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Studies on the Relationship Between

Water-satured State and Crystallinity


by the Diffraction Method for
Moistened Potato Starch
By S. Nara and T. Komiya, Tsu (Japan)
~ ~~

Crystallinity was measured by X-ray diffraction method and water- Untersuchungen uber die Beziehung zwischen Wassersattigung
saturated state was determined by means of the moisture contents und Kristallinitat mittels der Beugungs-Methode fur feuchte
calculated from the crystallinity for moistened cellulose and potato Kartoffelstarke. Die Kristallinitat von feuchter Cellulose und
starch. In the X-ray diffractograms the upper areas which were Kartoffelstarke wurde mittels der Rontgenbeugungs-Methode, und
separated by the straight line joined the points of intensity at 37" and der Wassersattigungs-Zustand wurde mit Hilfe der aus den Feuchtig-
4" (8") of diffraction angle was the relative reflection area in the keitsgehalten errechneten Kristallinitat bestimmt. In den Rontgen-
crystalline and amorphous portions, and the lower area was the beugungs-Diagrammen waren die oberen Bereiche, die durch die
background of the non-relative reflection area. The upper area gerade Linie zwischen den Intensitatspunkten 3 7 und 4" (8")
separated by the smooth curve joined the minimum intensity at 4" to Beugungswinkel getrennt waren, der relative Reflexionsbereich der
37" of diffraction angle corresponded to the crystalline portion and kristallinen und amorphen Anteiie, und der untere Bereich warder
the lower area to the amorphous one. The ratio of the crystalline Hintergrund des nichtrelativen Reflexionsbereiches. Der obere
portion to sum of the crystalline and amorphous portions was Bereich, der durch die flache Kurve die minimale Intensitat bei 4" bis
considered to be crystallinity. Crystallinity of the air-dried and the 37" Beugungswinkel abgetrennt war, entsprach dem kristallinen und
moisture-saturated (28%) samples of cellulose were 0.68 and 0.71, der untere Bereich dem amorphen Anteil. Das Verhaltnis des
resp. The crystallinity of the air-dried and water-saturated (49%) kristallinen Anteils zu der Summe aus kristallinem und amorphen
samples of potato starch were 0.24 and 0.32, resp. Anteil wurde als Kristallinitat angesehen. Die Kristallinitat der
luftgetrockneten und der feuchtigkeitsgesattigten (28YO)Cellulose-
proben betrug0,68 bzw. 0,71. Die Kristallinitlt der luftgetrockneten
und wassergesattigten (49%) Kartoffelstarkeproben betrug 0,24
bzw. 0,32.

1 Introduction atmosphere were passed through a 200 mesh screen. The


cellulose sample was the powder one for chromatography
The authors reported on crystallinity by the X-ray diffraction manufactured by Whatman Co. and was sieved through a 100
method [l], moisture regain [2], specific volume [3] and mesh screen.
deuteration [4], and also did sorption phenomena [5] and acid
resistance [6] for starch granules. Since crystallinity of starch 2.2 Moistened materials
granules increased with an increased sorption water, it seemed
to become maximum in water-saturated state. The water- Preparation of moistened materials was done by the vapor
saturated state of starch granules was given by the vapor [7,8] and the centrifuging methods [8,9]. The vapor method was as
and centrifuging methods [9], but determination of the follows: About 10 g of air-dried samples in a dish of 8.5 cm
saturated state has not been made clear yet. Moreover, a diameter were placed in the desiccator where at the bottom
general determination method of crystallinity of starch was appropriate amounts of water were placed under low pressure
not elucidated because the 100% and various ratio crystalline at room temperature. The samples were stirred some times
starches were unknown. with spatula and sorbed water vapor for 10 to 30d. The
Consequently, crystallinity of starch granules was expressed centrifuging method was as follows :About 1 g of the air-dried
by the relative crystallinity and the crystal index [l, 103. The sample was put the centrifugal filter tube fitted with a filter
authors discussed the measurement of crystallinity of starch paper (Toyo Filter No. 2 ) at the bottom and sorbed water
granules by separating the crystalline and amorphous added in the tube at room temperature. After 24 h, the water-
portions in X-ray diffractogram and moreover, did the sorbed sample was hydroextracted by centrifuging for 50 min
determination of water-saturated state on the basis of using the p F measured centrifuge (No. 55 - 1)manufactured
crystallinity. by Sakuma Manufacture Co. Japan. The centrifugal effect
was expressed by the value of pF, that is, the logarithm of
2 Materials and Methods centrifugal effect ( g ) . For example, pF 4 is log lo4 (8).
The p F value was calculated from the equation (1) and the
2.1 Air-dried materials relative humidity at p F value was calculated from the
equation (2) [9, 113:
The starch sample used was commercial potato starch refined
with cold alkaline solutions by the same manner as described
in the previous report [l] and the refined materials dried in

