- vented from fo raing. A great qu?:ntity of work has been done on how to maJce, or fona, permanent emulsions, but the litera- ture contains but fe-w references as to the prevention of them. This work deals with the prevention of tiie lorfartion of emul- sions with n refined oil in water. rfy% <' I 69 Vt. > M. ■ ' j S'* ^ 'iia3|_ • tp* Y x«trc J J6«.LiKL oi£^' '^4 . V /J ' i' * * 'iV^B « n '4Hl .' ) . i> ^ , i ,(f I'-'-' £F^- ^ lii ' ■ V- ' 5- • ' f . «v. . '. ', 1 ,. '**j' *^ tl4ii*Qi . > /.I ifcflJr ^ - i ''^ ■ JL. I. '■ -#I S . t .u • H>. .-u P%im‘ <»!4*d» , I .'. V" 1 / M 'll . f •#- Vi^l^ -■ nV A M 'a .. • i ’ '-./■- ■V’Si':. \: h 4 0 .f •'■ '’S'f C'‘:;-»r -s') H » > < » I ‘i*, f -^' V- "■"If?' ik*'-*- f .j . I /U« . 4 itl*» '>»»<» M. .. .iij' pt. il*.-''- • *’y ■-' ■<.* i,'‘i. '4'' ‘ . 1 rf' .'■ ‘ ‘ ' ' ' ‘* ’’■ ‘*'' ' ■“ »■ i .9^ 6 r^^x-ri' t .♦ If;, ’ <4 i’ 1^5 - R’' ivt -j-U A fl^r . #AVfs .1 • .ita; i^a>3 jg ^ 4 .. - |j I'l #• -i J ‘ ^1' j^Ci rA'itf* ' ^ ,r.4UJUilA4^^ ' ■ > - * 1 *"'r '■ ^ ^-1 ■ . . * 'S/r i\ *" J I . .5 '' ‘* -. • v^ •'Si' r f* •al'# > ^ 'Cmiji. *t Sv-a •^J '■'( ■< ' -V'* ' a l^5 W , JO ’ i» Clficsi* ■ '' . > AS .«M,jf #.' 1^ iifiiLi.j '$rUi».fm.i 9 f ; » nJi ^ t '• ' 4 i }%$ , 'Adlliiwi^^ i ^ ^ •» i ' o u i V t . » t i a i .' ‘ > .-> ; ’ «• jriilii', ’ t-'i ’ ^1*' ■• . . • .* 'a.-* _ , ■ -r/Tk.JS ^ I'- ' •*'<^ l»Iif^ i.l -a* aittl «,r ■ ' ' ' . • '• * • * ' ‘V, ■ 'r'v :A;M:4''. ' •-.A', 1 ^ a iy ’a>iir'^.' 1 ''»-w)U ^4i9 ^ V' ?><• 4. .A 'r<|ilii ^/•‘^ j I -♦“Hi “, ;i/' Mb' .;t'''vV^»i 341^4 (’< 5^1 '■; t ' - .7 -i», (.■■.■• <» 4i V *./'l. ' lU ;ar.' t^r4t' # c. • ib r a brief review of tiie literature of emulsions A* W, Thomas (l) has done some valuable viiork. This article states that an emulsion is a heterogeneous systea consisting of one liquid dispersed as tiny droplets in another liquid. It has been definitely established that three phases are essential for the foivaation of a stable amulsion: (l) Liquid A, (2) ijiquid B, and (3) sn emulsifying e>gent. The two liquids must be immis- sible, or nearly so, in one another. The two main types of emulsions are those wherein water constitutes one of the li- quid phases, end two main types are recognized: (l) a liquid (oil) dispersed in water, and ( 2 ) water dispersed in oil. The factor which oontrcls the type of erauision, i. e. , wlietlier wR.ter or oil is the external phse, is the nature of the effiul- sifying agent. In general, if the emulsifying agent is more easily wetted by water than by oil, th®i water will be the external phase and oil the dispersed phase, while if the emulsifier is more easily wetted by tne oil, the reverse will be true, Ban- croft *2* puts it this way: If the surface tension between Liquid A snd the emulsifying agent is lower than the surface tension betwseh Liquid B and the emulsifying agent. Liquid A will be tiie dispersing and Liquid B the dispersed phase. Since the emulsifying agent is almost always recognized as a colloidal substance, it is fairly safe to say that a hydrophile colloid as and emulsifying agent will e;fiulsify oil in water »nd a hydro- phobe colloid will emulsify water in oil. This latter state- ment is subject to modification, however, wtiich will be consid- ered later. '..■ 5 -. % L M J .}' rr ^Ji■' - r.| ':si^. • ' f /> » 1 / -• « n: t/, . V •• <■ Wv A f '*' 'r.\' .‘1. ' " u « . ■-< 1 ■' T Ji, ? . , f ». 't , ■ ; vSr ■':' '■'■'• 'ri ■.-■■ . ■ 'Hi- : .■■’ ■ .. ' -v < V. c ' ■> j f ■ ^ ’ 1- !A ^ V ■; ' I ' ^ ..;1 '' " 7 i'^'. vl ’/ ■" ^ irf . fc ,*v ^■ai 4 ♦/ •d f' r •t. ,1"; r *■'■ tn ■ . ..:!