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Balke 1969
Balke 1969
S . T . B A L K E , A . E . H A M I E L E C , A N D B . P . LECLAIR
Chemical Engineering Department, McMaster Uniuersity, Hamilton, Ontario, Canada
S . 1. P E A R C E
Shell Oil,Ltd., Montreal, P. Q., Canada
A search technique and computer program (Fortran IV) have been developed
to determine the calibration curve for a gel permeation chromatograph using
broad molecular weight distribution standards. Two average molecular weights
(number, weight, or viscosity) for one or two polydisperse standards are required.
A Rosenbrock search is used to find the calibration curve constants. This search
has been tested for a variety of cases on an IBM 7040 computer. An evaluation
of these results is presented.
THEuse of the gel permeation chromatograph (GPC) data: one broad MWD standard and its number- and
for the determination of molecular weight distribution weight-average molecular weights; two broad MWD stand-
(MWD) of polymers is developing rapidly. T o interpret ards, given two number-average molecular weights, two
the GPC chromatogram it is necessary to establish a weight-average molecular weights, two viscosity-average
quantitative relationship between molecular weight and molecular weights, and one number- and one weight-
elution volume. The GPC is usually calibrated with narrow average molecular weight. Searches for nonlinear calibra-
MWD standards ( M , / M , 5 1.1) using the elution volume tions are also discussed.
a t the peak position. I t is not valid to use the peak
Development
position for broad MWD standards. For many linear
homopolymers narrow MWD standards are not readily Linear Calibration Curve. A linear calibration curve may
available, thus presenting the problem of determining the be expressed as
calibration curve with broad MWD standards. Rodriguez VOL = C1 - C2 logm(MW)
et ai. (1966) suggested a graphical procedure, but with
little elaboration. Cantow et al. (1967) proposed a pro- where
cedure for finding the calibration curve given the complete
MWD of one broad MWD standard. They are also able VOL = elution volume in counts
MW = molecular weight of a monodisperse
to correct their calibration curve for the effect of concen- sample
tration. C l and C2 = constants to be found by search
More recently, Frank et al. (1968) developed a technique program
for finding a calibration curve using a number- and a
weight-average molecular weight of one broad MWD The method involves the injection of one or two broad
standard. Their technique involves a graphical approxima- MWD standards into the GPC under conditions where
tion which makes it difficult to employ. the effect of correction for imperfect resolution on the
I n this paper a precise computer technique is presented, molecular weight averages of a polydisperse sample is
tested, and evaluated for several cases. These include negligible. [If skewing and symmetrical axial dispersion
searches for linear calibration curves given the following correction may be estimated, the true calibration curve
VOL. 8 NO. 1 M A R C H 1 9 6 9 55
standard. The effective calibration curve constants
Table 111. Results of Program Test automatically accomplish necessary resolution correction.
output Another possibility is to use a series of broad standards
Cl c2 over the range of elution volumes desired and combine
(actual (actual the linear segments so obtained to obtain a complete
Run value value No. of APP~X effective calibration curve.
No. = 37.55) = 3.62) iterations time Remarks
A nonlinear calibration curve search would provide even
1 37.54 3.62 166 2 min. more flexibility in the above procedures. None of the
28 sec. above are evaluated in this paper.
2 37.56 3.62 409 4 min.
8 sec. Evaluation
3 37.52 3.61 209 3 min.
36 sec. I n this evaluation samples of high and low polydispersity
4 41.34 4.32 195 3 min. Slowb were used (Table I). Maximum computer time permitted
27 sec. per run was approximately 6 minutes. Previous programs
5 37.43 3.60 348 4 min.
0 sec. using a Hooke and Jeeves pattern search had required
6 72.31 9.42 198 4 min. Very slowb 7 to 30 minutes to reach an optimum. Tables I1 and
21 sec. I11 show that, in general, convergence to the correct
7 47.71 5.59 136 4 min. Very slowb optimum (&0.7%) occurred after about 200 iterations
44 sec.
8 49.79 6.00 58 5 min. Very slow* within approximately 3% minutes using an initial step
11 sec. size of 0.005, an acceleration factor of 2.5 or 1.5, and
9 49.79 6.00 219 5 min. Very slow6 a deceleration factor of -1.
