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Instructions for Time‐Temperature Shifting of Rheological Data Faith A. Morrison Professor of Chemical Engineering Michigan Technological University, Houghton, MI 39931 26 September 2014 1. Record data of and ′′ over a fixed frequency range (for example, 0.01‐100 rad/s) for a variety of temperatures. Alternatively, take data of over a range of shear rates . For the data to be equally spaced on a log‐log graph, use the sequence: 1‐2‐5, 10‐20‐50, etc. for the chosen rates (or if you want more data points, 1.6‐2.5‐4‐6‐10; 16‐25‐40‐60‐100, etc.) 2. Plot the data in Excel using a scatter graph and log scaling (Figure 1). If the data are for viscosity, construct and plot versus (Figure 2). 3. Set up new cells at the top of the y‐data columns that will have the values of in them. Initially populate these with “1”. 4. Insert a column next to the shear rate column and enter the instructions to multiply the shear rate by the value of for each temperature. 10
viscosity, Poise
1 300K 339K 380K 425K 0.1
0.01 0.1
1
10
100
shear rate, 1/s
Figure 1: Viscosity versus shear rate at the four indicated temperatures for a polybutadiene melt. From (Gruver and Kraus, 1964); see also Figure 6.28 of (Morrison, 2001). 26 September 20141
(viscosity)(shear rate), dynes/cm2
10
300K 339K
1
380K 425
0.1 0.1
1
10
100
shear rate, 1/s
Figure 2: Data from Figure 1 plotted as versus . When the material function to be shifted has viscosity units, this is the appropriate configuration for the shift.
(viscosity)(shear rate), dynes/cm2
10
300K 339K
1
380K 425
0.1 0.1
1
10
100
shear rate, 1/s
Figure 3: When appropriate values of are arrived at, the data will shift to a common curve. The values of used were: 300K, 1; 339K, 0.245; 380K, 0.107; 524K, 0.042. 26 September 20142
10
(viscosity)(shear rate), dynes/cm2
1 300K 339K 380K 425 0.1
0.01 0.1
1
10 shear rate, 1/s
100
Figure 4: Final of shifted data, presented as viscosity versus shear rate. The shift is not perfect; compromises were made with fitting low and high
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The next step is to enter guesses for the values of , one at a time; this is a little easier if you go to File‐Options‐Advanced, and uncheck “After pressing ENTER move selection:”. , ′′ if you’re using these functions or the Figure 2 plot if you are using a Copy the plot ( viscosity related function. In Excel, change the x‐vector for each curve from the unshifted to the new column with the shear rates multiplied by . Now we guess the shift factors. For your reference temperature, =1. For the next temperature, enter a value of and check if the curve for that temperature has shifted closer to the reference temperature curve. Revise the guess until you are satisfied with the shift. Repeat for all temperatures. You may need to make some compromises between fitting low and high rates. if you are plotting , ′′, then when you are satisfied with the superposition, the master curve is done. If you are working with viscosity data, you will need to construct the master curve from data by dividing the data by the column. For the shift in this the shifted versus example, the master curve is given in Figure 4.
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References: J. T. Gruver and G. Kraus, Rheological properties of polybutadienes prepared by n‐butylithium initiation,” J. Polym. Sci. A‐2, 797‐810 (1964). Faith A. Morrison, Understanding Rheology (Oxford University Press, New York, 2001) This Document: Faith A. Morrison, “Instructions for Time‐Temperature Shifting of Rheological Data, “ handout for CM4655 Polymer Rheology Laboratory, Department of Chemical Engineering, Michigan Technological University, Houghton, MI, available on the web at www.chem.mtu.edu/~fmorriso/cm4655/TimeTempSuperpositionWithExcel.pdf; accessed 26 September 2014.
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