■. :. \v ' ■ ■ . v.f :t’ • ♦. •••a.'if;' I iV'l ;< i , ,'■. -rx'fli ’.at'M . Hlhi - 3 - There is a very airnple and reliable metliod of dete mining the type of emulsion. Upon the addition of an emulsion of oil- in-water (i. e. , oil the dispersed phase) to water, it will dis- perse. Similarly, a water-in-oil emulsion will mix v/ith oil. In short, an emulsion will freely mix or dilute with more of its external phase, but not with more of its internal piiase. Uil In Water JSmuisions There are three main classes of this type of aaulsions; (1) The emulsifying agent is an electrical charge on Uie oil particles, probably due to selective adsorption of the OH- ion of the water by the oil particles. (2) The emulsifying agent is a water-soluble colloid. (3) The emulsifying agent is an insoluble, or very slightly sol- uble colloid. There are many cases also where a combination of two or even three of the above saay function as eraulsification agents. (l) <",lectrical Charge as .Emulsifying .-gent«~These emul- sions are the simplest. They are identical with those observed in the condensate from steam engines. They laay be prepared in three ways *3*» (a) 3y snaking a small a'Xioufit of Jiitieral oil (2 cc.) with a larger volume of water ( 100 Gc. ) f o r 48 liours. (b) by boiling a drop of mineral oil with excess wpter under a reflux condenser for 30 liours. (c) When a small amount of mineral oil dissolved in al- cohol is poured into water on ernulsion results iramediateiy. Lewis found the si:4e of tiie particles in tnese etaulsions to be alike no matter now made, and of tne order of 0,4 micron. Ud V i- S . - i. ■'v". ( ■ I* 1 1 ^ ^- -Tii: y 4 * ^ .,.• ' >/// ”' ^*s . -I m'ii r- \ y:- V, -t * 4 - . ' '>. ;/ .r* I if . *!?' f I,. , : ^ wi ill V -i i f - . ^ ,.' » • • v’‘J;.'l^' u;’! uV i-=st=m' - 4 - They are negatively charged, the potential difference of the double layer (Helniholtz effect) being - 0.05 volt, his measure- ment of the size of the charge on the droplet, by electrophoresis method, indicated 4. 4 nc 10-7 el ectix) static units. These emul- sions owe their stability to the electrical charge and Bro't'mien movement . ‘The origin of this electrical charge is obscure* Ellis *4* ascribed it to difference in dielectric constants, according to the rule of Coehn that a substance of high dielectric constant is positive to one of a lower dielectric constant widen one is dispersed in the other. This, to be sure, does not explain. He prepared mineral oil e’/iulsions by the shaking method and obtained a concentration of one part oil in 10,000 parts of water, the size of the particles being 1 to 2 microns in diaiaeter, and tiie specific conductivity of tiie emulsion was l8 x 10-6 mhos. He found the potential of the double layer to be -O.O^ volt, as Lewis did; but his measurement of elect. rical charge showed 2.12 X 10-6 electrostatic units for the 1-micron particles. He also noted that they were ?aost stable in the presence of n/lOOO sod- ium hydroxide. He ascribed tne stability of this type entirely to the electrical charge and stated that surface tent ion had nothing to do with it. Hatschek *5* suggested that the stability of such miner- al oil emulsions migiit be due to the fact that the specific gravities of the phases were close to eaaVi other, but Grosohief •6* contested this view. Powers *7* prepared this type of eiUlsiori by the shaking method and detenained the double layer potential to be -0.046 • 5 - volt, .vhicli ciiecks fairly well witn Lewis and illliB. lie studied the effect of tiie addition of eleotixjlytee to tne eaulsion and noted that aiiions ha/e tae powers to increase tnis negative potential, while cations decrease it. Very stoail airiounts of Kcl and K 4 Ve(cn )6 (up to 0.001 molar) increased it, while larger aaouats deoi'eased it. yalts with polyvalent cations always de- creased it, due to the predoMinating positive charge of the cations over the anions. He noted later tiiat vdiile an iwu/iediate Gh 8 x*p change in the contact potential occurred Ui)on the addition of salt, there always ensued a secondary slower change; in tne ’ case of o. salt like iiacl 2 the change is continuous in tiie saiae sense, whereas in cases like