1. Introduction
The viscoelastic relaxation spectrum provides deep insights into the complex behavior of polymers [
1,
2,
3]. The spectrum is not directly measurable and must be recovered from oscillatory shear or relaxation stress data [
1,
3]. During the last five decades, a number of models and methods have been proposed for the recovery of the relaxation spectrum of a viscoelastic material from oscillatory shear data. The contributions by Baumgaertel and Winter [
4], Honerkamp and Weese [
5], Malkin [
6], Malkin et al. [
7], Stadler and Bailly [
8], Davis and Goulding [
9], Davis et al. [
10], and Cho [
11] are most frequently cited, as they laid the foundations for several parallel directions of research on the identification of discrete and continuous relaxation spectra based on dynamic modulus data.
Far fewer methods have been proposed for spectrum determination from time-measurements of the relaxation modulus collected in the stress relaxation test, where time-dependent shear stress is studied for the step increase in the strain. Additionally, some of them only address specific materials. A concise discussion of these works, among which three directions of research can be distinguished, is given in [
12]. The three indicated classes of approaches are: (1) differential models and algorithms based on applying the Post–Widder formula [
13] of the inverse Laplace transform to designate the relaxation spectrum models proposed in the papers of Alfrey and Doty [
14], Ter Haar [
15], Bažant and Yunping [
16], Goangseup and Bažant [
17]; (2) the models derived directly from the known pairs of Laplace transforms proposed by Macey [
18], Sips [
19,
20] and Yamamoto [
21] and (3) models based on the expansion of an unknown spectrum into a series of basis functions forming a complete basis in the space of real-valued square-integrable functions developed by Stankiewicz [
12,
22,
23] and Stankiewicz and Gołacki [
24]. Some articles are also discussed below.
The relaxation spectra of real materials are non-negative for any relaxation time and any relaxation frequency. However, most of the known models and identification algorithms do not take into account this non-negativity property. Therefore, the resulting spectrum model may take a negative value for some relaxation times or frequencies. The exceptions are those methods that use the spectrum approximation by non-negative definite simple functions, represented by the Macey [
18] exponential-hyperbolic model of the spectrum, the Sips [
19,
20] model given by difference of two exponential functions, next augmented by Yamamoto [
21] to consider long-term modulus. However, resulting spectrum models are positive for all arguments; the scope of their effective applicability is limited due to rather narrow classes of models. The Alfrey and Doty [
14] simple differential model, the Ter Harr [
15] approximation of the spectrum of relaxation frequencies by the modulus multiplied by the time inverse of the relaxation frequency and other methods using the Post-Widder inversion formula to designate the relaxation spectrum model, as Bažant and Yunping [
16] and Goangseup and Bažant [
17] two-stage approaches of approximating the stress data by multiple differentiable models of relaxation modulus and next, applying the Post-Widder formula to compute the related spectrum model, guarantee the positive definiteness of the recovered relaxation spectrum whenever the relaxation modulus is a completely monotonic function [
25]. Thus, the ranges of their applicability are restricted, also due to the necessity of multiple differentiation of the noise corrupted measurement data. A wider range of applicability has been obtained by Stankiewicz [
22] for the non-negative model based on the expanding of an unknown spectrum of relaxation frequencies into a series of basis power-exponential functions. However, article [
22] was based on such a definition of the relaxation spectrum, which is not often used in the literature.
Therefore, the goal of the present paper was to formulate and solve the problem of determination of the non-negative definite model of the relaxation spectrum based on discrete-time measurements of the relaxation modulus obtained in the relaxation test.
It was assumed that the approach’s proposed and developed identification scheme will be applicable to determine both the relaxation time and frequency spectra. The approximation of the continuous spectrum by finite series of non-negative basis functions was applied. For modeling, the relaxation time spectrum model introduced in [
12] was used, while for the spectrum of relaxation frequencies, the basis functions described by the product of power of time and square exponential functions were applied. The components of the relaxation modulus model are given by compact recurrence formulas expressed in terms of the products of power of time, exponential, and complementary error function. Both classes of models depend on some time-scale factors. The main properties of the basis functions of relaxation spectrum and modulus models have been studied; positive definiteness, monotonicity, and asymptotic properties have been examined. Ranges of applicability for different scale-time factors were determined.