starch/starke 35 (1983) Nr. 12, S. 407-410 0 Verlag Chemie GmbH, D-6940 Weinheim 1983 407
0038-9056/83/1212-0407$02.50/0
+
pF = 4.036 log (2 -log RH) + log (273 + t ) (a, the equation (3) was 0.025 for cellulose and 0.004 for potato
where r =radius, 6.307 cm, g = gravity, n = revolutions per starch at 37" of 2 8. The value of 0.004 was considered to be
min, RH = relative humidity (%), t = temperature ("C). negligible. The value of 0.025 was slightly large to be
neglected, but the value was considered to be negligible
2.3 Moisture content because it decreased with a decreased 8. The normalization of
intensity was not done because of IN= I, for cellulose and
The moisture content of starch was measured by vacuum potato starch.
drying at 120°C for 4 h and that of cellulose was done by +
The ratio of the each value of a, a,and ac/u,(u, = a, a,)of
drying at 105°C. The moisture content was expressed as the the moistened sample to that of the air-dried one was
value per dried materials (dry basis). calculated to give the relative crystallinity (in this case, a
decrease of a, meant an increase of crystallinity).
2.4 X-ray diffraction method
The X-ray diffraction method was almost the same as
3 Results
described in the previous reports [l, 61. Copper K radiation
The Figures 1 and 2 show the diffractograms ofthe moistened
passed through a Ni filter was generated by a Rigaku Denki
cellulose (by centrifuging at pF 3.93) and potato starch (by
X-Ray Diffractometer D-3F type. The cellulose and starch
vapor processing for 30 d where the separation methods of
powders were held in an aluminum cell (thickness 0.15 cm) their crystallinity (a,)
and amorphous (a,) portions are given.
and exposed to the X-ray beam (30 KV, 15 mA) with the Table 1 shows the moisture contents, and the relative
symmetrical reflection technique. Both width of the divergen-
humidity in a. a, and a,/at for the moistened cellulose and
ce and scatter slits were 1" and that of the receiving slit was potato starch which were prepared by the vapor processing
0.4 mm. The scanning regions of the diffraction angle were 4"
for 10 and 30 d and by centrifuging at pF 3.93 to 4.20.
to 37" of 2 8. The chart speed was 2 cm/min and 1 cm of chart
width corresponded to 1"of 2 8. The height of full scale on the
chart was 24cm and the maximum intensity was 1600
counts/min for starch and 4000 counts/min for cellulose.

2.5 Relative crystallinity


The measurement of the relative crystallinity to which the
Hermans method [12 - 171was applied was done according to
the same manner as reported previously [1,6]. The separation
methods of the crystalline and amorphous portions in the
X-ray diffractograms of cellulose and potato starch were
shown in Figures 1 and 2. The upper area (a,)which was
L" 10' 15' 20" 25" 30" 35"37"
separated with the smooth curve connecting each point of the Diffraction angle(2 8 )
minimum intensity corresponded to the crystalline portion
and the lower area was background containing the amor- Figure 1. X-Ray diffractogram of cellulose hydroextracted by
phous portion (a,). a, was assumed to be the upper area centrifuging at pF 3.93. u, and u, indicate the crystalline and
separated with the straight line joining the two points of amorphous portions in the X-ray diffractogram, resp.
intensity at 37" and 4" (8") in the background. By assuming
that the all integral intensity from 4" to 37" was constant, the
areas of a,and a,were corrected to be the value of250cmz as
described in the previous report [6]. Correction of air
scattering and utilization ratio of X-ray first beam was not
done.
The normalized intensity (IN)of reflection intensity (I,) was
expressed as follows :

1-exp (-2 Dcosec 8)