Icl^, it reverts hack a little, due to loss of on account of hydrolysis. (2) 1?ater- sol able colloid ns jJaulsifying Agent--Good eTaulsif iers of this class are sodium and potaesium soaps, egg alhuiiien, gelatin, etc. The emulsions \wierein soap is i-he eraul- cifying sgent will he tue only ones taken up. Previous to l899» was classified ea an excellent emulsifying a...ent for fatty oils in water, romian's ’S’ investi- gation showea that its emulsifying powers were really due to the soap formed hy the interaction with the small ajaourrfc of free fatty acid that is always found in fatty oils. In 1907 Pickering '9* did some noto.ble work upon emulsions. In all cf his experiments he aiiulsified a parsffixi oil iii water, by puapiug it back and forth throUrgli a rose noa;ale gard@ii syritige. lie found pot^ish soaps tc be better than aodiujti aoaps as emulsi- fiers and noted that a certain critical concen tration of soap was required for each proportion of oil and water, e. g. , to " • ■ ■ ~ V . ‘ * <-iw ^ rt.“ . . . • (.yW .. tt* ‘t /if*’ -t • , iiM i* 1>^ i) ■■• ’ ■ .' .*lX • ' V, . • ' 0 - m . .. ■ M ' •■ — ■•• V 4 . ‘ .• .- * 0 f ; -\i.* ' • ; / ; " , '• • A -nr a f I *• 1 % ' t ‘ ; ■' '"f.;''7 (Kl ■'■ ' V ,■* i I'., C «1 " ■ 'r ■■' % • -■' u ■■■' ;*' ■'■]• " t.^ i • 6 « emulsify 7!^ volwatjs of oil ’arith 25 voiuass of the latter must contpin 0.7 tc 1.3 per ceat of potas}:i tjoap. ”br 40 volaraeo of oil to 6o vo-lumes of ^'iter, 0.3 to 25*0 per cent soap can be used. He noted tliat soaps vary ^sreatly in esuaisifying power, some brands being useless, and. In fact, tiiso batches of the same brand nay Tary in emulsifying power. He noted also that wiiile rise in terapemture facilitated emulsification, it had no influ- ence on tiie noiQixj aitioa. (3) Insoluble, or only siif^htiy soluble, colloid ns e.a’Jil- aifying agent— There are p n jir>iber of bneic me tai.lio salts that raot as Q''collent emulsifiers. Pickering ^10* states tiint wiile viFcoaity and low surface tension of a liquid facilitates the enulBific’^tion of an oil in it, yet it is :.x^ssible to raake ?in emulsion In a ?.iquid which dees not possess these properties. The T.iost imi>ort::int condition Is the pre»^ence of small particles insoluble in the dispersion raodiu?n which coat over the oil parti- cles and prevent tneu from coalescing* In order that such pr rti- cles have the power to form emulsions thej'^ must show only a slif^ht tendency to unite with one enother, must be readily wetted by water and must not be crystalline. Water in Oil jilmulsionB This type of amulsion is coiamon in lubricating greases and is eaeily produced with the aid of ciulciu:’! tnd m.agnesiuia soaps. Clowes 'll' performed some striking experiments v4th soap emulsion of olive oil and water. By addition of calcium chloride to an emulsion of oil in water (with sodium oleate a© emulsifying agent), ha found that when the calciuiw concentration I • 1. «; ■f-if *Ar -rr* T.^, m, i< - *-*ifiSMRi(ML^ ■'•? ' '‘ •• « >■ '• Ki“ * ’ ■■■ • - 'P n^ '^1^ -• '».*’•■ , f'”' • 7 ■ •■ - , • *,,. 'i* •. ) * f4 • ■• ^- j» %*' 1 P' , ^ Hi ^ * ' . >■■■■ '' , ^ i|T( ¥ * Iff ♦■ ■. ■ '< T' , * ■' *» > ■ .'iwJrSjr !i».WiT rf?, ■ _'i^.' tt-tHiiiJ . ...... >^:. J -tf- . • bit' ,. ■ ..V •. V, 'V.'- ■‘.M i’ .fcwl5«.!»^''i* ;ooi#ii~.?, '/ ; , ->.T I A '- <’■ ■ - ' ■'■’■ ■' ^v. __ r .. -i'..'- «ie.'. *• i > • ',jLaij>.' • r». U;., !■ ' V. , ■...; . ;:■ , J., - 4^- ■ -j: v*^. . • ■ ■ ■ , "'; ■' • • ;■ i •' IP>’ «4fil.J,.'’k'i.'7! ..-VTT.