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JOURNAL DE PHYSIQUE Colloque C10, suppl6ment au n012, Tome 46, dgcembre 1985

page C10-31




Los Alamos National Laboratory, Los Alamos, N.M. 87545, U.S.A.

RCsumh- O n d t c r i t une nouvelle m t t h o d e d'analyse des pics d e f r o t t e m e n t i n t i r i e u r e n fonction d e la temperature. Elle p e r m e t d'obtenir u n e a p p r o x i m a t i o n d u spectre d e s t e m p s d e relaxation responsables d u pic. O n m o n t r e q u e c e t t e m i t h o d e , a p p e l i e analyse directe d u spectre (DSA), s'applique I d i f f i r e n t s types d e spectres: (i) elle fournit des a p p r o x i m a t i o n s d e certaines formes d e spectre q u i reproduisent la position, l'amplitude, la largeur e t l a f o r m e avec u n e bonne p r i c i s i o n , q u i est d e l'ordre d e 10% (ii) elle ne c o n d u i t p a s I d e s a p p r o x i m a t i o n s a l i a t o i r e s d e la forme spectrale des pics. Abstract - A new m e t h o d for analysis o f a n i n t e r n a l friction vs t e m p e r a t u r e peak t o o b t a i n a n approximation of t h e s p e c t r u m of relaxation times responsible for t h e peak is described. T h i s method, referred t o a s direct spectrum analysis (DSA), i s shown t o p r o v i d e a n accurate estimate o f t h e d i s t r i b u t i o n of relaxation times. T h e m e t h o d is validated for various spectra, a n d i t is shown that: (i) I t provides a p p r o x i m a t i o n s t o known i n p u t spectra which replicate t h e position, a m p l i t u d e , width a n d shape with good accuracy (typically 10%). (ii) I t d o e s n o t yield a p p r o x i m a t i o n s which have false spectral peaks.
I - Introduction T h e problem of analyzing i n t e r n a l friction vs t e m p e r a t u r e peaks t o d e t e r m i n e t h e distribution o f relaxation t i m e s responsible for t h e peak has been a difficult o n e for m a n y years. T h e t r a d i t i o n a l method of analysis has been t o a s s u m e various forms for t h e relaxation t i m e spectrum a n d then choose t h e best f o r m based u p o n goodness-of-fit t o t h e data. T h e problem with t h i s m e t h o d i s t h a t none of t h e trial forms for t h e spectrum m a y be close t o t h e t r u e distribution. I t would be preferrable t o directly analyze t h e d a t a t o obtain a n a p p r o x i m a t i o n of t h e spectrum, t h u s avoiding unnecessary assumptions. Such a method, referred t o a s direct spectrum analysis (DSA), has been developed a n d validated for approximating relaxation t i m e spectra for processes with first-order kinetics / l / . With t h i s method, nonlinear regression least-squares is used t o unfold the integral e q u a t i o n for exponential decay with a d i s t r i b u t i o n of relaxation t i m e s a s t h e t i m e c o n s t a n t s within t h e integral. I n a later paper 121, t h e s a m e m e t h o d was applied t o t h e Debye function a s t h e kernel. T h i s allowed analysis o f i n t e r n a l friction (or dielectric relaxation) peaks when measured a s a function of frequency. I n t h e present paper these m e t h o d s a r e extended t o t h e measurement of i n t e r n a l friction vs temperature peaks.

