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ZXSSQ of the International Mathematical and Statistical Li- The equilibrium moisture content (X.) of the samples in the air-
braries (IMSL, 1984), which estimates the solution of a prob- dryer was determined by extrapolation of the drying curves, using the
lem by solving nonlinear least squares of given functions. In graphical technique, described by Jason and Peters (1973).
this case, the average moisture, estimated by integrating the The bulk porosity (a) of the samples was estimated from the equa-
tion,
moisture profile at all nodal points, was compared to the ex-
perimental values of the drying experiment. Therefore, the c = 1 - PdPp (10)
moisture diffusivities, estimated by the computer program, are
the values that best fit the transient moisture distribution at the where, pb is the bulk density and pp is the particle (solid) density of
nodal points during the entire experimental run. the sample. The bulk density was determined from the weight and the
Inputs to the computer program were the drying time and geometric volume of the sample (slab or sphere) at various moistures. I
the moisture, the shape of the sample (slab, sphere or cylin- The particle density was determined using a steropycnometer (Quan-
tachrome Corp. SPY-2), operated under helium pressure.
der), the sample dimensions, the equilibrium moisture, and the
initial guess of the ten moisture diffusivity values to be esti-
mated. RESULTS & DISCUSSION
The computer program can also be applied with different I
initial and boundary conditions: for example if, in addition to Method of slopes
diffusion, the mass evaporation from the surface to the air- All drying experiments were performed in the falling rate
stream is also important, then boundary condition (4) becomes: period of drying, since the initial moisture of the starch ma-
terials was relatively low (Xc 1 kg water/kg dry starch). Under
-D g = k, (X-x) the experimental drying conditions used in this investigation
(high air velocity, low relative humidity, drying of individual
slab or spherical samples) the controlling resistance to mass
where, k, is the interphase mass transfer coefficient. transfer was internal diffusion of moisture. The nonlinear shape
Under the experimental conditions of the presentinvestigation, of the drying curves (Fig. 1) indicated a variable moisture
water diffusion within the starch samples was the controlling diffusivity. The method of slopes yielded indicative values of
mechanism of mass transfer. This was confirmed by the very the effective moisture diffusivity (D), assuming that the dif-
high Biot number, which is the ratio of internal to external re- fusion equation could be applied to sections of the drying curve.
sistancesto mass transfer. For wet spherical samples of diameter The approximate D values, obtained at various moistures, were
d = 2cm, dried at 60°C and air-velocity 2 m/set, the estimated used as first guesses in the computer (numerical) method.
mass transfer coefficient was k, = 0.035 m/set (Saravacoset al., The effective moisture diffusivity (D), estimated from drying
1988). For a moisture diffusivity D = 10 x lo-lo m*/sec the Biot data, represents an over-all mass transport property of water
number (Bi) becomes Bi = k&D = 0.035 x O.Ol/lO x lo-lo = 350 in the material, which may include liquid diffusion, vapor dif-
000. fusion, hydrodynamic flow and other possible mass transfer
mechanisms. The experimental D values of the starch samples,
MATERL4LS & METHODS obtained by the method of slopes of the drying curve, varied
Materials considerably with moisture content (X) and the physical struc-
Two native granular starches were the principal materials used in ture of the material (0.1 x lo-lo to 70x lo-r0 m*/sec).
the experimental measurements: Hylon 7, a high-amylose starch pow- Two different patterns (types of curves) of D vs X were
der containing about 63% amylose, and Amioca, a high-amylopectin obtained. The first pattern characterized the drying behavior
powder, containing about 98% amylopectin. Both starches were sup- of the Amioca (high-amylopectin) starch gels and the second
plied by National Starch and Chemical Corp. In addition, mixtures of type was observed on the Hylon 7 (high-amylose) gels and the
the starch materials with 25% aucroaewere used in some experiments. hydrated starches (both Hylon 7 and Amioca). A typical pat-
Two types of samples were prepared, hydrated and gelatinized tern of the moisture diffusivity of Amioca gel, which decreased
starches. The hydrated starches were prepared by thorough mixing of gradually as the moisture content was reduced is shown in Fig.
the starch materials with distilled water to moisture of about 0.8 g 2. Low moisture diffusivity values were obtained in Amioca
water/g dry solids. The gelatinized samples of Amioca were prepared
by heating a starch/water mixture (starch : water = 1:l) at 100°C for and Amioca/sucrose gels, which increased with temperature,
10 min. Hylon 7 required more water (starch:water = 2/l) and heating following an Arrhenius-type equation (Marousis et al., 1989).
in an autoclave at 120°C for 10 min for complete gelatinization. The The results of the method of slopes were compared to the
degree of gelatinization was checked by determining the loss of crys- diffusion equation using a numerical solution of Eq. (1). Equa-
tallinity, using polarized microscopy and differential scanning calor- tions 1 to 4 were solved for variable moisture diffusivity, using
imetry. the finite differences method. A good agreement was found
Most of the experiments were performed with either slab or spher- between the estimated and the predicted moistures in the drying
ical samples. Flat samples (slabs) were prepared in 90 mm-diameter of a typical starch gel (Fig. 3), supporting the validity of the
plastic or glass dishes. The hydrated mixtures were spread in the method of slopes.