- - 7 - eicoeeds tha chenioal equivaleijce to 3ociiu;xi, the e/iulsion passes through a oritioal and chanties i-o one of iue water dis- persed in oil type, lie round that uodiha, po taesiU:/!, aiid lithuta soaps e'nulsify oil in .n?ter mxiie raagnesiuia, strontiUia, barium, iron and aiaainha aoapa eiauisify water in oil. he e-tplainea this phsnoiaena by the fact tixat the alkali uoaps are watted more by water tliaii by oil and since it is Uiouijjht that the surface ten- sion is lower on tae water side tnan on the oil side of the globules, tne films will hand convex to tne water and concave to thecil, enveloping the oil particles, because the area of tne inner surface of a sphere is ieoo Umvi that of the outer sur- facfi. aimilar reaoc/iiing holds for the diuperoion of water in oil by the oth>r soaps mentioned. Langmuir ’12’ has v very interesting theory' as to the cause of emuloions, f.e otsirts vdth the view point thi.t all the forces involved in the structure of solids and liquids are really chem- ical in nature, end that not only chemici^il cosiibination , but alec the phenomei^a cf condexisation, evaix>ration, adsorption, co- hesion, 0 ry stall i saii io h , liquifaction , viscosity, surface tension, etc., are mciiif estatione of either primary or secondary valonce { Werner) , the conclusion is reaciieu that adsorbed films on plane surfaces cf solids or liquids should in general be one atom or one group mole in thickness. The experiments of Levaux, iiaieigii, fl£arc©lin, and jPockels have shown tnat very small aTaoutits of cei'taih oils on the surface of water have xio appreciable effect on its eurfaot tension, but that the sui'fact tension begina to decrease suddenly when the amount of oil per unit area is in- crexased beyond a certain sharp lirait. This result leads to the " . -Zr - It' * * ■ il Llrx .aaeu**: ' -ftfeasiiat: ;s*jrK:;:t:^iS.n‘s f.-' I ••• .-t.v' -c.; ivi..-? 'V- ■ ti .•■ s / ..mV ♦* '« te> II ■ ■ ^" 'V® ,i^'. ■.'• ... '■'• . .. , . ‘'4 ) * !^ 4 . *J 4 B k ' V > trJj I « '■! ' J .^1- t. -;j ; . w f ^ ^vi .\ f I T* •' 1 . l.,,'*- *• . , '* 1'- ■J^ Ww U.i^ '’*' 9 :-.,*’.f/..:- I'l ;'^9n rt yjt^^ 4lilU ' ■ ■ ^ i4 ' !|l . . .. •■ . _-..'x }x'i ■^. ' f» - ^*. .S * ' ♦ J ^ ■#<- • 0 '< 3 i' ••V / ■ii^'\*/%sm--. ^ g^vii' ■ . n I j ; R !* . U f "!; '. ■ J‘ v-i >•. -.-■ .■ M'k t -.. -Ao^vVr^ .'A .'.>■■■*4 >:U' u '43! j,-' r{ , .<*^4-7 ... 5 . I ■ ■ '• ■’• ■ ''i’ ''•.■■^'^, ''■ . .'^y :*^ ■ i/M ^>i»r v'Wn-vJ»' i k -'r :/,.' - .V I? iVv'^rs^; . t .\i£yr^if t>' V . \. •■> > L. ■'■ ■ ' >. ■•- )HGcm . z ii?... I '■ , ■'^v#•■/|vrvIi•‘? 5 l^^ -V -• ■ , w ' i f.. *^ '. 111 . 8 . conciusion thrt the ataoaic of oil necessary to affect sarface tension corresponds to a layer one ioole in thicicnees. yurthenrio re, Langnrair reasons that since tne oil apreads on mtei- and since tne presence of -OUOH, -00, or -OH gi'o ups in an organic i-aoie tends to render a substance soluble in water (tnus indicating a strong affinity of water for -COuii, etc.), we must regard the -COOH groups in the oil film as cnemicaiiy coiabined with the adjecent il^p iaolecules and that therefore the oil film cjonsists of oil molecules standing on end, the -GOOH groups being next the water and the hydrocarbon chain extending upwards fipm the sur- face. Pure hydrocarbon chains do not spread upon the surface of water. Thus, when an oil spreads upon water it is an inaication that a soluble group is present in the hydrocarbon chain. ijrom the fore.joing resuine it is readily seen thj.t the lit- erature on emulsions is a collection of data on specific problems that may have a general application, and maybe not, most of it has an indirect bearing upon the subject as a Wiole. ’orae of the meons used to breaic up emulsions are: 1- Addition of excess of dispersea phase. 2- Addition of a liquid in which the two liquid phases are soluble. 3- T/eat ruction of the enulsifying agent. 4- iTilt tion. Heating. 6- .^’ree^ing, 7- ?0.ect roly zing. 8- 0 en t r i fug ing . In this work all eaulsions were broken up by impinging upon a hot plate. Trv-WTx.' ,• ^ ,-■1 .'v,'y._;', ’• V ■ r-'Pc. " '' ■ ifjHll rf ' «» . ■•■ ; .: ■ ■ rf£ IP WiiA A^u ”^1 i ’ ’yB !’.''%•■< t»i '.- :, lU ck^> j } ■t'ti A<> ' .;■ .A '-> . ■* 5- -ir;;: . A •l’''»- i.y »*«f- I* ^ •;*’ ■■•■■■ \i' *,:.’