1-'
where PIP, = corrected value of first beam intensity, D =
Figure 2. X-Ray diffractogram of potato starch moistened by the
vapor processing for 30 d.
X-ray optical density.
The initial and terminal intensity ofthe first beam were almost In the case of cellulose, when each relative crystallinity of the
constant by checking with astandard ofsilicon powder and as air-dried material in a, aaand a,fa, was assumed to be 1, the
relative crystallinity of the moistened one having the values of
a result, it was assumed to be P, = P.
The values of the linear absorption coefficient (p) [12] for 0.90 to 0.95 was slightly smaller than that of the air-dried one
cellulose and potato starch were 12.03and 11.75, resp., which in a,.But the relative values having 1.01 to 1,06 and 0.78 to
were caluculated with the respective density (y)of 1.551 and 0.87 in a,/a, and a,,respectively were slightly larger than the
1.517 [3,5]. The apparent density (4.1') of cellulose and potato respective relativecrystallinity ofthe air-dried one in ac/u,and
starch wasOSOand0.75,resp. and thickness was0.15 cm. The a,.For the cellulose sample moistened in atmosphere for 15
optical density of cellulose and potato starch was 0.58 and after dehydration in a desiccator containing P,05 at room
0.87, resp. which was calculated from the equation, D = p't temperature, the relative crystallinity in a, was 1.06 and

= (t. ') .
y t. The maximum value ofthe exponential part in
slightly smaller than that ofthe air-dried one in a,,but those in
u,and a,/a, were 1.09 and 1.01, resp. and were slightly larger
than those of the air-dried one in a,and a&,.

408 starch/starke 35 (1983) Nr. 12, S . 407-410


Table 1.
Moisture Contents and the Relative Crystallinity of the Moistened Cellulose and Potato Starch.Samples : Moistened Cellulose and Potato Starch.
a, and an.Indicate the Crystalline and Amorphous Portions in the X-Ray Diffractograms of the Samples, resp., at = a, + aa.

Moistened Vapor Method Centrifuging Method


Air dried after d 10 20 30 PF 3.93 4.00 4.08 4.20
Dehydration RH% 100 100 100 RH% 99.4 99.3 99.2 98.9

Cellulose
Moisture
Content (YO) 5.15 4.90 17.47 20.19 22.15 27.92 26.63 25.63 24.00
r c (cm2) 105.3 115.1 94.6 97.2 98.8 97.9 98.4 99.7 96.2
1 1.09 0.90 0.92 0.94 0.93 0.93 0.950 0.91
%a (cm2) 48.5 51.3 42.4 38.8 39.8 37.2 39.0 42.3 40.0
1 1.06 0.87 0.80 0.80 0.78 0.80 0.87 0.82
a,/at (ratio) 0.683 0.691 0.691 0.715 0.713 0.725 0.716 0.702 0.703
1 1.01 1.01 1.05 1.05 1.06 1.05 1.03 1.03

Potato Starch
Moisture
Content (%) 19.80 16.57 44.60 44.97 49.99 54.63 54.15 53.74 49.14
E c (cm2) 25.6 21.9 34.1 35.7 33.8 27.4 28.1 27.3 28.5
1 0.86 1.34 1.40 1.32 1.07 1.12 1.07 1.11
a, (cm2) 80.9 102.7 61.7 66.8 71.7 62.5 63.9 66.2 65.5
1 1.27 0.84 0.83 0.89 0.17 0.79 0.82 0.81
aJat (ratio) 0.240 0.176 0.335 0.348 0.320 0.304 0.310 0.290 0.303
1 0.73 1.40 1.45 1.34 1.27 1.29 1.22 1.26

