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Wood Sci. Technol. 23:251

258 (1989)

Wood

and Technology

9 Springer-Verlag 1989

Science

Evaluation of

of equilibrium moisture content in wood

"three-variable" models for the prediction

St. Avramidis*, Vancouver, Canada

Summary.Four sorption isotherm models that express moisture content as a function of both relative humidity and temperature were evaluated by fitting them to a set of sorption data between 21.1 and 71.1 ~ with the help of a nonlinear curvefitting program. All of them predicted the sigmoid shape of the sorption isotherms and the shift towards the x-axis as the temperature increased. The calculated root mean square error was used as an indication of the goodness of the fit.

Introduction

Sorption isotherms of wood are graphical representations of the relationship between the equilibrium moisture content (EMC) and the relative humidity (H) at a given temperature (T). These are of great importance in wood drying technology as well as in the prediction of the dimensional behavior of both solid wood and composite panels under the influence of a changing ambient environment. The phenomenon of adsorption has been investigated extensively in the past and numerous mathematical models have been derived to describe the relationships be- tween EMC, T, and H. Most of them have been derived for hygroscopic polymers and some have been applied to wood with success (Simpson 1973). The reader who is interested in the derivation and development of the sorption theories applied to wood, is referred to the publications by Venkateswaran (1970), Skaar (1972), and Simpson

(1980).

Simpson (1971, 1973), by using a nonlinear regression technique, fitted nine theoretically derived models to the Wood Handbook sorption data at different tem- peratures. In all models, except that of Anderson and McCarthy (1963), the indepen- dent variable was the relative humidity whereas the dependent one was the EMC. Such a model requires fitting to a set of EMC-H data at the same temperature; as a result, the curvefitting must be repeated for every sorption isotherm producing pa- rameter sets which are different for each temperature. Then, in order to obtain the appropriate set of parameters at a particular temperature, a second degree polynomial

* The author would like to thank Dr. John F. Siau, Professor Emeritus, State University of New York, College of Environmental Science and Forestry, for reviewing this manuscript

252

St. Avramidis

regression was required. Here, temperature was the independent variable and each of

the parameters the dependent one. Therefore, every time the EMC was needed for an

H-T set of values, the parameters had to be calculated from the second degree polynomials and then used in the models. This procedure resulted in additional error due to the nonlinear and polynomial regression, as well as repeated curvefitting of each models to the sets of EMC-H data at each temperature. The purpose of this communication is the presentation and evaluation, using wood sorption data, of four sorption models that have been used in the past to predict EMCs of hygroscopic biopolymers. The advantage in these models is the existence of

the temperature factor as an independent variable, therefore, only one curvefitting run is required for a set of sorption isotherms, each at a different temperature.

Materials and methods

The models evaluated are the following,

(a) Henderson (/952),

I -

h =

exp (AM B)

(1)

where A = -a ~T; B = a2; h is the relative vapor pressure; T the Kelvin temperature;

M the percent moisture content; and a t a2 are the parameters for evaluation. This

empirical model was established rigorously by a thermodynamic procedure which included the effect of temperature upon the moisture sorption isotherms. The two parameters have been evaluated for sorption isotherms of numerous agricultural products, resulting in observed and calculated data points that were in close agree-

ment.

(b) Day and Nelson (1965),

I

-- h =

exp (A M B)

(2)

where A = b 1Tb2; B = b 3 Tb4; b 1, b 2 , b 3 , and b 4 are the parameters for evaluation. This model was derived from the basic Henderson's model as described above, due to the need for a more adequate mathematical representation of the wheat desorption isotherms to be used in grain drying computations.

(c) Zuritz et al. (1979),

h

(3)

=

1 -

exp (A M B)

where A = -(c 2/T) (1- (T/To))~ B = c3 T~ Tc is the critical absolute temperature

of water, 647.1 K; c 1, c2 , c 3 and c4 are the parameters for evaluation. This model was also derived from Henderson's model with the help of an empirical relation proposed

by Van der Waal (1894). The resulting model showed a very good fit to desorption

data obtained for rice at different temperatures.

(d) Chung and Pfost (/967),

(4)

h = exp [d 1 T a2 exp (d 3 T a4M)]

Evaluating models for prediction of wood EMC

253

where dl, d2, d 3 and d 4 are the parameters for evaluation. This model is based on the dipole attractive forces between sorption sites and water molecules and the formation on the surface of many adsorbed water layers under compression. Comparison of this model to that derived by Bradley (1936), reveals that its form is practically equivalent to that of the latter, however, its derivation is simpler and the functional behavior of d 3 T a4 part is different from the K 1 in Bradley's equation. Before fitting, the models were rearranged in terms of moisture content, as fol- lows,

Henderson

M

=

[-

in

(i - h)/(a 1T)] 1/a2

(5)

Day-Nelson

M

=

[ln (1

-h)/(b 1 Tb~)]1/(b3rb4)

(6)

Zuritz et al.