■ ' • *f ' '-;| •'■■Vj.‘: ( i i ‘r . I'f ' '|a ;**<» \ ' • 'Y I ^ ^ 4^ ; ?!♦ * -A'- ' I •. >:■ • • * . . S \i - V. .i. V- '>T„ ' ^ '-_t? ... ■ ^'■.' t »-v‘’ .«sli .' l»‘«iWi^ii?i s'< J'- "' 'r ■*.^ I • .^. * * Lv*: .>IH - • 4r -S) «*•#! ,1;" > • « ■' 1. ; ■ rf^' -.. <•4 ".,19 i ■ .' 'v’i 'i ’’.v', ■ '■ tv*:. / I ■r»>ff . -■ ^ '-v-m iBNhJkw* i IH g r ^ T^fa ■ * k£; J - ■ '• ■> yi- i. 'J w '. '■' 4'4, .■ I * * ; ■•/A 1 ^ i^vi' • 6e ./ k. <. j • , t ' » " . V }i t ,f 4. , .'; , '■ ft f ’ . U />' J 1 ‘ .. ' • ■'.; '•'' ■■ 1 •' i.i' if 3 ^%xa jxperi Mental 9 • In revievrinft' the literature two tlieories were selected ohat appeared to hrve the Most "bearing upon this problem. They are ; (1) Jjllectrical charge on the droplet. (2) Water soluble group in the chain. ith the aboTe t"?o theories in mind it \mn neceBnary to procure rn oil th.^t could be used as a blank test oil. An oil with a straight paraffin chain structure that had not been com» pounded v.lth any other oil or a fatty acid was found in Wujol, which responded with a demulsification niaaber of lOBO out of a possible 1200 for e, mejcimuiA, ^hat little emulsification there was was due to the electrical charge on the particle and could be dissipated by adding a little water. The Bureau of dcandarda* metno d for deteraining the demul- sification nuiabor was used. It consists in tniiint? 27 cc. of oil and 5^3 cc. of wfiter in a 100 oc. graduate cylinder, stir with a paddle rotating at 1J>00 h P. lU for five minutes, keep- ing tile temperature at C. A record is kept of the number of cc. of oil that settles out. This number times 6o divided by t e number of minutes taken in the settling out is the demulsi- fi cation number. Example : 'Tin. after stopping X « 5 . 10 . fable !lo. 1 ppddle-- cc. of oil settl ed out--««yo. I. t)0. 6. 72. 10 . oO . The maximum rate of settling is ta^ien as the demul sification number, in the above ease tne nuuriber aouIc be 72. Thus an oil » .| f r -TJi- ■ »y V •?'v^^s5p^‘v];55ii t .7 . '^1^r.':’ v-' \^v % ; -'u*' .-^iil t^/ ,•. • “■”" ■ ^., Vji S^:.t^44f*/t* r. > ** :./; ■t'..^"/ :- ,KV' M, f •• . ‘ \ ■ M * Vii I ■ ■ 'j ' «-!■: V d: n*?’ C ;'’ ^ ' ‘i'iw; ^i' ! .^ ^ Ct * * 6 * • t ’ ' ^ # Vu IK ^ ^ ^ S < 4 *1 ' < ■ , ^ . JlT’ff f.,- ▼ ji 1 ' \-n -f^ ri> *» -fv •' ■ i'-t' r )<• ' Jk !>‘ ;wi A : •/ .-'v/' ’%L *^ 'v ■ >4 ' I ^ ZCi '}i : ■*, n ,V ♦ 1^; r __ • tC- .1 f 1 ^ S>f . n‘;:0’t *1 1^ " ' , * ^*, 'V* ^ * * " • -. : r <%iii 'V'\* ; 'L >*'M ’ .7 * ' ^ U H' '’■' !' ’ '. ■ iLi V* I *‘i’ « ■*'i'^ ' ^ *' ..&; ffr " ■:' '.tt. -•',. .-»■• '>:ti ^''v"'’ei$ipii^ ., l! ■I •V ■ ■ .. .J •■Hl*fS>’ f :'? ■'■' j V’ i#*^vO,v. ‘V ^iv? -: •• .V ■:* ■ ' ■ „ K ‘ t i,'. 1 - . , - ' . ,»t,- V ■/■; w,; »i/' ■ •’' . -‘ u » V r t ... . >> V , '.A. 1 •! V ■ ... ' , , •Uf?. •.•'*-• , ■', . , i; Ij ■ '^?j| c. '•'••-/V 4V*'" “‘‘‘ •'•-‘■•s *' ..J .> ir'. .. ; i.’4. rV.r L. . :.., .:■ -’^av ■.hf 'i .l'--Vi'^jt»v ■ -- t|^ ji ' t '*' ■'/ U,i^\i^. '*'' "'' ' - ■* •' ' * . - a" ./'./-J ’v"' ' '.. ■ .'‘■■-‘v -'-■*■ ■> . . '■ '■ '' 'UlMk • ■' :A-4:>A.'i^i.'- -‘•v -i 1 M.t^-\yJ‘t> • ..; .•i';' ■•'. : . ftWl ' ' ■V/. ■ ^xu-yA .'■ j.t^ V '. V ■» ■ Sii •.*; - 10 • tUat was 100/S dejnulsifiabl e would ha'/e its 23 cc. of oil settle oat in the first ainute after stopping the paddle. Upon running a number on HaTolins B it gave a dernul si fi ca- tion number of 5^«5* analysis of the oil proved it to be a compounded oil and that it contained 1*42.