From the results mentioned above, the crystallinity of A,, respectively, Hermans proposed the relation between
cellulose was not changed by the moisture drying and these areas and crystallinity as follows: uc= x . A,, CL, =
absorbing as reported by Morsi [18]and recognized generally. (1 -x) .A,, a, and u, were the areas of crystalline and
The crystallinity of cellulose was considered to be almost amorphous portions in the X-ray diffractogram of a
constant, even if the moisture content of cellulose changed crystalline polymer, resp.
from 17 to 28%. In our experiments, it was assumed that the reflection
In the case of potato starch, when each relative crystallinity of proportional constant for the crystalline portion in the
the air-dried material in a, u, and uc/u,was assumed to be 1, material was the same as for the amorphous portion because
the relative values of the moistened materials in u, a, and the starch samples having 100% and various ratios of
ctc/ct,were1.07to1.40,0.77to0.89and1.22to1.55,resp.and crystallinity were unknown. When the areas of =,and 01, were
were relatively larger than the corresponding relative given as the following equations: u,= x . u,, u, = (1-x) . a,,
crystallinity of the air-dried one. The relative crystallinity of a, = a, + u,, the relation of A, = A. = a, was given from the
the air-dried materials which sorbed moisture in atmosphere above assumption.
for 15 d after having been dried in pz05 were 0.86,0.75and On the cellulose,the values of ct,/u, shown in Table 1 were 0.68
1.27 in ct, uJu, and a,, resp. and all of them were relatively for the air-dried material and 0.69to 0.73 for the moistened
smaller than the corresponding relative crystallinity of the so- one. These values were almost the same as the crystallinity of
called air-dried one. cellulose hitherto reported [21- 261.Therefore, the value of
From these results, it was considered that the air-dried potato u,/u, was considered to be crystallinity for cellulose.
starch which sorbed moisture only for 15 d in atmosphere On the potatostarch, thevaluesofu,/u,showninTable 1 were
after having been dried in PzO5was not restored to the level of 0.24 for the air-dried material and 0.29 to 0.35 for the
the so-called air-dried one. Also,crystallinity of the moistened moistened one. Each value was almost the same as the values
potato starch seemed to have about similar values in the of 0.24and 0.28to 0.32in the references [l, 18,19,27].Thus,
moisture contents of 44 to 54%. the value of u,/u, for the potato starch was considered to be
crystallinity in the same manner as in the case of cellulose.
4 Discussion Moreover, the authors measured the value of u,/u, for the
Niigeli amylodextrin whose study was reported previously [6].
4.1 Crystallinity The Nageli amylodextrin was prepared as follows: l o g of
The studies on the crystallinity of starch by X-ray diffraction potato starch were hydrolyzed in 100ml of 16% sulfuric acid
method were reported only by Sterling [I8 -201 and Lelidvre at 30°Cfor 10 to 90 d. The acid treated material was washed
[21]and there were a few reports on the crystallinity. This is with distilled water and then hydroextracted by centrifuging
because a general determination method of crystallinity of at pF 3.93 to 4.20.Table 2 shows the changes in the value of
starch was nlit elucidated, and 100% and various ratio u,/u, and the hydrolysis ratio for potato starch by hydrolysis
crystalline samples of starch were not obtained. The authors time. The values of u,/u, were about 0.34,0.43and 0.46at the
studied the measurement of crystallinity of starch by means of hydrolysis time of 0, 60 and 90 d, resp.
the separation of crystalline and amorphous portions from The hydrolysis ratios at a hydrolysis time of 60 and 90d were
background in the X-ray diffractogram and moreover, by 1.25 and 1.33 times as many as that at hydrolysis time of 0 d,
referring to the reports by Hermans [12,15 - 171. resp. The increasing ratios of crystallinity at 60and 90d were
By assuming that the areas ofthex-ray reflection intensity for 1.18 and 1.28 times as much as that of the original one,
lOO%crystallineand 100%amorphous materials wereA,and respectively when calculated from the reciprocal of hydrolysis

starch/starke 35 (1983) Nr. 12, S . 407-410 409


Table 2.
Crystallinity of Niigeii Amylodextrin Prepared from Potato Starch by the Acid Hydrolysis Method. ac and ua Indicate the Crystalline and
Amorphous Portions in the X-Ray Diffractogram of Niigeli Amylodextrin, resp. Niigeli Amylodextrin was Prepared from Potato Starch by
Treatment with 16% Sulfuric Acid at 30°C.
Hydrolysis Time (d) 0 15 30 45 60 75 90
~

Hydrolysis ratio (%) 0 3.3 7.6 11.3 15.2 18.7 22.0


Hydrolysis residue (ratio) 1 0.967 0.924 0.887 0.848 0.813 0.780
l/Hydrolysis residue 1 1.04 1.08 1.13 1.18 1.23 1.28
a c (cm2) 37.5 43.9 45.3 47.9 48.3 48.8 50.5
zd. (crn’) 12.0 61.4 63.6 66.4 64.8 60.4 60.6
ciL ‘zt (ratio) 0.342 0.394 0.416 0.419 0.421 0.447 0.455
1 1.15 1.22 1.23 1.25 1.31 1.33
-