A quadratic identification index, which refers to the measured relaxation modulus, was adopted. In result, the original continuous, infinite-dimensional, task of determining the best non-negative definite function, was reduced to a static, finite-dimensional, linear-quadratic optimization problem with a non-negativity constraint imposed on the vector of model parameters. The smoothing constraint for the vector of model parameters was introduced to achieve the well-posed optimization task. It is proved that the smoothness of the optimal parameters vector implies smoothness of the fluctuations of the relaxation spectrum model. Direct formula, upper, and lower bounds for the square integral norm of the smoothed spectrum model are derived in terms of the smoothing parameter.
Next, the dual approach was applied to solve the stated linear-quadratic constrained optimization task, resulting in the two-stage hierarchical identification scheme. The existence of the dual problem solution was proved. A parametric approach of successive optimization was applied to solve the dual maximization task. The optimality condition for the partial dual task was derived in the form of a simple algebraic equation. A hierarchical two-stage identification scheme was proposed. The maximization dual task was solved in two levels of the first stage, while the optimal model was determined in the second stage of the scheme. The numerical realization based on applying the singular value decomposition technique is discussed. A complete computational algorithm is outlined. The identification scheme can be easily implemented in commonly used computing environments. The numerical studies were conducted for examples of Gauss-like spectra. Both unimodal spectrum, typical for many polymers, e.g., example polymers used in food technology [
26], and bimodal spectra equally often used to describe rheological properties of various polymers [
27], e.g., polyacrylamide gels [
28] and polymers used in food technology [
29,
30,
31], were modeled. The examples and other numerical studies have proved that using the algorithm, it is possible to determine non-negative definite unimodal and bimodal relaxation spectra for a wide class of polymers. However, the examples also show that, in practice, the non-negative models of the relaxation spectra or models non-negative for almost all arguments can be obtained also using the classical approach, without the additional constraint of the non-negativity of the model parameters, if the basis functions of the relaxation spectra models are non-negatively defined.
In
Appendix A, the proofs and derivations of some mathematical formulas are given. Some tables have been moved to
Appendix B, to increase the clarity of the article.
3. Results and Discussion
In this section, the optimal identification problem (27) with additional smoothing constraint (28), is solved by applying the dual approach. The existence of the solution of dual maximization task is proved. Next, the idea of parametric optimization [
49] is applied to solve the dual task. The necessary and sufficient optimality condition for partial dual tasks is derived in the form of the algebraic polynomial equation. Hierarchical two-stage identification scheme, with the solution of the dual maximization task in two levels, is proposed. Their numerical realization and application of the singular value decomposition technique are discussed. A complete computational algorithm is outlined. The analysis of the smoothness of the relaxation spectra models is presented.
3.1. Dual Problem
By introducing Lagrangian multipliers, a vector
and a scalar
, we can define the Lagrangian for the optimization task (27), (28)
where superscript ‘
’ indicates transpose. The multiplier
aims at providing a fulfillment of the inequality
. The multiplier
is the price imposed to satisfy the smoothness constraint (28). The Lagranian is a differentiable function of all arguments.
The dual problem takes the form:
where the dual function is defined as follows:
For an arbitrary
,
and
, the Lagrangian
is a strictly convex function of
, which has a unique minimum with respect to
given by:
with symmetric matrix
where
is
dimensional identity matrix. Therefore, the dual function defined in Equation (31)
by Formulas (29), and (32), after simple algebraic manipulations, can be expressed in compact form as:
Before we solve dual problem (30), we will give the algebraic background of the method. The algebraic formula describing will be used to derive the basic result regarding the existence of a solution to the dual problem.
3.2. Algebraic Tools
Following [
12,
23], the singular value decomposition (SVD) technique [
50] is applied here. Let SVD of the
dimensional matrix
(26) takes the form [
50]:
where
is a diagonal matrix containing the non-zero singular values
of the matrix
, matrices
and
are orthogonal, and
. Due to the diagonal structure of
and orthogonality of
and
, matrix
(33) can be expressed as:
where
diagonal matrix
is as follows:
Whence, the parameter
(32) is given by:
3.3. Existence of the Dual Problem Solution
The following proposition, proved in
Appendix A.3, is fundamental for the existence of the solution to the optimization task (30).
Proposition 1. The dual function (34), defined by Equation (31), is strictly concave function of both arguments , whenever .
Now, the existence of the dual problem solution is resolved by the next result proved in
Appendix A.4.
Theorem 4. If the smoothing parameter is such thatwherethen there exists a solution of the dual problem (30), such that .