I1 - Method
T h i s method has some m i n i m a l requirements of the data. First, i t is necessary t h a t t h e internal friction vs t e m p e r a t u r e d a t a h a v e had background subtracted. I t is i m p o r t a n t t h a t this subtraction be d o n e with t h e highest possible accuracy because t h e DSA m e t h o d t e n d s t o find c o n t r i b u t i o n s t o t h e relaxation t i m e spectrum for a n y i n t e r n a l friction which m a y be present o v e r a n d above t h a t for a given peak. Second, i t i s necessary t h a t there b e roughly 20 o r m o r e d a t a points; a s h a s previously been shown /1,2/, t h e resolution capabilities of t h e method increase with b o t h n u m b e r a n d accuracy of t h e d a t a points. T o discuss t h e method we will use t h e n o t a t i o n a n d development of Nowick a n d Berry / 3 / . We consider d y n a m i c experiments i n which stress i s applied periodically a t frequency o s o t h a t for a n anelastic solid t h e r e will be a phase lag of t h e strain behind t h e stress. T h e angle o f t h i s phase lag is cp, t h e loss angle, a n d the compliance is described by two d y n a m i c response functions, a real p a r t , J , ,

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In the examples which follow. First. we consider J l J. After choosing n and the 7 limits for the spectrum. First. We next divide the range of 1og10. with later tries this is adjusted keeping the range sufficient to show the tail regions of the spectrum. (ii) Input the experimental value for w. there is only distribution of To's and Q is a constant. The internal friction is given by tan ( P = J ~ / J. Q is the activation energy and k i s Boltzmann's constant.ri in Eq. hut with the constraint n<=m. typically this will be the temperature of the peak. For the first attempt a wide range is chosen..ri need to be corrected to their values at Tdist.(210-32 JOURNAL DE PHYSIQUE and an imaginary part. although the second has been used and found to provide good spectral estimates. and then applying the DSA method to the data t o test how well the input spectrum is recovered.rscale) of the bin. Eq.. .e. Second. 3 will exhibit a temperature dependence according to the Arrhenius relation. certain corrections for temperature-dependent parameters are required. A=6J/J.the . The crux of the DSA method is to make a sum approximation for the integral (see Ref. T=ro exp(Q/kT). T. The number of bins chosen depends upon the resolution desired. The .rinto n bins of equal width and designate the relaxation time of the ith bin as T . adding random (Gaussian) error with a desired standard deviation.-J.. is the strength of the anelastic relaxation and J. we continue as follows: (i) Choose Tdirt. Since the value may not be known. We terminate the calculation by either choosing a desired number of iterations or by a statistical evaluation of convergence.the spectrum of relaxation times at Tdlrt. J2. 2) which contains the function N(ln T). . this is estimated as twice the .We first speci'fy the upper and lower T limits for the spectrum. we must correct w and A to this temperature. We now proceed to obtain our approximation of N ( l n ~ ) . Nowick and Berry again provide an excellent discussion of these temperature corrections 131. Analysis involves making two approximations both of which are valid for the usual experimental condition that tan cp<<l. Because the internal friction is measured as a function of temperature. the input distribution of relaxation times was either a single lognormal or a . the midpoint value (10g~o. We will use the first of these models in the discussion which follows. The second model is just the opposite of the first. the relaxation strength in the ith bin.. I t will iterate adjusting the Ai to minimize the least-square differences between the calculated and the experimental points. (iv) Estimate the total relaxation strength. Ai=A/n. (3) is the same as given by Nowick and Berry 131 for multiple relaxations with discrete relaxation times. respectively. Thus. the reader is referred to Weller. is the relaxation strength i n the ith bin. these two dynamic response functions are given by where GJ=J. 111. : . Typically. where 70 is the pre-exponential factor..VALIDATION The validation method is one of generating an artificial set of internal friction data from a known relaxation time spectrum. so that tan cp*J2/J. I t is typically 10<n<100. This is done using either of two models for the distribution of relaxation times as discussed by Nowick and Berry 131. For implementation of these two corrections. et a1 /4/. Q all to the same value. This gives - where A. i t is required that a value be chosen for the critical temperature. Tdi*. . A. For a given measurement of the internal friction a t some temperature other than Tdlot. are the relaxed and the unrelaxed compliances. (iii) Provide a n estimate of T o . Correction of A to Tdirtinvolves a Curie-Weiss temperature dependence. we consider that the T which is measured (the relaxation time a t constant stress) is equal to the average T (the one in the above equations) /3/. The first model considers that the distribution is only due to a distribution of activation energies and that TO is constant. i t is important t o d o the analysis using upper and lower limiting estimates of this parameter. and J. where m is the number of data points. The nonlinear regression least-squares method is now ready to be used. i.IFor a standard anelastic solid /3/ responding to periodic stress. since we want our approximation o f the relaxation time spectrum a t some constant temperature. peak height. Thus. using this equation is the same as considering the relaxation to be made up of n different discrete relaxations all of which are equally spaced in log T. T o start the iteration process we set the Ai.