^ of fatty acid. To this fatty acid might be ©ttTibuted the low de’tiulsification number. This was partly prcven by adding 1.21^ of stearic acid to llujol i-^hioh reduced its member from i080 to 27^. Havoline being a eompounded oil was found unsuitable for this work. In looking for a commercial oil siiitable for the work Polar- ine No. 2 was selected. It is a straight fire distilled paraffin base oil --^nd should give a higli demulsificat ion number. The num- ber was found to be zero. It was now a ^iUestion of finding the cause of the emulsification. „^br fear thai Uie oil haa not been sufficiently refined it was treated with varying proportions of concentrated sulfuric acid at different t^fiperntures. hone of the treatments had any appreciable effect on the de:uuisifioation num- ber. Treatment with liquid sulfur dioxide at -lO'^ C. and subse- quent tno.ro ugh washing iailed to produce any results along the oesired line. Taking into account Langmuir’s soluble group theory it was decided to treat the oil with various chemicals to try and de- BlToy the soluble group or re*ider it less active as a cause of emulsification. All of the salts used had a higii solubility in water. In each case the oil was t^gituted. with the metallic salt for thirty minutes at a tenpei’uture of 120® C. The oil was then f M n .. U.i - .11 •■'*■' r * 1 1”’ . • ■' • ' -^ ' ^ ‘ ^ i#i^ 0- \i\'-i*tt. ■:1^^^■■ni^t■ ,tjni - i .j'C^ti'?!: t.yl* V’^nc^qi' ^ ■•“ ' ;ic.r.A n<* ■,;t -,-1 ou .24 ‘JftV.flllt- 'tlft '.' iU, ’r "l\’ . ■ r_sa?j '"v ;i,V i: • K'- ■ #4 ■ i , (' f 1 ' •i ,T*^ ■ ■ • *•■» .'• ^ ' .■“ ■ ‘4’^i- •/''.► 4 If , ' >. ■ i.!:! *1%,../ '•',fn* ;1 -Jf i A ■ .-^ jU' ts 'j!.*-' *ut:v'»u^^^ TiW ' ■'i ' r ' * , ••' .'’^I_a . JT,| i*'?/# 41. 1^-^. • ‘ ^ ^ v%HJa /: . '4 i$u' MIt A *XK |: jli^V^' & " A i . : 1. k’.fj W ** ’ ^" ^' *’'* ''* ! K , • . >»i- A. ^ .r/lfe’ni, \ 1' * ' ' '4 ”^Y -'f '', Y,'a*. '»4SJf . ■ ■■ -. fcvTVr ./ "li- c'** , ...*» V 'i*.v;;.i. Bf-.,t. /. ^ .**. J&.-V, * •;>•;-»'. .'ll f«,; '5||w ,4 4»* 4 ^ v\y; i.or.n-i n * "4 • ; . iT' . '. ' ^ ., 1' '■■ '■ .V-' , L xi- ' ;,WMi>>"'''5^' ■' '■^'«j;'*;-^ 4 . ■- ' u i .%i- iiQ«*A ^ i?*v/ ^ Ik 1 4: " ■'>■•■ <^--'jiv,. ■■\'''^’^>? '.'-•■ -’'.'f'l: I * ■ 'I ■*••.,- '#*.,( vV--. ' •■\ tv»',. ». > I la-ur I I 'i .rm r j~a '^£* .vTT'' l._. V' . ■ ,. f ■!* '', . ^’' / ••- ft ’ .11 giten a thorough wa'»iiing and filtered through A-’nller^s earth that hao juet heen rcjiiiored from a orucihle wiere the te-jxper' tujv ’ras aroanu ^00^ 0. The results from the various trentraeuts are tabulated ba.low in Table II. Table II oil Ghe'.r.lchl jOeraul , No . 50 C cc. i/s lb. 25 . 25^0 cc. 25 ^r. Cu{no)^ 6. JOO CO. 7oi . sat. 0 CC. CO. 25 15 gr. gr. Oaalg 0 • 66. IpO cc. 15 gr. e c 1 T 0. IpO cc. 11 gr. Cacl| 0 . i!?0 CO. 26 gr. 'jaclp 0 . IpO cc. 22 rr'Y* 0 • Cacio c. 150 cc. i6 gr. Zno 0 . 150 CO. 11 gr. Ca) 0. IQO CO. gr. 0^.504 iH^O 0. 150 ac* 0. 1 mole : 2n0 ♦ 0.1 mole OaO 0. 150 cc. 0. 05 •’ Zncl 2 - 0.05 0. It f is readily 3 e en ti :iat tile above che-.iiaai tr eatment 'was ttie \nlU 3 as an aid in iao rea s in g t he demul s i f i cation nusib The above treatment does by no means extiaust the ohewlcal pro- cesses througji which an oil raay bo put, but the lack of oatisfact- o ry results tended to discouriige further treatment iii this manner. Ic-Jia the behavior of the oil in the various treatraents it was suspected tnat the unaatura-tfon in the oil was a factor that was causing some of tiie emulsification. With this 'theory in view ib was iiiidertaken to prove or disprove it. An iodine number by the Hanus method was run on the oil cOid a value of 1.64> obtained, in deternnining the structure of the compounds in the oil, it was found that the oil gave a iibrmalite nuraber of 9'/, which is to say that the oil is composed chiefly v - 12 - vf cyclic: hydro carbon aj. An to thp effect of cyclic hycirocarbone on emulsification, the dctuli^ifi cation nii(nl)er before their reiaoval was sie;ro , imd after their rer«>val Evidently tne cyclic hydrocarbons were not cauaini? the trouble. In an attempt to eatur«te the oil with hydrogen, organic method®, were used at first, h^indred oc. of the oil was brcminated and then treated '/dth zinc and hydrochloric acid. .Aft?r washing with dilute alkali until neutral it gave e number of 1200. The oil layer contained some water but it is readily seen that a gre*?t advance has been made. In nnother method 200 cc. of oil was brofninated and then trsated with 200 cc. of alcohol ♦ 30 . gr, iSino dust * 100 cc, of one-, eight loth .tole of Cu;?!)