Document 37epjjqX7k4LBkMwOVYMjNj1E

A :T V-C7-INIA 25303 D. R. Montgomery, 5X5 C. E. Moyers, 515 M. E. Eisenhour, 515 G. M. Bryant August 3, 1976 R/D .... Proposed Publication on Monomer Removal From FVC Resins Gentlemen: Enclosed is a copy of an article, "Phenomenological Studi s of Vinyl Chloride Monomer Removal Fror. Suspension PVC Resin" which is being submitted to the J. of Appl. Poxym. Sci. for publication. Do you recognize any of the authors, Cheng, Langsam or Mantell as an mployee of one of our competitors? Surprisingly the manuscript do s not identify the authors' industrial or academic association. I do not have a lot of time to review this manuscript, so it will be bri f and sent back soon. If you have any comments you would like to mak cone rning the paper, please let me know within two weeks. Since the manuscript has just arrived and not read, I am not sure that it off rs anything not discussed in the eight or so patents issued on this sub ject. I am forwarding it on the assumption that it may be helpful to your efforts. I am also enclosing the summary page of a recent article on th Washburn equation in J. Coll. Int. Sci. The equation was used in the porosimetry-plasticizer work (i&bd). Since you have recently received your porosimetry you may be interested in this work. In association with new additions to our staff to work on Enhanced Oil Recovery program, I would appreciate having my surface ch mistry books returned. With warmest personal regards to all, JEG:sm J. E. Glass UCC 056464 Editorial Board: H. Mark, W. Coopar, M. Morton, B. Ranby, P. Wain Editorial Offleo: Polytechnic Inttituta of Naw York, 333 Jay Straat, Brooklyn, Nav York 11201 July 28, 1976 Dr. J.E. Glass Research & Development Dept. Union Carbode Corp. Chemicals and Plastics South Charleston, West Virginia Dear Sir: We are enclosing with this letter a manuscript (author and title given below) which has been submitted for publication in the JOURNAL OF APPLIED POLYMER SCIENCE. We would appreciate receiving your comments on this manuscript and your opinion regarding its suitability for publication in the JOURNAL OF APPLIED POLYMER SCIENCE. Since we are trying to hold the interval between submission and publication dates down to a minimum, I should be very grateful if you could kindly return this manuscript, together with two copies of your comments (one unsigned), to me within the next three weeks. A self-addressed stamped envelope is also enclosed for your convenience. Very sincerely yours. H. Mark Editor AUTHOR(S): John T. Cheng, Michael Langsam, Gerald J. Mantel! TITLE: PHENOMENOLOGICAL STUDIES OF VINYL CHLORIDE MONOMER REMOVAL FROM SUSPENSION PVC RESIN An Interscience* Publication, published by John Wiley & Sons, Inc. ucc 058465 Rate of Penetration of a Fluid into a Porous Body II. Verification of the Generalization of the Washburn Equation, for Organic Liquids in Glass Capillaries1 KOI1EKT J. (iOOIJ \M) N. -J. UN Department of Chemical f.o^ineerih^t State University of Arcw York at fiinfafo, Httjfafn, A'fw York [421-4 ki-tcivcfl I'dtruiiry IM, 1<>74: acicptcfl August 3!, l*>75 1 lu* rau* ni iti-nEi nilmii ni ,i li(|ui<l Inlr*<iri mn ur an alt ohol in (a a dpi liars i* more rupi<l if tlu* iiipilkiry ha** '.htu iIiaii if ilt* surface is unerctl with a iluplcv film of the lu(iikl. The imreasc in rale is iu* lartfe as UK ,. If ihe pore walls are enveref! I>y an mlsorlKul film, the 1 hie ness of whkh is tomparahle to the pore ratlins, this leads to an ;utolerated rate of penetration in cor parison to systems in whit h the pore radii are large. In the systems studied, there was a notable < .{Terence U-iwecn hvdrotarlxtus and octyl alcohol, which ap|>eared when the glass was out gassed .t 2tM)C under vacuum. i xt ko i) c cnox spreading pressure: It was recently slio vn (1,2) that, for the {endration of a fluid into cylindrical [tores of radius r, if the [tore surfaces are initially not covered with an equilibrium adsorbed lilm of the [tenetrating liquid, then the rate of [tenetration can be f:ister than that predicted by the Washburn equation (3,4,5). In the absence of gravity, Hi, cos dr il(x:) r --------------- <-------- < -- 2tj ill 1r) X {yi. COS Oy + T, -- To). [1] - T. -- T.o [2] Tti = 7. ~ 7.U-0I, [3] where 7. is the surface free energy of the solid in the absence of adsorption of molecules of the penetrating liquid, y,, is the solid surface free energy in equilibrium with the saturated va[tor, anti is the solid surface free energy at zero time; 7. 