1 2 sec. I n the only exceptional case slow convergence occurred
10 42.11 4.50 250 6 min. Very slowb
15 sec.
when two very broad molecular weight samples, each of
11 40.66 4.22 219 4 min. Lax criterion" known but of almost equal weight-average molecular
6 sec. weights, were used. These samples were examined in runs
12 36.74 3.47 260 5 min. Slow6 6 to 13. In none of these instances was the search criterion
6 sec. for compfetion, Y1 - Y2 = 0.1, reached although values
13 37.53 3.62 470 5 min.
30 sec. as low as Y1 - Y2 = 2.0 were obtained a t values far
14 37.35 3.58 234 3 min. from the correct C1 and C2-that is, the criterion was
39 sec. almost satisfied far from the optimum of these runs. I t
15 37.33 3.59 403 5 min. was evident from examination of the calculated molecular
16 sec.
weights that the objective function was not satisfied. This
situation was attributed to the automatic step size reduc-
tion in the search, which usually resulted in very rapid
"Search criterion was 20 rather than 0.1. bSearch criterion of
objective function variation (Y1 - Y2) = 0.1 not reached. convergence. Attempts to remedy this situation by
changing the three search parameters, the search criterion
for convergence and particularly the initial guesses of C1 technique has been developed and used to determine a
and C2, met with considerable success. Run 12, although linear calibration curve for a wide number of cases (Tables
slow, was very near convergence when the time limit I1 and 111).
expired. The program may be very easily modified to search
Using the values of C 1 and C2 obtained with the search for parameters of a nonlinear calibration curve. Results
technique and PVC sample 1 (Table IV) the GPC results of program evaluation and specific recommendations for
calculated assuming infinite resolution (Table V) differ in its use are presented. A source program listing is available
M , from -5.0 to +19.4’% compared with osmometer values, on request.
and in M, from -19.9 to -1.070, compared to SOFICA
Acknowledgment
light scattering measurements. Considering the sources
of uncertainty in all three methods of measurement as The authors appreciate financial support from the Chi-
well as the fact that the search technique was used only nook Chemicals Corp., Ltd., and the National Research
for sample 1 (no attempt was made to optimize a C1 Council of Canada. Data on PVC from Imperial Oil Enter-
and C2 for the range of molecular weights of interest), prises, Sarnia, Ontario, and the original Rosenbrock search
these results were comidered satisfactory. program from John D. Sheel of McMaster University
are also gratefully acknowledged.
Recommendations for Use crf Search Program
literature Cited
Use search parameter values of
Balke, S. T., Hamielec, A. E., Reprints, Sixth International
CC = 0.005 Seminar, Gel Permeation Chromatography, Miami
Beach, Fla., 1968.
A = 2.5 Cantow, M. J. R., Porter, R. S., Johnson, J. F., J .
BB = -1 Polymer Sci. 5 , Part A-1, 1391 (1967).
Duerksen, J. H., Hamielec, A. E., J . Polymer Sci. 6,
Use a t least two different sets of initial guesses of C1 Part C, 83 (1968).
and C2 to test each case. Frank, F. C., Ward, I. M., Williams, T., Reprints, Fifth
International Seminar, Gel Permeation Chromatog-
Use a search criterion of Y1 - Y2 = 0.1 and a computer raphy, London, 1968.
time limit of 6 minutes.
Rodriguez, F., Kulakowski, R., Clark, 0. K., IND. ENG.
Adjust initial guesses of C1 and C2 to speed convergence. CHEM.PROD. RES.DEVELOP. 5,121 (1966).
Altering search parameters, or criterion for convergence, Wilde, D. J., “Optimum Seeking Methods,” p. 151,
are less effective solutions to the problem. Prentice-Hall, Englewood Cliffs, N . J., 1964.
Conclusions
A program to determine a linear calibration curve from
polymer samples of known weight number- or viscosity- RECEIVED
for review May 20, 1968
average molecular we:ights utilizing a Rosenbrock search ACCEPTED November 4, 1968