^. .feeliing witii alkali and neutral- izing ani taking u nanbar on the oil, it gave » nwaber of l^bO out of a uos,.iibi6 l 620 , The oil contained but little water bug. cleared up compietexy in a few lainutos. for fear that come of the reagents were responsible for t,he results, a straight hydro- genation was made, The -uicisel cutal/ot was prepared ’Ij* by dissoiviug pure nickel in dilute nitric acid, making a syrupy solution by adding sugar diropping upon a dot plate. This gave a voluiaicoua nickel oxide. iuve grams of this catalyst was added to 3^)0 cc. of oil, the temperature was kept at iBO® G, and a stream of hy- drogen was passed tnrough the oil for 2 hours with oonstoiit agit^^tion. After filter.tng turough .fuller’s earth the oil gave ei number of ipoO. inis means tuat t/Ue oil is de’.auisif iable. The ioiiiiie nuiaber was reduced Isom to 0,40;^, , ; >i^r.*- — ■ .’ y p ■ ■-VJissAiS* >.^Jk i— ^ ■ ^ 'V. ^';::k :m^ > , ^ a .': i««i4^ c< .3>^ T f , , ^ "> .% fi^ < , ♦ u ■ Ji /<>ii ■ fi 1 ••<» 6 -ij) Of «■ ' "' . MV ■ ■ T* ■ > -*>L • -t ■• ‘}” -. i ■ ' . iS i^-..-, s: * ^ si’ »« ■ ” - ■ ' "'•;' •' I Csl ’ . • V ■ i..'t\ |v ;*it^ i i .1 • -V % ,' ‘i->J * ^ ~ -rUi ' ■ iW^, -•-.< - % ^ -^Jl:. n»M/kKjif' /a3j ■ ■■' ■-■ •• ' .',■ ' • T" ‘‘•fc'"' "'im •i~. \ « PI* '> '■ ■ ' ■s ' ;■ U. t 'i -i. r <- ■ > ■* '1 t'-'H W ; *• . ,w>.io '«:4^.- . ., • ' - .■ ' - '••■■v; ■ ’ ■ ' ... . . . • . T '. HIT" xV'.^ E ' l' > ■^' I'- . - ■• 4 * .* • ■ \ *1 ^ ^ t w r • *y ■ .V \ ^ * . 1 ■ f \ ^ i H I .'» . ■ . / J' ' * > *. . A-i -• vf /I.S utfca ' rj . S» '.A ». " f fr V 'UJiJMl'/ ;Ai JTiB£ - * .... .: .. V ...»1 .. . XX i. t... ..V _„.a...: ^7 HI :«4'l A. *' \ • V:. : :'^^^t)^'|R*'’''‘’X' '■“.S; ,.j» • ■? ^ - ' ' ' li''- .-^ ■ '. \ v>-' . il.W<-'’' ..Ai>#»S>*^ |H'' -y. ■ r 'fi-'C’"' > X ’ ■* >< .••■ ■'.••• >" . ■ -■"■•■■rtis'W r'if*’ ',■ %iSn. J 4*’ I ;■•■> .■ #.•. -V :r 'i* i- *.? _ - 13 • Applying the sa-ne method the results were not eo satis- factory. Pols.rine ilo. 2 was coiupcmudcd \fith blo-m rape seed oil in tne p-coportion of 34 /^ loiaririe to l6^ rax^e oil. Ihe iodine number of this oil was 3.41?;^, mid its deiauisifioitc-ion njiu'oer wp.s 0. :>y hydrogenating for two hours oy the aho'/e method the deuulsif ication niimber was raised to a value of 1 ^ 00 , out the oil contained a consiciorabie quantity of v;ater. :Tever- t^i.eies3, the compounded oil wao materially helped from & e’emul- sification atandpoint. Hiysioally neither oil wae changed to any great extent. Mscusfeion "Tom -he foregoing v?orl<' one may readily foretell Just will hapj^en if an oil that contains soluble groups, or has been com|>ounded with a fatty acid is agifeatect witn ■^ater for a few minutes. Even «ui oil tiiat has not been cc. a pounded rnid thst theoretically shoulo contain no soluble groups can be eiT/ulsifi ed. This ■»iay be oue to an electrical aharge on the perticle, but soiie of the emulsion© formed in tiiis wox'is. cou3.d not be broken up by auding more of ine exieriial i,uxase, wnich seldome fails to break up emuiaions of this type. ‘liiis leads one to ^sttribuie tne cause to some other factor. .And tnie v'Crk has established tnat factor as unsaturation. It is a fairly well estr/blished fact tnat cyclic hydro- carbons with a s)aall percentage of ihirxaturption ioake the best lubricants. '13* One of tns tbeoriee advanced for cjo .C iJo and- ing oils wiln fatty acids is that the fatty acid reacts with the bearing metal and holds tiie oil in place. Taether there ia a reaction or not the fatty acid enters the space around *■ Xi, - yi, ’“■;!; . ; ■f.H ’ ' fi*' i. f'i ; f t. .. -:i.-.v itfl %''. 