3.4. Solution of the Dual Problem
Application of the parametric approach [
49] to solve the dual problem (30) results in the scheme:
where the function
is defined by the following task:
From the proof of Theorem 4, it follows that, if the condition (39) is satisfied, then for any fixed the maximum, with respect to , of the strictly concave dual function is positive. Therefore, is the unique necessary and sufficient condition for optimality in task (42), which, in view of Equations (A19) and (33), immediately yields the following optimality condition for partial dual problem (42).
Theorem 5. Assume the condition (39) holds. The optimal Lagrange multiplier solves uniquely the optimization task (42) if and only if the following equation is satisfied The above optimality condition means that for any given
and respective optimal
, the smoothing constraint (28) is satisfied as an equation for the resulting model parameter
described by (32). For any fixed
Equation (43) can be solved by an arbitrary method of solving nonlinear algebraic equations. By Equations (33), (35) and (36), Equation (43) can be expressed as
where, in view of Equation (37), diagonal
matrix:
Introducing
element vector
composed of the elements
, Equation (44) can be rewritten as:
whence equivalent polynomial equation of unknown variable
follows:
To solve Equation (45) of order
, in general, any numerical method of solving polynomial equations can be applied [
51].
In view of Equations (42) and (34) we have:
In the
Appendix A.5, the following formula is derived:
where
satisfies Equation (43).
By SVD (35) and Equation (36), function
(46) takes the form:
while the gradient (47), in view of Equation (36), is equivalently given by:
For solving the optimization task:
numerical methods of constrained nonlinear programming [
52] can be applied.
3.5. Solution of the Smoothed Identification Problem
If the saddle point of the Lagrangian
(29) exists, then the dual approach can be successfully applied to solve the optimization task (27) with the smoothing constraint (28), i.e., to solve the stated identification problem. In the case considered, the existence of a saddle point to the Lagrangian follows immediately from Theorem 1, cases (ii) and (iii) in [
53] due to the uniqueness of the minimum of
with respect to
, given by Equation (32). Thus, the vector:
or, equivalently,
where
, is optimal solution of the optimization task (27), (28), i.e., the vector of the best model parameters. According to Theorem 4, the price
and, by Equation (43), for optimal
(50) we have
i.e., the smoothness constraint (28) is equally satisfied.
3.6. Two-Level Solution od the Dual Problem
To solve the dual problem (30) according to the optimization task (41), i.e., by successive maximization with respect to and , the following two-level algorithm can be applied.
Lower level of the dual problem solution:
Given the Lagrange multiplier , find the multiplier maximizing in the optimization task (42) by solving Equation (43).
Upper level of the dual problem solution:
Find the multiplier solving the optimization task (49).
The resulting pair , , solves the dual problem (30). The numerical computations must be arranged hierarchically, i.e., in each iteration of the maximization procedure at the upper level, the algebraic equation (43) must be solved in the lower-level task. The complete computational procedure for determining the dual problem solution and, next, the optimal model of the relaxation spectrum is given below.
3.7. Identification Scheme
The determination of the model of the relaxation spectrum involves the following steps.
Perform the experiment (stress relaxation test [
3,
28,
40]) and record the measurements
,
, of the relaxation modulus at times
.
Choose the number of model components and, depending on the relaxation spectrum recovery problem considered, the time-scaling factor for identification of relaxation time spectrum or for spectrum of relaxation frequencies determination, comparing, for different values of or , a few first functions from the sequence or with the experiment results .
Compute the matrix (26) and, next, determine SVD (35).
Compute and choose the constant .
Determine, in the following two-level computations, the solution of the dual problem (30).
- 5.1
Choose the initial multiplier for the numerical procedure applied to solve optimization task (49).
- 5.2
Let be the -th iterate in the numerical procedure solving (49). For solve the Equation (43) according to the chosen numerical procedure and determine . Polynomial Equation (45) can be solved instead of Equation (43).
- 5.3
Using
, compute the new multiplier
, being the next approximation of
, according to the numerical procedure selected to solve the task (49), with the maximized index
given by Equation (46) or, equivalently, by Equation (48). If, for
, the stopping rule of the chosen numerical procedure is satisfied, i.e.,
or
where
and
are preselected small positives, take
and
as the solution to the dual problem (30), and go to Step 6. Otherwise return to Step 5.2 and continue the computations for
.
