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JOURNAL OF APPLIED POLYMER SCIENCE Editorial Board: H. Mark, W. Coopar, M. Morton, B. Ranby, P. Weiu Editorial OKlea: Polytachnic Inititut, of New York, 333 Jay Street, Brooklyn, New York 11301 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! PHENOMENOLOGICAL STUDIES OF VINYL CHLORIDE MONOMER REMOVAL FROM TITLE: SUSPENSION PVC RESIN An Interscience Publication, published by John Wiley & Sons, Inc, Rate of Penetration of a Fluid into a Porous Body li. Verification of the Generalization of the Washburn Equation, for Organic Liquids in Glass Capillaries1 ROBERT J. GOOD and N. -J. LIN Department oj Chemical Engineering, State University oj New York at Buffalo, Bujfalo, New York 14214 Received February 18, 1974; accepted August 31, 1975 The rate of penetration of a liquid hydrocarbon or an alcohol into a glass capillary is more rapid if the capillary has been outgassed, than if its surface is covered with a duplex film of the liquid. The increase in rate is as large as 10%. If the pore walls are covered by an adsorbed film, the thickness of which is comparable to the pore radius, this leads to an accelerated rate of penetration in comparison to systems in which the pore radii are large. In the systems studied, there was a notable difference IxMween hydrocarbons and octyl alcohol, which appeared when the glass w^s outgassed at 200 L under vacuum. ! INTRODUCTION spreading pressure: IL was recently shown (1, 2) that, for the penetration of a fluid into cylindrical pores of radius r, if the pore surfaces are initially not covered with an equilibrium adsorbed film of the penetrating liquid, then the rate of pene tration can be faster than that predicted by the Washburn equation (3,4,5). In the absence of gravity, ryi, cos By i/(.v2) r ----------------- <--------- < -- 2if ill 2tj X (yi, cos By + t, -- to). [1] Here, x is distance penetrated, 71, is the liquidvapor sur%ce tension, j; is the viscosity, By is the equilibrium contact angle, and * is the * Part of this work was reported at the 48th National Colloid Symposium, Austin, Texas, June, 1974. The fact that the excess driving force for penetration could be expressed in terms of the free energy of immersion was bn>ught*but in the open discussion of that pa|>cr. If the party who made the suggestion will identify himself to the senior author, due credit will be given in the next pa|icr in this scries. *-. = 7. -- 7.., [2] *-o = 7.-- 7.<i-o), [3] where 7, is the surface free energy of the solid in the absence of adsorption of molecules of the penetrating liquid, 7,. is the solid surface free energy in equilibrium with the saturated vapor, and y.u-m is the solid surface free energy at zero time; 7. 7,0-0) 5 y,,. l'or the systems . reported in this paper, the ad vancing contact angle was indistinguishable front zero. Setting By = 0, we write ryi. <i(x*) r -- < -------< -- (71. + * - *0) 2ij dt gn T = --(7-o), -- 7i)- 29 [4] * The left equality (which is the Washburn equation) holds provided that the solid surface is covered with a duplex film of the penetrating liquid, or that dissipative transportmechanisms maintain such a film, advancing well ahead 52 Jonrmal of Colloid and Interface Science, Vo). 54, No. I.Jainiiuy 1976 Copyright Q 1976 by Academic lMt'sa, Inc. All rights of reproduction in any form reserve*!. tody uotion. ;A( A'r..' York 14214 llary is more rapid i of the liquid. The m, the thickness of ition in comparison l notable difference lutgassed at 200C 7.., [2] 7*(i--0)i W ec energy of the solid ition of molecules of ,, is the solid surface in with the saturated he solid surface free ^ 7.-o) S 7..- Fr i this paper, the adwas indistinguishable 0, we write T, -- To) - ft'.(i-o) -- 7*t)- W 1 ch* is the Washbum . that the solid surface ft1 in of the penetrating l ransport mechanisms tdvancing well ahead * Aralt'iuir Pirsj*, In*\ luction in any form reserved. KATE Of PENETRATION,' Of EL LTD IX A TOKOLS HOOY 53 of the liquid front. An example of a dissipative transport mechanism, which in many cases may proceed rapidly enough to maintain such a lilill, is evaporation from the liquid, followed hy diffusion or flow down a pore, and finally, adsorption or condensation on the walls of the pore. The left relation holds as an in equality if the additional free energy, associated with the welting of the solid in the absence of a duplex film, can contribute in a nondissipalive manner to the ejfectual driving force fur flow. The free energy change during flow of a liquid into a cylindrical tube may be identified as the free energy of immersion [6]: If the walls are covered with a film that is in equilibrium with the saturated vapor, we have Since deviations from the Washburn equation have not been reported before, it is to bo expected that a is commonly small. The maximum conceivable rate would be given by Eq. [103 with o=l. We have set out to test 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. For a vertical tube of radius r, the rate, when the meniscus is at height x above the liquid surface, is given by: 2[7i, + o(t, -- T11)3 PS* [11] AG'!'nt> = y,, ~ y,,. [5] If the walls are devoid of adsorbed film, e have AG1' = 7. - 7[6] AG1' - AG(l"`> = t,, [7] If the walls are initially covered with a film Midi that the surface free energy is 74(1-0), the free energy- change is given by AG,D = 7,d_o) -- 7,1, [83 