Lube-Tech err ae eu eca aod iscosity Blending quations Boris Zhmud, Ph.D., Assoc.Prof., MRSC Sveacon Consulting, Stockholm, Sweden ‘ABSTRACT: In lubricating and specialty oil industries, blending Is routinely used to convert a finite number of distillation cuts produced by a refinery into an infinite number of final products matching given specifications regarding viscosity. To find ‘the right component ratio for a blend, empirical or semi-empirical equations linking viscosity of the blend to viscosities of the individual components are used. Perhaps the best known among viscosity blending equations are the double- logarithraic equation of Refutas and the cuble-root equation of Kendall and Monroe. The kinetic theory led the way to a deeper understanding of viscosity blending principles for binary mixtures, culminating in Grunberg-Nissan, OswaF-Desai and Lederer Roegiers equations. These equations have lifted viscosity blending calculations to a practically useful accuracy level. ironically, despite being the most accurate one-parameter equation, the viscosity blending equation due to Lederer {and Roegiers remained largely unknown to the oll research community until recently. INTRODUCTION Viscosity blending Is parhaps the most ‘common operation in lubricant ‘manufacture, All blenders rely upon their vscosity-blending calculators, often used {5 a magic biack-box giving the right blend compostuon [1,2]. Accurate viscosity prediction for binary mixtures of two components with a large difference in viscosity remains a challenging task because viscosty blending curves may show a large degree of nor-linearty. Strongly non-linear viscosity blending ‘curves are often observed for binary systems such as base oil / polymeric thickener or viscosity index improver, Which are quite common in lubricant formulation practice. VISCOSITY BLENDING EQUATIONS COMMONLY USED IN THE PETROLEUM INDUSTRY In the petroleum industry, empirical or proprietary blending equations are common. The best known are the 0.5, ‘the contribution of component 1 to the flow activation energy is less than that, ‘of component 2. indeed, from a hydrodynamic viewpoint, viscosity reflects the momentum flux from one liquid layer to another when two. adjacent liquid layers slide against each ‘other. Since the molecules of the components 1 and 2 differ in molecular ‘weight, size and electron density distribution, the energies of pair-wise interactions 1-1, 1-2, and 2-2 are also different. Putting «= 7 / (1 ~7), the Lederer-Roegiers equation is arrived at. For p =0.5, a= 1, and the Lederer. Roagiers equation (6) becomes identical to the Arthenius equation (1), ‘The presence ot highly polar compounds with strong orientational forces such as hydrogen bonding may result in S-shaped viscosity plots. Such behaviour is often observed when blending polymer-thickened oils having a sufficiently large difference in solubility Examples are polyalphaolefin / olefin copolymer / fatty ester or polyalphaolefin / fatty ester / polyester systems. In this case, changing the Component ratio has a strong effect on the solvent power of the mixture, which, in ts turn, has an effect on the random coil configuration of the polymeric thickener. For instance, the ‘mean radius of gyration of a polyester ‘molecule in polyalphaolefin solution is Smaller than it sin fatty ester solution, Vice versa, the mean radius of ayration of an olefin copolymer molecule in polyalphaolefin solution is greater than itis in fatty ester solution. Generally speaking, such systems normaly reveal ‘non-Newtonian theology - their viscosty becomes a complex shear-rate- dependent quantity. However, this is outside the subject of the present communication. As long as the mixture bochaves nearly lke a normal iquid (and rot as a ge), the effect of random coil radius change on viscosity can be described by an asymmetic correcting function of the type si(t -sa}2x1 - 17", as has been done in eq.(10) by Oswal- Desai [10 It should also be commented that the above blending equations refer to dynamic viscosity, ». The corresponding equations for kinematic viscosity, , are ‘obtained using the relationship = pu where p is the density. To link the density of a binary mixture to the densities ofits components, the excess ‘volume of mixing should be determined Luckily, most mineral oils behave as normal fluids, for which the excess volume of mixing Is close to zar0. Furthermore, since the densities of ‘components in mineral ail blends are usualy clase to each other, rarely falling outside the range 0.8 to 1.0 g/cm’, the term Inpr2 - xilnpn ~ mary is dose to zero. Therefore, in practice, the above- ‘mentuoned viscosity-blending equations (6). (9), (10) and (11) can wall be applied for calculation of kinematic \iscositles. For the same reason, mole fractions are substituted by weight fractions, Lupe MAGAZINE No.121 JUNE 2014 | 25Lube-Tech Seats cre ec na heed APPLICATIONS OF LEDERER-ROEGIERS EQUATION a. Determination of the intermol- ecular cohesion parameter The easiest way to datermine the intermolecular cohesion parameter for a Given blend is via measuring the blend \scosity for component weight ratio, ‘50:50, in which case 3) Inds Ins An —In14) 5 = 2 = 99) and hence, ult!) 4) Int tha) ‘A more scientific way isto treat a as a fiting parameter and to base its determi- ration on the method of least squares. b. Calculation of viscosity for a blend of two components with a given intermolecular cohesion parameter. (Once the intermolecular cohesion parameter for a given pair of ‘components has been determined, the entire viscosity blending curve can be Gleulatad, The typical values of intermol- tecular cohesion parameter for various base cil types are as follows: ght hydrocarbon / Heavy naphthenic 03-04 Light hydrocarbon / Heavy paraffinic 05-09 ght paraffinic / polyol ester 10-14 Light naphthenic / polyol ester 13-17 Determination of the weight ratio of components for getting a certain blend viscosity ‘The desired component ratio is obtained by rearranging terms in eq(11), fot) toga) 5) In order to demonstrate remarkable accuracy of the Lederer-Roegiars equation in describing viscosty of binary blends of various hydrocarbon fractions, viscosity measurements were cartied out {ase Oil oF Petroleum Distilate Property Method eacioto | pace ]se | scm | SC | ran aemarsouen [atom ore [one [aa [ ome [as | ox costa asTHOMS [iad [510 [ras [aa [ea | om tse an air [asioonrar [vans [iach [sare [saa | 4405 [15 ‘pat (C) vsinos fs fer (ws fro (ae [ar Table 7: Psa properties of base os an petroleum dss used OS Study ‘for a number of paraffinic, naphthenic and synthetic ols. Some physicochemical properties of olls used in ths study are ‘summarised in Table 1. Kinematic viscosity of the individual components and thelr binary mixtures was measured {at 40°C according to ASTM D445. From the theoretical viewpoint, the Grunberg-Nissan equation and the Lederer-Roegiers equation are the most substantiated single-parameter viscosity blending equations. In the following, we ‘compare accuracy of thase two equations. 02 04 (O Exo 60/4000 | A PROZITAOOD (© N88, T4000 ‘9 100N/TeCO0 ‘© Bight stock T4000 06 08 1.0 WEIGHT FRACTION OF T4000 Figure 1: vscosycunes for tna midues of vars peo produ th 3 Ney naphent bac acon Teoria vicar Cunes tare wig Te Rowers ean ae shown ote ines “ates ft ett parame wea eos 02) DeOrT2007 = 030 er PROD, 39 for 1OONTA000 = 0.40 for Bet tokIT40, a= 031 Fr NSELTADD. The average eo 9%, the marina eer 15% able macy ales.Lube-Tech Seats cre ec na heed Figures 1 and 2 show experimental ‘CONCLUSION REFERENCES viscosity blending curves for PAO? and a | OF single-parameter viscosity blending | 1. RM. Diaz, MLL Bernardo, AM. ‘number of petroleum products ranging | equations, the Grunberg-Nissan equation Fernandez and MB. Folguetas, from light solvent distilate to bright ‘and the Lederer-Roegiers equation are Prediction of the viscosity of stock - with a heavy naphthenic base oll | probably the only equations which afford lubricating oll blends at any T4000, The system Exo! DGO/T4000 ‘2 meaninaful theoretical rationalisation temperature, Fuel 75 (1996) 574-578. resembles the system hexane/Mobilol | and give an accuracy lovel adequate for | 2, M. Rogers, 8. Zhmud, Property bight stock studied inthe original work | practical applications. For mixtures of Blending Relationships for Binary by Roogiers, Sr. [12]. Due to a big components with greatly differing Mixtures of Mineral Oil and difference in component viscosities and | viscosities, which show large deviation Elektrionised Vegetable Ci: ‘molecular size, both the systems show | from ideal behaviour, the Lederer Viscosity, Solvent Power, and Seal uite significant devation from the Roeglers equation give a significantly Compatibility index. Lubrication ‘Athenius equation. The Lederer-Roegiers | more accurate blend viscosity prediction Science 23 (2011) 263-278. equation demonstrate remarkable than the Grunberg. Nissan equation, 3. RE Maples, Petroleum Refinery accuracy in predicting the blend viscosity Process Economics, Pennmwell in this case (Figure 1), whereas the Publishing, Tulsa, 1993, GGrunberg-Nissan equation fails to 41H Gary, GE Handwerk, adequately account for such a level of Petroleum Refining: Technology and on-tinearty (see Figure 2), Economics, Marcel Dekker, New York, 1984. 5. ASTM D7152 Standard Practice for Caleulating Viscosity of a Blend of Bleu Pesce AT Bek ot Sas les MH. Rahmes, W.L. Nelson, Viscosity Sit tips eo Peta schon 30 (1948) 912-915. 2. Ma fate 16 Bono vest se Orsini sere chem eg East (1967) 427-431 5 Bester taller Ei The hun ce ec thst i Ye a Uber At hen Tre crags el epost en ed esr ids Tors. sy Bitsy sy to, $1 ban Osa tues o isco and ces nl sone © tO Tn of bay nts, Hud Phase paca 40 Ena (9m 208376 6 pees 1 ea tater Ukstt ion fsogtte, Koll 2 aM soe Se get 2058 ta. Rfosgis nh Roca bo costs Ses ges ai vere Sects aes oo 02d wt Co Ronis Coe 146 tp, hi seagen eh pecaath ol WEIGHT FRACTION OF T4000 fundamental equation of viscosity, Industrial Lubrication and Tribology Sin. LOG (u) agro 2: vcosty canes for brary ius of ares peteum products with 2 hea napienk basa ‘4000. Teoria scot ending res ob us the undo Msn equation at stow by token fines: als of he best gaaretr mere as folows. «= oy Eo DTr4000. «= 3.0 for PRODI. {€=-20 for JOONTF00,e "0.8 for Bight toe4000 € ~:2 2 for NSB. The ate ee TK, Ne Imasmuen err 90% m anole vos Tbe