Compute the vector of the optimal model parameters
according to Equation (50) or (51) and, depending on the spectrum recovery problem, determine the optimal model of the relaxation time spectrum given by:
or optimal model of the spectrum of relaxation frequencies described by:
where
are elements of the vector
.
The schematic framework of the above procedure and communication between the two levels solving dual problem and the remaining tasks and relaxation test experiment are shown in
Figure 3.
3.8. Remarks
The SVD (35) of the matrix
, of computational complexity
[
50], must be computed only once in Step 3 and should not be repeated during the two-level computations of Step 5.
The matrix depends on the choice of the basis functions as well as the measurement points ; however, it does not depend on the relaxation modulus measurements . Thus, when the identification scheme is applied for successive samples of the same material, Step 3 should not be repeated while the same time instants are kept and the same model parameters or and are used (selected in Step 2).
Since the normal solution
, where
is the Moore–Penrose pseudoinverse [
54] of matrix
(35) with
matrix
, the norm computed in Step 4 is as follows
where
are elements of the
dimensional vector
.
The basis functions (7) are the products of power of time and the modified Bessel functions of the second kind, while the basis functions (14)–(16) are expressed using complementary error function. The modified Bessel functions of the second kind are accessible, for example, in Matlab as besselk function. The function is accessible practically in every computational packets either directly or by the error function .
In the models proposed the parameters
and
are the time-scaling factors. For the relaxation time model the following rule holds, the lower the parameter
is, the greater the relaxation times are [
12]. For the relaxation frequency model, the larger the parameter
, the greater the relaxation times, the lower the relaxation frequencies. Through the optimal choice of the scaling factors, the best fit of the model to the experimental data can be achieved. In [
12], the hierarchical algorithm with the optimal choice of the time-scaling factor
was presented. However, practically in many cases, the selection of the time-scaling factors in Step 2 based on the data concerning model applicability summarized in
Table 1 and
Table A1 for factor
and related tables in [
12] for factor
or based on the comparison of a few first functions from the sequences
or
for different values of
or
with the experimentally obtained function
, is quite enough. Similarly, the number
of the models
(6) or
(12) series elements can be initially evaluated. This rough selection strategy of the model parameters selection was applied in [
23]. Thus, the choice of
and
must be carried out
a posteriori, after the preliminary analysis of the experiment data.
Only the values of and , not the related parameter described by Equation (32), are used in iterations of the numerical procedures solving the dual problem tasks in Step 5. The vector of optimal model parameters is computed only in Step 6.
3.9. Smoothness Analysis
The smoothing constraint (28) was introduced to stabilize the resulting vector
(50), for which the equality (52) holds. Since the non-negative basis functions
(3) and
(11) for any arguments are bounded by one, the following inequalities:
hold for the optimal models (53) and (54) with arbitrary time-scale factors, which means that the smoothing of the vector of model parameters imply the boundness of the respective relaxation spectra.
The norms
and
are also the measures of smoothness of the spectra models, where
means here the square norm in
. Proposition 1 in [Belssel] characterizes
as the square form of
with the matrix dependent on
. In the
Appendix A.6 the analogous property for the spectrum
is proved.
Proposition 2. For an arbitrary time-scale factor and arbitrary vector of model parameters for the relaxation spectrum model (10) we havewhere is symmetric, positive definite, real matrix of the elements:where and the values of the basis functions (14)–(16) at are as followsfor even indices and for odd indices, where . Matrix is a positive definite.
The basis functions
(57), (58) for the time
do not depend on the time-scale factor, in fact. Propositions 2 and 3 in [
12] specify various useful estimates of
, which can be directly applied to obtain the respective estimates of the norm
and, for the optimal models, results in the next property.
Proposition 3. For an arbitrary time-scale factors and and the vector of optimal model parameters (50), for the optimal models (53) and (54) the following upper:
and lowerbounds hold, where , are the largest and , are the minimal singular values of matrix (56)–(58) and matrix defined in [12] (Equation (53)). The square roots of the singular values
and
for
are summarized in
Table 2. Since
grows with
, the greater the number of model summands are, the greater time scaling factor should be, to achieve pre-assumed multiplier
in the estimation (59). However, this increase is relatively much weaker than in the case of the model
(53). Similarly, as in the case of
(for details, see [
12]), estimation (60) is useful only for small
and small time-scale factors. Thus, the smoothness of the vector
(50) of model parameters guarantees that the fluctuations of the respective spectra of relaxation
and
are also bounded. The time-scale factors
and
affect the smoothness of the models.