dishes applying light pressure to form slabs of uniform thickness of
about 44 mm. The hot starch gels were placed into the dishes and The second pattern of moisture diffusivity, observed on hy-
allowed to stand at 4°C and 100% relative humidity for 24 hr. Spher- drated granular Amioca, is shown in Fig. 4. The effective
ical samples of hydrated or gelatinized starches were prepared using diffusivity increased gradually as the drying progressed, reach-
spherical plastic molds of 2 cm diameter. ing a maximum near 10% moisture and decreasing sharply near
the end of drying. The anomalous behavior of the moisture
diffusivity in granular and porous starches might be the result
Drying experiments of the changing mechanism during drying: In the first stage of
The drving experiments were performed in a pilot-plant tray drver drying liquid diffusion of water might be the main mass trans-
(Sargent’s S&s Corp.), which was operated at an air velocity bf 2-m/ fer mechanism. As the drying progresses, a porous structure
sec. temperatures40-100°C and relative humidities S-20%. The drving is formed, in which vapor diffusion of water may predominate.
data (m&sture ratio W vs time t) were obtained by periodic weighing Finally, at low moistures, the diffusivity decreased sharply,
of the samples with a Mettler PE 160 balance, placed on the top of because water was bound strongly on the sorption sites of the
the dryer. The thickness of the samples during the drying was mea-
sured with a micrometer. The hydrated slabs were dried from one (the food polymer.
top) side in the plates, while the gelatinized slabs were dried from The diffusivity of water was related to the porosity of the
both sides on a perforated plastic support. The dry solids of each starch material, which might change considerably during drying.
sample was determined after each experiment by the vacuum oven The porosity of a hydrated and a gelatinized high-amylopectin
method at 70°C for 24 hr. (Amioca) starch is shown in Fig. 5. The low porosities of the
04 . I . . 1 . * . 1 ’ . . 1 l
0.5
0.4
HYDRATED MIXlURE
0.3
\
E
m
2
8 0.2
0.1
O.Or
0 5 10
0.0
I I 0.2 0.4 0.6
Amioca gel corresponded to the low moisture diffusivities. tive function F) was less than lo-‘.
High porosities were observed in hydrated starches and in ge-
latinized high-amylose (Hylon 7) starch. The void space (po- F = C (K,exp- Xi.ca2 (11)
rosity) of the hydrated starches evidently facilitated the transfer
I
of water vapor within the samples, resulting in high effective where Xi is the moisture at the i-th experimental point.
moisture diffusivities. The optimization of the diffusivity values converged to a
unique solution. The assumed initial values of moisture dif-
Computer simulation fusivity did not have a large effect on the final solution, al-
though better predictions resulted in faster convergence and
A typical plot of the predicted and experimental moistures smoother curves of predicted moisture content (X) vs time (t).
during the drying of a sample of Amioca gel at 100°C is shown The moisture profile of a spherical sample of starch gel,
in Fig. 6. In most cases, the sum of squares of the differences predicted by the computer model, is shown in Fig. 7. A uni-
between the experimental and the calculated moistures (objec- form moisture profile was.assumed at the beginning of drying,
. o SLOPEMElMOD
. q COMPUTERMIZHOD
roo”c q .
.
0-l . . 1 . 1 . . I I . ’ 1 ’ . I . I ’ .
0 3 6 9 12 15 16 21 :14 0.0 0.1 0.2 0.3 0.4 0.6
TIME (hr)
MOISTURE CONTENT (g WATER/ g DRY SOUDS)
Fig. 6:-Mean moistures of a soherical sample of 75% Amiocal Fig. 8. -Effective moisture diffusivities in spherical samples of
25% sucrose gelpredicted by the computer’method. 75% Amioca/25% sucrose gel (computer and slope method).’
50
0 hr
0
. 0
.
.
I . a
60°C .
. 0
0 .
.
IMSL. 1984. IMSL Library (Edition 9.21, International Mathematical and Singh, R.K., Lund, D.B., and Buelow, F.H. 1984. An experimental tech-
Statistical Libraries Inc., Houston, TX. nique using regular re ‘me theory to determine moisture diffusivity. In
Jason A.C. and Peters G.R. 1973. Analysis of bimodal diffusion in fish “EnFg and Foo$” Vol 1 , p . 415, B.M. McKenna (Ed.). Elsevier
muscle. J. Phys. D: Appl. Phys. 6: 512. App ied Science Publ., London.
Marousis, S.N., Karatharms, V:T., and Saravacos, G.D. 1989. Effect ofsug- Viliaiobos G.S. 1986. Nonlinear transient state moisture sorption of de-
;r ;tg\he water diffusivlty in hydrated granular starches. J. Food Sm. hydrated food. Ph.D. thesis, Rutgers University.
MS received 6/23/88; revised 5/30/89; accepted 6/l/89.
Perry, R.H., Green, D.W., and Maloney, J 0. 1984. “Perry’s Chemical En-
gineers’ Handbook,” 6th ed. MC Graw Hill, New York.
Saravacos, G.D. 1967. Effect of the drying method on the water sorption
of dehydrated apple and potato. J. Food Sci. 32: 81. Presented at the 49th Annual Meeting of the Institute of Food Technologists, June
Saravacos, G.D. 1986,; Mass transfer pro 19.22, 1966, New Orleans, LA.
Pr;grt;e; of Foods, M.A. Rae and S.S. New Jersey Agricultural Experiment Station publication No D-10544-9-68, sup-
ported by State funds and the Center for Advanced Food Technology, Rutgers Univ.
Saravacos, G.D., Marousis, S.N., and Raouzeos, G.S. 1988. Effect of ethyl The Center for Advanced Food Technology is a New Jersey Commission on Science &
oleate on the an-drying rates of foods. J. Food Eng. 7: 263. Teehnolom Center.
Saravacos, G.D. and Raouzeos, G.S. 1984. Diffusivity of moisture during
air dryin of starch gels. In “Engineering and Foods,” Vol. 1, p. 499,
B.M. MC B enna (Ed.). Elsevier Applied Science Publ., London.