'J 4 t 1 -" .g. >. '*y'f r''< 5 P"'!r " .'l-i"i**, . j^srj >■■ i'v »'i A^*v»f» i|.^'^-V^- *'i^>.'.^/-«*y> ?>'V ft' .- Vf .'niii.l •r ^ ’ m‘ » n ft j — • ■ Is JC . •-5' -* t Ifc* .its ' 4 o -» ' rs*' . 4 . t. ; .:ir* j 5 ,KV' ■ ■*■ i *l^-r.^» ••^ ■ , 5 ^^ 1 ^' ■ '»*» s t A ■• ■'•,'■ r ^ * # !- r: .> .-v.at».i *-- x^* -sr vi. 3f . . x:* ■ ,vrfti - .v^ ‘‘s'cij r 44* ^-f4>^.r t?;v *rjf : m- y- .'^ -3; • .“. '■' -' ' ‘ * - ^Mi**-’^ 'A .' .'►i^' - ia?-- i. .‘u’ ' <^,->.34f •»#Jii' fc^lr, ,1 •*' » •<. - J'/ u- ■ 11: ^ >>> , r 4. • *• *' 'i. ,*. ^ *t+*v‘. ■ * '^7 " ' "* /^f‘ 7 . (ifti .*! I *. ;\tf.-.Tf.XjJt<'- *-i ■«■' ‘ J>'' . '.: •- ■•”•"■ ^ ^'V ' J ^ V ri. , i . .. V4l0my, V* . ■s » * “ J- .. i/. : .. - 1 :.* . •: .*. » .v* 0 > li » ,-.A ^ ,., ,* . ^ u-«i. S^r^r jh S. • • * ^ ii .- t r ' ik I ’ - ' Ai ■ ^JL. vjH • sri ■* ■*■ * ft 1 '.r ■■■ ^ L- t. .s,,: „ !l . r ■„ i'-. , S /a * • «m {^19 •>.». ftiii- '• X ' *‘ 1 : J-, *: .; - ; Sv ▼ >;s.- -. -.~ ; ■■• ' - ’ Vv /■•■.,• -■'.<-> .Ufr’ •.fci/^‘r-'^iWL V. H AiiiiRiMfw aj> ■•*;.«*■ T's •* '■ '.T 3 ■t&airli$>? 'i V. 14 t.ic or/atf;l‘3 of tha bearing snd this t«nd3 to hold the nydro- Cfirboii end of the oil up eg thv<-t the benrint^ .caiis on a i'ili/i of this oil, iTunt ho-^ thia tneory epplxes to a straieiht chain mineral oil, or oils composed chiefly of cyclic hydrocarbons rl th a aiia.iJ. ano vU'jt of ’insetur^ition , is beyond tne scope of this work. Jtiov/ever, it, ia corrjronly icncwn th;>t oils with a small per- cent.age of (insat uration are 'better as lubricants than oils that are saturated. Granted that a percentage of iinoaturaticn in an oil c’^uees the oil to function better as ?. lubricant, just how much can this pereexitage be reduced be;i'ore tne value of the oil as a lubricant is affected? fUia question arises directly us a result of the wi'k on uaia prcbleiii. in reducing tue percent of unsatuimition in fin oil by hydro jienat ion the viKccsity is in- creased in proj,*ortiori to the ar'setuit that the percentege of un- f;F tu7.“atlon is reduced. I'bia wtrl: sho’rs that hydrogenation also increase*; the de-iul si fleet Ion nu^jiber. A natural question \vould ?ris9 as to how much hydrogenation it wuld tni:.e to raise the demulsi fication nuriiber. to a aatl sfe etc ry value rnid how this ’/rouid dfiffect the vi,3cosity, or iubricatihjj j^ower in geneiml. On the i?ol;i.rine ho. 2 the unsaturation •wub reduced fxou 1.64;;^ to the demulsification iiamb>3r raised from &ero to nid the viscosity was not materially changed, ‘fhie tends to Shew that enough hycU'ogcnation to th.o oil safe from axj emui-aificat Ion stanapoint would not affect tuo tfiuco »ity or the iuorioating value. It ia imown tnat tne viscosity xs uo'i mfjteria.ily changed, out tne j. uuricat ing vaxue before end after treatment was not worked out. yrom the appearance of tne oil, |iA:'r'!-i=ai? ‘ v'^' ill*ifiS^ - J“' * >■ r C^‘ i4.*t ‘■. r .•••. ■*^!'' •^‘ *' y:-'i I' A?** ‘ ‘ 4 ‘a •• "' •' • •■ -.‘J-- *"■ ' "‘' ' • ' ■( . ■ ’ ■' 'X.'' « -i: . ■ ••■u: 4/;i. V'. ’’* .'^ *9UW''l..-‘ &B«— '-:ak . ’>{K-^ll>flHir' I /■ V,'' " I . X r‘u»i>i 'W4 'i^<» tj4*V; '' 4 ^ i -t \^.. • ^kfx/ j»#j^ < *' , A »T»^ -i' * •«! '.if* li !t I %.A f : 4 . . ' ’'' N ,v fr«-m* -^ n* » • I, \ i ' - ' 'I*. = ' ■ V'>"«]- f-*;*' -.'■ »> r? •■*4 'iiu , H ' t ■ . ‘ d ■ - ■■ ' ■'S . ,» f I ■ M i» *»■ c r. Uv. ^*»i . X ' .-1* 1 I5(j , r .: ' ■i ’ < V 1^ (j» ia ) - . ^ ’J V ■ '• '» - . ' , ' ' ,.' i ’ > a '' '^- *"'W> 'rXv v' ' ® ^'31 ^■Uj- .4 V . i 4t>. ' ,v*.> ♦ ,;'« v f ^n /{•*• " >'••♦ - ')* ■ ■ *^{!' '■^•■%Fif'"WC ‘ii ..Mi''/-, ,«►»■' '''. , ■' ^ 1 - ' ^■♦‘•'V'f ' » ,1^ . .--■ C"' ■ ^ A ^ ** A' * '/» Fy , ,,( w ' njf *1 ' ■ V t i- p- ^ At • /;. n>»’C4 ‘ . » y I -• 4*tV: -^fUS^ i i i.;Li^'' „i;il.4. '10 ' «'5W|.‘|1 .Of %*. '• vrivXf!* ' ■■■ *'v''^!Wsi_jr -*ci. , 3 (l917)» 251* Cer. lot,, (£ 60.0C0 j, l9ll« CiiQU, ind, , 40 (1921), 24, p. 23?. J . ao o » ijX-L< 3 ^cia Ind. , l