3.10. Examples
Three examples are presented below. In two examples, the relaxation spectra described by the double-mode Gauss-like distributions are considered since spectra of this type describe the viscoelastic properties of various polymers: [
27] (Figures 4b and 8b), polyacrylamide gels [
28] (Figure A4), cold gel-like emulsions stabilized with bovine gelatin [
29], fresh egg white-hydrocolloids foams [
31] (Figures 6 and 14) and are tested when developing new identification methods; for example, in [
8] (Figure 2), [
9] (Figures 9, 11 and 17) and [
10] (Figures 2, 3, 6, 7–11 and 14). In the third example, one-mode Gauss distribution was taken; typical, for example, for relaxation spectra of some native starch gels [
26] (Figures 6b, 7 and 9a).
As in [
12], in all examples for numerical experiment
, sampling instants
were generated with the constant period in the time interval
seconds and additive measurement noises
were selected independently by random choice with uniform distribution on the interval
. The real spectra and modulus and the basis functions
(3),
(11) of the spectra models and
(7),
(14)–(16) of the modulus models were simulated in Matlab R2022a using the special functions
besselk and
erfc. For the singular value decomposition procedure,
svd was applied.
The relaxation time and frequencies models are determined in the class of models defined by
(5) and
(10). In all examples, the same workflow is applied. First, the optimal models were determined by a two-level regularized least-squares identification scheme proposed in the previous paper [
12], i.e., neglecting the non-negativity requirement. This means that, in particular, the optimal time-scale factors
and
and the optimal regularized model parameter vectors
were determined resulting in the unconstrained, i.e., determined without non-negativity constraint, models of relaxation time:
and relaxation frequencies
where
are elements of the vector
.
Next, for the optimal factors and , the best models with the optimal parameters are determined with the non-negativity requirement using the scheme proposed above. As a result, the relaxation spectra (54) and (54) were obtained for time scale factors and with the non-negative optimal parameters (50). The smoothing parameter was selected several times until a satisfactory accuracy of the fit of the model to the experimental data was obtained. Since some elements of the vectors are negative, i.e., the respective components of the models (61) and (62) are negative too, smaller than the norm are applied.
3.10.1. Example 1
Consider viscoelastic material of relaxation spectrum described by the double-mode Gauss-like distribution considered in [
12,
27]:
inspired by polyethylene data from [
27], especially HDPE 1 sample from [
27] (Table 1 and Figure 8b), where the parameters are as follows [
12]:
,
,
,
,
and
. It is shown in [
12] that the related real relaxation modulus is
Following [
12], the time interval
seconds is assumed for numerical experiments. In [
12], the optimal models
(61) with the parameter vectors
and time-scaling factors
were determined for
. Detailed data, including
,
, regularization parameters
, the square norms
and
, as the measures of the solution smoothness, and mean square identification index
were summarized in [
12] and (Tables 3 and A3). Only
,
and
are rewritten here in
Table 3; the last two to compare with respective data for the constrained non-negative model
(54). The vectors
are given in [
12] (Table A3), from which it can be seen that some of their elements are negative. For
one element, for
two elements, for
three elements and for
four elements are negative. Also, the spectra
(61) are negative for some ranges of the relaxation frequencies, see [
12] (Figures 4 and 7a) and also
Figure 4, below. The non-negative optimal vectors
are given in
Table A2 in
Appendix B. Only two or three elements of these vectors are non-zero, the corresponding elements of the Lagrange multipliers vectors
are obviously zero. Other numerical data for optimal non-negative models
, i.e., square norm
, identification index
and the Lagrange multiplier
are given in the last columns of
Table 3.
Figure 4 illustrated the course of the real spectrum
(63), the unconstrained model
(61) (blue line) and non-negative model
(54) (green line) for
. The non-negative models
are summarized in
Figure 5 for
. In
Figure 6, the models of the relaxation modulus
and
corresponding to
(61) and
(54), respectively, computed according to Equation (6) are plotted for
, where the measurements
of the real modulus
(64) are also marked. The optimal models
have been better fitted to the experimental data than
, thus
practically coincide with the measurement points. The deterioration of the identification index for the non-negative models changes from 5.97 times for
to 65.56 times for
.
3.10.2. Example 2
Consider again the double-mode Gauss-like distribution described by equation (63). Now the parameters are:
,
,
,
, and
. By the formula
, the respective spectrum of relaxation frequencies is as follows:
the corresponding real relaxation modulus
is described by Equation (64).