M

=

[ -

Tin (1 -- h)/(c 2 (1 - T/T c)~1)]1/(taro4)

(7)

Chung-Pfost M = in

(ln (h)/(dt Td~)/(d3 T d4)

(8)

It is interesting to evaluate the models at the points of maximum and minimum relative humidity. When h tends to zero, M also tends to zero if models (5), (6) and (7) are used, but in model (8) M becomes negative. When h tends to 1 (100% relative humidity), then M in all models approaches infinity, in other words, the isotherm curve becomes asymptotic to the normal at point h = i. This means that all four models break down at this point since an equilibrium at 100% relative humidity will result in total saturation of wood (Siau 1984). Since in all four models the parameters are raised to other than the first power, they are of a nonlinear form and therefore, a nonlinear regression technique was used for the parameter estimation. A state-of-the-art general nonlinear data-fitting routine was utilized (Moore 1984). The possibility of real convergence was greatly enhanced

because the first order partial derivatives of the function with respect to each param- eter were used. This is of great advantage in a routine when it is compared to a routine using numerical approximations of the derivatives.

Each

model

was

fitted

to five isotherms

at

21.1,

35,

43.3,

51.6

and

71.1 ~

obtained from the USDA Wood Handbook (1955). For the evaluation of the good- ness of the fit, the Root Mean Square Error (RMSE) for each curve was calculated. Since RMSE estimates the difference between actual and calculated values, the crite- rion used was that the best fit of the data is obtained with the model that shows the smallest RMSE value. Additionally, the Residual Sum of Squares (RSS) for each fit were calculated and also used as an indication of the goodness of the fit. The absolute values of the difference between actual and calculated data were obtained as well as their maximum, minimum, and average values. Curves generated by the models were plotted with the experimental points in order to visually identify a possible false convergence.

Results and discussion

The values of the estimated parameters and of the residual sum of squares for the four models are listed in Table 1. The RSSs ranged from 4.27 for the Zuritz et al. model to 64.04 for the Henderson model. These values compare very favorably to the RSSs reported by Simpson (1973), regarding the curvefitting of a set of one independent

254

St. Avramidis

Table 1. Estimated parameters and residual sum of squares (RSS) for the four models

Henderson

a 1

a2

=

=

0.10E-3

1.46

RSS = 64.04

Day-Nelson

b 1

b2

b3

b4

RSS =

=-0.34E-16

=

=

5.98

0.30E3

= -0.93

7.25

Zuritz et al.

c1

c2

c3

c4

RSS =

=--6.46

=

=

0.13

0.lIE3

= -0.75

4.27

Chung-Pfost

d1

d2

d3

d 4

RSS =

=-0.19E5

=-1.51

=-0.39E-3

=

1.07

13.79

variable (h) models to the Wood Handbook sorption data for the -1 to 99~ temperature range. Henderson's model, which showed the highest RSS value, had an average devia- tion between experimental and calculated data for the five isotherms of 0.50% of moisture content as shown in Table 2. The maximum deviation was 1.46% moisture content, which appeared in the 71.1~ isotherm. A plot of the model generated curves, revealed that the fit was very poor for the 21.1, 35 and 71.1 ~ isotherms, which led to the conclusion that this model is unsuitable for representing sorption isotherms of wood. The only reference to the application of this model to wood, is in the International Critical Tables (1927), where the values of the parameters a~ and a 2 at 25 ~ were 5.34 x 10-5 and 1.41 respectively. The former is half the magnitude of that obtained for the five isotherms, whereas the latter was almost the same. The Day-Nelson model gave a fairly good fit with a RSS of 7.25. The average deviation for the five isotherms was 0.17% and the largest deviation was 0.68% moisture content, obtained in the 43.4~ isotherm. Values for the b 1, b2, b 3 and b4 parameters previously reported were 5.73 x 10-lo, 3.37, 14.86 and -0.42 for wheat and -5.96 x 10 -sT, 21.59, 2.76x l06 and -2.45 for rough rice, respectively. Both these products exhibit a sigmoid shape (type II) sorption isotherm.