7*<t-tn 7,- For the systems reported in this paper, the ad vancing contact tingle was indistinguishable from zero. Setting Oy = U, we write Here, .r is distance [teitetraled, To is the liquitlvajair surface tension, t? is the viscosity, Oy is the equilibrium contact angle, and r is the 1 Part of tliis work was reported at the 4Klh National Cnlliiiil Sx mpoMUiu, Austin, Testis, June, 1 *>74. The fart that the excess driving force for penetration could lie expressed in terms of the free energy of immersion was brought out in the open discussion of that paper. If the party who made the suggesUuu will identify himself to the senior author, due credit will lie Riven in tile next pajier in this series. Hi, d(.r-) r ----- < ------ < -- (ft, + tr, -- *,,) 2)7 til 2)7 = -- (7.0-#) " y,t)- W 2a The left equality (which is the Washburn equation) holds provided that the solid surface is covered with a duplex lilm of the penetrating liquid, or that dissipative transport mechanisms maintain such a lilm, advancing well ahead j,.,, ../ ( "U'O'I ./ luh > l vi, \ -.1. St. No. 1. J.imi.iiv VHft 1 q.Miultt Q m;fi It\ A(`;nli`tltir Pn***. Im*. All "f t<`[r<t<lm turn itt any tarot ri**ctvv*L kATK or ri'.xi.tkatu t\ or i\,ni> ix a ruuurs r.M>v 54 ody ration. ... .Vru- York I UI I ,trv mnrr r;t|>nl '<i ihe I he i. ihe thu Kn<`-fc "f \<\i\ ia <nmpurww noiahk- dilfcrt'Hi c ti passed ill 200(J '>1 !he 1 iijio<J front. \n c\,impi<; of a dU-ap., I i ve Iranqiort iiiccii.uiixm, winch in many cases ma\ proceed rapidlc enough to maintain such a lilm, is evaporation from the liquid, followed In' (lilliisioit or tliiw down a pore, anil linullv, adsorption or condensation on the walls of the [wire, i he lelt relation holds as an inr<|uulily if the additional free energy, associated with the welting of the soliiHn the absence of a duplex lilm, can contribute in a nondissi[lativc manner to the eiftrlnat driving force for llow. The free energy change during llow of a liquid into a cylindrical tube may be identified as the tree energy of immersion [ft]: If the walls are covered with a lilm that is in equilibrium with the saturated vapor, we have AG1'"" _ _ Tt(. [.i] If the walls tire devoid of adsorbed hint, we have 1G'' = 7. ~ 7./, [ft] ,'iiiue deviations limit the Washburn equation have not been reported before, iL is to lie expected that t* is commonly small. The maximum eoneeivdile rate would be given by Kq. [ID] with a = 1, We have set out to lest these equations in perhaps the simplest possible system; vertical glass capillary tubes. Vertical orientation has an advantage over horizontal in that small deviations from horizontal can cause quite appreciable errors, Kor r. vertical tube of radius r, the rale, when the meniscus is at height ,e above the liquid surface, is given by: ,11 f' j 2(pyi, + <t(ir. -- ir,,)] Sij.e r PV i I [11] where p is the density of the lfuid. Integrating Kq. [11] between elevations -i'i and .v-, we obtain [2] C-^3 e energy of the solid of molecules of fthe solid surface ih the saturated ie solid surface free S 7.((-< S 7*- I*or this paper, the ad\.is indistinguishable we write Ji\ -- T,,) fy,u-n> -- 7 *') [4] h is I lie Washburn t li.it I he solid surface Ini of the jienetrating raiis|M>rt mechanisms 11 valuing well ahead 1 ,\ \| ,| Il'ItlH I 'l *-- | III . ............... in ,iii\ lot in ii' t v *1. AG' - AG'"-1' - T,. [7] l( the walls are initially covered with a him such that the surface free energy is y,((.>, the free energy change is given by AG1* 7,(/-) -- y.i, [8] u 7 r2[yi, + u(t, -- tii)] pijr- L pgr I 2[y<f + o(t, -- ti,)] 'pgr -- .vi | X In |------ ---------------------- ;----------- l 2[yi, + (, -- t)]/p*r -- a'i * A(,' - AC* - [9] - (.v, - ,,)] [12] The pur]H>sc of this study was to establish whether appreciable deviations from the Washburn equation, as indicated by Kqs. [1] ,1<I [4], are observable. THKOltV The following theoretical considerations, liwond those in (2), were develop'd for the puqrose of testing the new equations. It is quite general to assume that only a fraction, it, of the excess driving force, r, -- ir,, in Kqs. [1] and [4], is used in a nondi.vsipative manner. Then, we can write Kq. [4] in the form -/fa-) 'll r[y/, + i*(t, -- Tid] It) I) < o < 1. [ID] The thickness, 5, of the lilm on the solid is a variable that was found to be important. It may be assumed that there is some limiting thickness, Sd for a duplex lilm, such that for 5 < S,i, the vajHir pressure of the adsorbed him is appreciably less than the saturation pressure [>n: and for 5 > <5,(, the vapor pressure is not experimentally dilTerent from />. We consider, here, only capillary or pore radii in the range large enough that Kelvin equation corrections to the vapor pressure need not he taken into account. Kor clarity of the quali tative argument regarding i, we discuss only a horizontal tulre (see Fig. 1). If is comparable to the radius r, then at saturation, the effective radius will be r -- i.i, with respect to the driving force for pcnc- ./..in l.li i ,`ii'iti </ /*-,'*/ Mr f- in , \'nl, 5-1. Nu. I, J.illUril V