For experiment, the time interval seconds is selected in view of the course of the modulus and the Formula (22) important for numerical computations.
The optimal unconstrained models
(62) with the parameter vectors
and time-scaling factors
were determined using the two-level identification scheme proposed in [
12] for
, and
, regularization parameters
, norms
and mean square identification index
were enclosed in
Table 4. The vectors
are given in
Table A3 in
Appendix B for selected
, from which it can be seen that the number of negative elements is less than for Example 1. The courses of the unconstrained models
(62) are illustrated by
Figure 7, where the real spectrum
(65) and non-negative model
(54) are also given for even
from 6 to 20. For some
the spectra
(62) are negative for some ranges of the relaxation frequencies, see
Figure 7b–d for
. For
the number of model elements is too small to describe the real bimodal spectrum. Only the stronger maximum of the real spectrum is approximated by both models; however, the approximation is more accurate for the non-constrained model, similarly to the approximation of the relaxation modulus measured by identification index. For
the non-constrained optimal spectrum is negative for some relaxation frequencies, thus applicability of the proposed scheme is necessary to obtain the non-negative model. However, model
is unimodal. For
the non-constrained spectrum
is non-negative, becomes bimodal and better approximates both the real relaxation modulus and relaxation spectrum than the model
, being still unimodal.
The non-negative optimal vectors
are given in
Table A3. For this model, only two to five elements of these vectors are zero. Other numerical data for optimal non-negative models
, i.e., norm
, index
and the Lagrange multiplier
are given in the last columns of
Table 4. In
Figure 8, the models of the relaxation modulus
and
corresponding to
(62) and
(54), respectively, computed according to Equation (12) are plotted for
, also the measurements
of the real modulus
(64) are given.
For
vector
is non-negative, thus
also solves the optimization task (27), (28). The related spectrum model
is plotted in
Figure 9a, while the relaxation modulus model
corresponding to
(54) is given in
Figure 9b. The perfect approximation of the relaxation modulus does not match the good approximation of the relaxation spectrum, and the model has also lost its bimodal character. The model already has too many non-zero terms; exactly 21.
However, for , as increases, the models (62) determined without non-negativity constraint approximates the bimodal spectrum more and more closely, the model determined with the non-negativity constraint does not. Models (54), with increasing , better and better approximate the second, major, maximum, but it does not model the first, minor, maximum even for 20 components.
3.10.3. Example 3
Now, we consider viscoelastic material of unimodal relaxation spectrum described by distribution:
where the parameters are as follows:
,
, and
. The corresponding real relaxation modulus
is described by one component of the model of the form (64). In experiment the time interval
seconds was applied, which resulted from the inspection of the course of
.
For
, the optimal time-scaling factors
, the related regularization parameters
, the mean optimal identification indices
and square norms
are given in
Table 5. The vectors of optimal model parameters
are given in
Table A4 in
Appendix B; the elements of these vectors are both negative and positive. related to model
(62)
Next, for time-scale factor
the optimal non-negative models
(54) were determined; the smoothing parameter
was selected several times until a satisfactory accuracy of the fit of the model to the experimental data was obtained. The non-negative optimal parameters
(50) are given in
Table A4, while the multiplies
defined in Equation (30), norms
, and optimal identification indices
are given in
Table 5. For
, the real spectrum
(66), optimal models
(62) and
(54) are plotted in
Figure 10. The norms
are equal to the smoothing parameters
, which are assumed smaller than the norms
, since a quick inspection of the data from
Table A4 shows that many elements of the vector
are negative (even, six by eight for
). In
Figure 11 the optimal models of the relaxation modulus
related to unconstrained
(62) and non-negative
(54) relaxation spectra are plotted for
and
.
Figure 10 shows that the
model, determined without additional non-negativity constraint, is negative in some range of frequencies for any
. However, the identification index
is from 1.08 (for
) to 68.1 (for
) times greater than
obtained for unconstrained model (
Table 5), the inspection of
Figure 10 shows that model
well approximates the real spectrum, and the quality of this approximation improves with increasing
. For
two elements of the vector
are zero, i.e., for
only one element of the vector
is non-zero and in result index
is the biggest, see also
Figure 11a. Analysis of both the values of identification index
and
Figure 10 indicates that the best model with non-negativity constraint was obtained for
. For
, both the relaxation modulus models practically coincide with the measurement points and with each other, see
Figure 11b. Increasing the number of model components to
no longer corrects the model.