The Chung-Pfost model showed a RSS of 13.79 with an average and greatest deviation of 0.21% and 1.38% of moisture content respectively. The latter was observed in the 35 ~ isotherm. This model was fitted in the past to a set of rough rice isotherms from 10 to 50~ resulting in -3.88 x 109, -3.52, -1.12 x 10 -4 and 1.3 as values for the estimated parameters. Finally, the Zuritz et al. model yielded the lowest RSS value of 4.27, with an average and maximum deviation of 0.13% and 0.53% at 21.1 ~ respectively. Past curvefitting of this model to the same rice data mentioned above, resulted in - 23.44,

2.67

curves generated by this model for the set of wood sorption data used, are shown in Fig. 1. The RMSE values for each model at different temperatures are given in Table 3. For the range of temperatures and relative humidities analyzed, the Zuritz et al. model gave the lowest average RMSE value followed by the Day-Nelson, Chung-Pfost and Henderson models, respectively. Evaluation of the differences between actual and calculated data with the Zuritz et al. model and the Hailwood-Horrobin for one hydrate model, as described by Simpson (1973), revealed minor deviations; the maximum being 0.2% moisture con-

x 10 -v,

4 x 105

and -2.12 as values for the estimated parameters. Plot of the

Evaluating models for prediction of wood EMC

 

IIIll

e~

 

IIIII

g

9

 

IIIII

(D

+.~

e4

~D

J

255

256

26

~

22-

Temperature

316K

+

St. Avramidis

~18-

2

"E ~16-

K

o14-

312-

"GI0_

~E 8-

6-

4-

2-

0

0

D

[

012

i

i

i

0'.6

i

Relative hum[dRy

0'.8

L

1.0

Fig. 1. Actual Wood Handbook moisture content data and predicted curves using the Zuritz

et al. (1979) model. Temperatures are in Kelvin

Table 3. The goodness of fit as measured by "Root Mean Square Error" (RMSE)

T

(~

Henderson

Day-Nelson

Chung-Pfost

Zuritz et al.

21.1

0.32

0.20

0.23

0.21

35.0

0.26

0.18

0.30

0.16

43.3

0.17

0.15

0.24

0.15

51.6

0.15

0.14

0.17

0.15

71.1

0.25

0.14

0.13

0.11

Average

0.23

0.16

0.22

0.16

tent, approximately. It can be said, that the fit of the former was better at the medium and high relative humidity ranges and at higher temperatures. All models predicted the shift of the isotherm curve towards the x-axis as the temperature increased. Additionally, they all predicted the sigmoid shape that charac- terizes the sorption isotherms for wood.

Conclusion

Four models that express moisture content as a function of both relative humidity and temperature were fitted to some of the USDA Wood Handbook sorption data. The results revealed that the Zuritz et al. model gave the best fit for the sorption data between 21.1 and 71.1 ~ based on the value of the calculated Root Mean Square Error. The second best was the Day-Nelson model, followed successively by the Chung-Pfost and Henderson models.

Evaluating models for prediction of wood EMC

References

257

Anderson, N. T.; McCarthy, J. L. 1963: Two-parameter isotherm equation for fiber water systems. Ind. Eng. Chem. Process Des. Develop. 2:103-105 Anonymous 1927: International Critical Tables, Vol. II, pp. 321-325, 1st Ed. New York:

McGraw-Hill Book Co. Bradley, R. S. 1936: Polymolecular adsorbed films. Part II. The general theory of the condensa- tion of vapors on finely divided solids. J. Chem. Soc. 16:1799-1804 Chung, D. S. ; Pfost, H. B. 1967: Adsorption and desorption of water vapor by cereal grains and their products. Part II: Development of the general isotherm equation. Trans. ASAE. 10:

552 555 Day, D. L. ; Nelson, G. L. 1965: Desorption isotherms for wheat. Trans. ASAE. 8 : 293 297 Henderson, S. M. 1952: A basic concept of equilibrium moisture. Agr. Eng. 33:29-33 Moore, C. 1984: UBC CURVE. Curve fitting routines. Computing Center Technical note TN 174. University of British Columbia, Vancouver, B.C. Siau, J. F. 1984: Transport processes in wood. Heidelberg: Springer, 245 pp. Simpson, W. 1971 : Equilibrium moisture content prediction of wood. For. Prod. J. 21 (5): 48-49 Simpson, W 1973: Predicting equilibrium moisture content of wood by mathematical models. Wood Fiber. 5:41-49 Simpson, W. 1980: Sorption theories applied to wood. Wood Fiber. 12:183-195 Skaar, C. 1972: Water in wood. Syracuse: Syracuse University Press, 218 pp. U.S. Department of Agriculture 1955: Wood handbook. Agric. handbook 72; 528 pp. Van der Waal. 1894: Cited in: Adam, N. K. : Physics and chemistry of surfaces. 2nd Ed. Oxford 1938: Oxford Press, 166 pp. Venkateswaran, A. 1970: Sorption of aqueous and nonaqueous media by wood and cellulose. Chem. Rev. 70:619-637 Zuritz, C. ; Singh, R. P. ; Moini, S. M. ; Henderson, S. M. 1979: Desorption isotherms of rough rice from 10~ to 40~ Trans. ASAE. 22:433-440

(ReceivedApril 27, 1988)

Dr. Stavros Avramidis Asst. Prof. of Wood Physics Department of Harvesting and Wood Science Faculty of Forestry The University of British Columbia Vancouver, British Columbia V6T lW5 Canada