where p is the density of the (lin'd. Integrating Eq. [11] between elevations Xi and -T-), we obtain Ip -- 12 -- /1 _ 81; r2[7i, + a(T, -- To)] pgr1L pgr [ 2[7,. + a(rt -- Tii)] 'pgr -- .r. X In 12[y i. + a(r, - To)3/pgr -- .7,1 AC1' - AG10 = To* [9] -- (** -- ,)] . [12] The purpose of this study was to establish whether appreciable deviations from the Washbum equation, as indicated by Eqs. [1] :md [4], are observable. THEORY The following theoretical considerations, beyond those in (2), were (developed for the purpose of testing the new equations. It is quite general to assume that only a fraction, a, of the excess driving force, t4 -- t0 in Eqs. [13 and [43, is used in a nondissipative manner. Then, we can write Eq. [43 in the form ./(.v1) r[7i, + (t, -- t0)3 ill 2>j 0<< 1. [10] The thickness, 5, of the film on the solid is a variable that was found to be important. It may be assumed that there is some limiting thickness, St for a duplex film, such that for S < St, the vapor pressure of the adsorbed film is appreciably less than the saturation pressure po) and for S > St, the Apor pressure is not experimentally different from /o. We consider, here, only capillary or pore radii in the range large enough that Kelvin equation corrections to the vapor pressure need not be taken into account. For clarity of the quali tative argument regarding S, we discuss only a horizontal tube (see Fig. 1). If St is comparable to the radius r, then at saturation, the effective radius will be r -- St, with respect to the driving force for pene- /uKrrttil q/ Colloid mid inler/ntt Science, Yul. 54, Xo< 1, January 19/6 ucc 041477 jaarm JO t OF APPLIED POLYMER SCIENCE Edifori*! Offi: Polym*f R*t*rch Polytchft*c Ifttliiul* Nw YeH . 33) Jay StfMt, Ireofclyr* N*w Yor4 If20l Author: Dt: July 28, 1976 John T. Cheng, Michael Langsam. Gerald J. Mantel! phenomenological studies bf viityl chloride monomer removal from stnuesrpiAennes^ioAnH pntviAc resinM Is this paper acceptable for publication in the Journal of Applied Polymer Science? (1} YES 0 (2) With minor revision 0 {3J With major revision 0 (4) NO 0 If not. do you suggest another journal Possibly in Chemical Engineering Progress based on current interest, not technical merit. COMMENTS: porosity correlation is based on the assumption" and "we have not yet examined the effect of glassy particles in a systematic manner" defin in the authors' own words part of the deficiencies in this manuscript. The study examines only four resins which vary so extensively in particle size distribution (one bimodal and another excessively high in fines) and glassy particle characteristics that no definitive conclusion can b made about the mechanism(s) of vinyl chloride monomer removal. Characterizatior and interpretation of the particle's porosity and glassiness by the IPTU and density tests are questionable even when such measurements are applied to a series of resins with only minor variations in properties. The tests are totally inadequate in supporting the authors preconceived ideas on the mechanism(s) of monomer removal. The authors should re-evaluate the merits of the submitted manuscript with respect to their previous publication and the disclosures in numerous patents on the subject of monomer removal, e.g. NL 7,507,385, BE 830,689, NL 7,507,527, DT 2,429,776, U.S. 3,926,927 and DT 2,451,988. #It is diffi cult for this reviewer to find*any novel or contributive value in the submitted paper. r There are several minor inconsistancies and inaccuracies in th manuscript. For example, the first three parameters in Section B approximately define the limits of the added solvent's solubility parameter; therefor , it is not a required fourth parameter, by definitir ~ *7, diluting the slurry with increased amounts of water di le polymer to water interfacial area, etc. Data Returned Sign White Copy Only Please Return Signed Original end One Anonymou* Carbon uce 041478 II ywt H**c< Mum till, mtnmettpt villi cowimeeli In lw w,,U ptae reiwe H IrwiJUWf elltiia itnmali PUBLISHED BY INTER SCIENCE PUBLISHERS. A DIVISION OP JOHN WILEY A SONS. INC. JOURNAL OF APPLIECfPOLYMER SCIENCE Editorial Board; H. Mark, W. Coopar, M. Morton, B, Ranby, P. Weist Editorial Offica: Polytechnic Inrtituta of New York, 333 Jay Street, Brooklyn, New 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 m AUTHOR(S): John T. Cheng, Michael langsam, Gerald J. Mantell PHENOMENOLOGICAL STUDIES OF VINYL CHLORIDE MONOMER REMOVAL FROM TITLE: SUSPENSION PVC RESIN An Interscience Publication, published by John Wiley & Sons, Inc. JOURNAL OF APPLIED POLYMER SCIENCE Editnr'.sl OIKcm: Polymt Rsrch InttihiU. Polytechnic Imli'ui* o< Nw Yort. 3J1 Jey Sir**>. Brooklyn. Hmm Yori 11201 Author: Dt*: July 28, 1976 John T. Cheng, Michael Lanqsam. Gerald J. Mantell TiH: phenomenological studies of vinyl chloride monomer removal from suspension pvc resin Is this paper acceptable for publication in the Journal of Applied Polymer Science? (I) YES Q (2) With minor revision Q (3) With major revision 0 (4) NO 0 If not, do you suggest another journal _____ COMMENTS: *** m Date Returned Sign White Copy Only __ Please Return Signed Original and Ona Anonymous Carbon. ucc 041480 If ye* tuiwi nlim thle memnc/ipt vIHi cemiMh In Iwe v,,il, pie--* islwi It leneedUtely wltfco** iMmslL PUBLISHED BY INTERSCIENCE PUBLISHERS. A DIVISION DE JOHN WILEY A BOMB. INC. iiisri'wawwr*- -