3.10.4. Discussion
In Example 1, the peaks of the spectrum are more distant than in Example 2. For successive the maxima of the basis functions (3) are more distant than the maxima of the functions (11). Thus, the relaxation time model (5) was more appropriate for modeling spectrum in Example 1, than model (10). For the same reason, in Example 1, it was enough to use model components, while in Example 2, many more model components were necessary () to obtain a satisfactory approximation of the real relaxation modulus and spectrum.
The parameter vectors of the models determined with non-negativity constraint have zero elements. Therefore, these models are composed of fewer items than index would indicate. However, the model of full dimension must be determined on the identification stage. The proposed approach, effective for the unimodal spectrum, is less effective for the multi-modal spectra, because the additional non-negativity constraint reduces the set of admissible models and, therefore, makes it impossible to achieve such a good fit of the model to the experiment data as for the model determined without this constraint.
Additionally, the examples showed that a new model of the frequency spectrum can be applied for unimodal and bimodal spectra approximation when the regularized least-squares identification with optimal choice of the time-scale factor is used without additional non-negativity constraint.
3.11. Applicability of the Scheme to Discrete Relaxation Spectra Identification
Assume, as above, that the experiment resulted in a set of the measurements
at the times
,
. By (1), for any time
we have:
Let
, where
and
is the length of integration step. Then, for any
, the integral of the right-hand side of Equation (67) can be approximated by:
whenever the number of subintervals
and the integration step
are such that the integrand is sufficiently small for
. Denoting:
compare Equation (26), the set of discretized model equations takes the form:
with vector
of unknown relaxation spectrum at relaxation times
and known elements of the matrix
, where
is the vector of the relaxation modulus of model (1) at times
, defined by analogy to the vector of relaxation modulus measurements
. Now, the square of the model (70) error is described by identification index
(25) and the proposed identification scheme can be applied for determining the best nonnegative approximations of the discretized relaxation time spectrum. As a result, the set of pairs
, for
, where the optimal
are uniquely given by the optimal model parameter
according to Equation (69). The approximation of the the discrete spectrum becomes more accurate as more rectangles are used in the series (68). By analogous discretization of Equation (2), discrete relaxation frequency spectrum can be determined.
The simple rectangular (midpoint) rule with equally spaced points is applied here; however, other, more sophisticated quadratures can be also used.
4. Conclusions
In this paper, a new hierarchical identification scheme for recovery of the non-negative continuous relaxation spectra has been derived. The scheme can be applied to identify both relaxation time and frequency spectra using the relaxation test data. Two classes of models are considered; both are based on an expansion of an unknown spectrum into a series of non-negative basis functions. The continuous spectrum of relaxation times was approximated by finite series of power-exponential basis functions, with the components of the relaxation modulus model described by the product of power of time and the modified Bessel function of the second kind. For modeling of the relaxation frequency spectrum, the basis functions described by the product of power of time and square exponential functions were applied. The components of the related relaxation modulus model were proven to be described by compact recurrence formulas expressed in terms of the products of power of time, exponential, and complementary error functions. The quadratic identification index related to the relaxation modulus measurements was used, and an additional smoothing constraint was imposed on the model parameters to ensure the problem was well-posed. The numerical experiments showed that both considered classes of models can be applied for unimodal and bimodal relaxation spectra modeling with additional non-negativity constraints. The model of the relaxation time spectrum using the modified Bessel functions can be recommended for modeling bimodal spectra with the peaks more distant than the relaxation frequency model.
However, the examples showed that in many cases, the non-negative models of the relaxation spectra or models non-negative for almost all arguments can be obtained also using the classical approach, without the additional constraint of the model parameters non-negativity, whenever the basis functions of the relaxation spectrum model are non-negatively defined. Thus, the following procedure can be recommended for the non-negative relaxation spectrum determination. First, find the best model of the relaxation spectrum using regularized least-squares identification and check the definiteness of the designated model. If this model is non-negative over a significant range of relaxation times or frequencies, accept it. Otherwise, apply the proposed two-stage hierarchical algorithm and determine the nonnegative relaxation spectrum model.
However, the best non-negative model can be obtained by solving the original infinite-dimensional task of optimal approximation of the real spectrum in the class of continuous non-negative functions by applying the calculus of variations technique. It will be the subject of further work.