I t may be n o t e d t h a t t h e histogram a p p r o x i m a t i o n agrees well with t h e original i n p u t distribution which is shown a s a solid curve i n t h e figure. lWUT SPECIRIM.01. Fig.=1.14s - $F Z 0. R a n d o m fractional error with standard deviation o=0. but for values of P ranging from 0. 112 303 10" 100 RELAXATION T I M E . but overlapping. 2 Starting histogram for calculation of t h e DSA approximation to t h e i n p u t spectrum. 0 ~ ~ : j : I3 .N<. . Validation was also done for i n p u t spectra with a single lognormal d i s t r i b u t i o n . INTERNAL FRICTION PEAK INPUT LOGNORMAL OlSTRlBUTlON 8-10 Tm<1O S m ~ 5 DATA 0 POINTS FOR FRACTIONAL ERROR=O..OI Y .01 h a s been added t o simulate experiment.25 t o 3. 1 . r ( s ) 1 0 ' Fig. . -.~~v . T h e internal friction is normalized a s t a n q / A . Fractional e r r o r with s t a n d a r d deviation a=0.0 a n d r a n d o m fractional e r r o r with o=0. Each of t h e 40 bins has equal spectral a m p l i t u d e such t h a t t h e area of t h e histogram is unity (on a In r scale). The spectral limits f o r t h e calculation h a v e been chosen t o cover three decades with t h e center a t roughly r = I / o .. 1 . As with t h e result i n Fig. At the t o p of t h e figure the scale is for the equivalent activation energy.3 - .10. A lognormal fit t o t h e histogram gives r.25) t o d i s t r i b u t i o n s covering u p t o five decades i n r i s encouraging. 1. 3 t : - STARTING HISTOGRAY n~108111S OP\ ' G- . These spectra gave overlapping i n t e r n a l friction peaks which would be expected t o be very difficult t o deconvolute.. 2 shows t h e histogram for t h e s t a r t of t h e nonlinear regression analysis of t h e d a t a i n Fig.. 1 shows a n example of such a computer-generated i n t e r n a l friction peak plotted vs reciprocal temperature.l 4081NS r. 1.:0031 5 0 0 ITERATIONS - Td. 500K 1"' . 50 d a t a points h a v e been used for o=1. 3 .=1. 1.0 s from a single lognormal distribution centered a t r.. ' 05. t h e DSA method was found t o p r o v i d e a good a p p r o x i m a t i o n o f t h e i n p u t spectra o v e r this range of p. Q=1. Fig. T h e f o u r separate peaks a r e eachgenerated from a lognormal distribution.0. 4 a s a broad i n t e r n a l friction peak made u p a s t h e s u m o f four separate peaks shown a s dashed curves." 71 SINGLE LOGNORMAL B.I n p u t relaxation t i m e spectrum a n d o u t put histogram approximation after DSA of d a t a i n Fig. The d a t a a t t h e various temperatures have been calculated from t h e Arrhenius relation with a n activation energy.01 has been added t o the d a t a .0. d a t a were generated from multiple.I n t e r n a l friction v s temperature d a t a generated from a lognormal distribution t o check the capability of t h e DSA m e t h o d t o recover t h e i n p u t spectrum. Again.IO .r) distributions. lognormal spectra of varying widths.4 eV a n d preexponential. 3. An example of such a complex peak i s shown in Fig. 2 0 5 - 3 A a ~ - : AREA. T h e capability of t h e method t o give good spectral approximations for symmetrical d i s t r i b u t i o n s with widths ranging f r o m t h a t of a nearly discrete relaxation (P=0. These vary i n fractional strength a n d width a n d are centered roughly a factor of four a p a r t a s shown i n Fig.combination of several lognormal (Gaussian in log. 3 shows o n t h e s a m e axes t h e histogram a p p r o x i m a t i o n of the i n p u t spectrum for Tdlst=500 K after 500 i t e r a t i o n s using DSA a n d assuming t o be 10-l4 S. . 5.03 i n good agreement with these parameters for t h e i n p u t spectrum.0 s and with width P=1. . T h e vertical dashed lines a r e t h e spectral limits.~-.. r.02 s a n d P=1.4 1.'T~ h e 50 d a t a points have been generated for w=1. T o examine t h e recovery of asymmetrical spectra. Fig. Fig.003t 4 W a LL B a:I.IOI-l l g LL .. ~ ~ = 1 0 S. Fig.5 l6 i 1 WP"T nlSTOGRAM.

. and Berry. B. X. Zhang. Y. J. Fig. /3/ Nowick.. Phys. 5 demonstrates t h a t the amplitude.. width a n d location of the peaks are all reconstructed with acceptable accuracy. (b) I t is shown that this method provides approximations to known input spectra which replicate t h e position. 4.Internal friction data generated from 4peak input spectrum.. (c) Validation of t h i s method for a wide variety of spectra shows that i t does not yield approximations which have false spectral peaks. / 5 / Cost... J. Li. Ke. shape. TMS-AIME. New York (1984). J. Only a minor difficulty is evident.. I t may be seen that the DSA approximation shows very satisfactory agreement with t h e spectrum which was used t o generate the data. particularly when the i n p u t peaks were close together. Anelastic Relaxations in CrystallineSolids. J. - REFERENCES / l / Cost. R. G. Here they may be compared with the input spectrum (solid curve) which defines the internal friction peak. G. New York (1972).. but the peaks tend t o be displaced away from each other a s shown i n Fig. The only assumption used for the calculation was t h a t . in no case d i d the results of the DSA show extra peaks o r miss peaks which were of reasonable magnitude ( . the method resolves input peaks which are a factor of two or more apart.C10-34 JOURNAL DE PHYSIQUE The results of the calculation using the DSA method o n the data in Fig.10% of the total spectrum). J. The histogram shows this peak t o be a t a relaxation time which is roughly 40% too high.. Appl. V CONCLUSIONS - (a) A new method is described for analysis of an internal friction vs temperature peak t o obtain a n approximation of the spectrum of relaxation times responsible for the peak.Input relaxation time spectrum and output histogram approximation after DSA of the data in Fig. i. these validations never gave false approximations t o the i n p u t spectrum. 4 are also shown in Fig. Academic S. I t is particularly satisfying t h a t the analysis is able t o reproduce the four peaks which make up the input spectrum. J.=500 K for 40 bins of T. 54(1983) 2137. S.e. S.... 5. The historgram approximation of the input spectrum is done a t Td. amplitude. Similar validations using i n p u t spectra of two a n d three peaks also showed this good resolving power. 4 . width a n d shape with good accuracy (typically 10%). Nontraditional Methods in Diffusion. S. R. /2/ Cost. Typically. 29 (1981) 1055. A. T. a n d Diehl. /4/ Weller... proceedings of this conference. ed. The a's are the fractional contribution of each lognormal spectrum. this is f o r the location of the third peak. Many different kinds of spectra have been validated using the method described here. The validation described in Fig. R. M. Acta Met. . Importantly. 5 . This tendency was observed in other analyses. b y Murch. Fig. 5 .