residue. The respective values of uc/ctt,1.25and 1.33 at 60 and Bibliography


90 days were very near t o the corresponding values of 1.18 and
1.28. From these results, the value of CI,/CI, for the Niigeli [l] Naru, S., A . Mori and T. Komiya: Starch/Starke 30 (1978),111.
[2] Nara, S.:Starch/Starke 30 (1978),183.
amylodextrin was considered to be crystallinity in the same [3] Nara, S.:Starch/Starke 31 (1979),73.
manner as in the cases of cellulose and potato starch. [4]Nara,S.,H.Takeoand T. Komiya:Starch/Starke33(1981),329.
Consequently, crystallinity was 0.71 k 0.02 for the moistened [5]Naru,S.:J.Jap.Soc.StarchSci.28(1981),24;in Japanese: Bull.
cellulose, 0.32 0.03 for the moistened potato starch and 0.46 Fac. Agr., Mie Univ. 64 (1982),39 in English.
for the Nageli amylodextrin. [6] Nara, S.,M . Sakakuraand T. Komiva: Starch/Starke35 (1983),
266.
4.2 Water saturated state [7]Hellman, N . N . , T. F. Baesch and E. H . Melvin: J. Am. Chem.
SOC.74 (1952),348.
The water contents of the moistened cellulose samples [8]Nara, S.,Y . Yabumoto, K. Yamaguchi and I. Maeda: J. Agr.
prepared by the vapor and the centrifuging methods [8, 91 Chem. SOC.43 (1969),570.
varied from 17 t o 28% but crystallinity ofthe samples showed [9]Nara,S., K . Yamaguchiand K.Okada:J.Jap.Soc.StarchSci.16
the nearly constant value of 0.71 f0.02. (1968),1.
Also, the crystallinity of the moistened potato starch samples
[lo] Kuge, T.,S.Suzuki and M . Nakamura: “Experimental Method
of Starch Science” (Jap.), Asakura (Tokyo) 1979,p. 132.
gave the nearly constant value of 0.32 k 0.03 in spite of the [ll]Barver, L. D . : “Soil Physics”, John Wiley and Sons New York
variation of the moisture content from 45 t o 55%. Conse- 1948, translated in Japanese by Y . Noguchi and H . Fukuda,
quently, it was difficult t o determine the water-saturated state Asakura (Tokyo) 1948,p. 222.
of cellulose and potato starch from the crystallinity by the X- [12]Alexander, L. E.: “X-ray diffraction methods in polymer
ray diffraction method. The relationship between saturated science”, John Wiley and Sons, New York 1969,translated in
moisture content (R) and crystallinity (x) was shown by the Japanese by F. Hamada and K . Kazi: I. Kagaku-dozin (Kyoto)
following equation (4) reported by Nara [2]: 1973,p. 64,74,pp. 150-155.
[I31 Hermans, P . H.,andA. Weidinger:J.Appl.Phys.19 (1948),491.
+ 1 -x)
R = 0.0667 ( 0 . 1 8 ~ (4)
[I41 Hermans, P . H., and A. Weidinger: J. Polym. Sci. 4 (1949),135.
[IS]Hermans, P . H . , and A. Weidinger: Makromol. Chem. 44-46
The saturated moisture content of cellulose was 0.279 when (1961),24.
calculated from the equation (4) with 0.71 of the average [16]Weidinger, A.,and P . H . Hermans:Makromol.Chem.50 (1961),
crystallinity. The value of 0.279 agreed with the fiber 98.
[I71 Challa, G., P . H . Hermansand A. Weidinger: Makromol. Chem.
saturated point of 0.28 [28]. Since this value was given by
56 (1962),169.
centrifuging at p F 3.93, it was considered t o be the moisture [I 8) Movsi, M . K. S., C. Sterling and D.H . Volman :J. Appl. Poly .Sci .
content of cellulose in the water-saturated state. When the 11 (1967),1217.
moistened materials were dehydrated by centrifuging at more [19]Sterling, C.:Starch/Starke 12 (1960),182.
than p F 3.93 and also when the air-dried ones sorbed moisture [20]Morsi,M. K . S.,and C . Sterling:CarbohydrateRes.3(1966),97.
by the vapor processing for 30d, these moisture contents [21]Leliivre, J . : Starch/Starke 26 (1974),85.
became smaller than that in the water-saturated state. [22]Hermans, P . H . : “Physics and Chemistry of Cellulose Fiber”,
The saturated moisture content of potato starch was 0.49 Elsvier, New York 1949,p. 316.
when calculated from the equation (4) with 0.32 of the average [23]Howsmon, J . H . : Textile Res. J. 19 (1949),152.
[24]Kast, W . : Z.Elektrochem. 57 (1953),525.
crystallinity. This value of0.49 was almost same as 0.509 and
[25]Oda, R . , S. Makizima, M . Imoto, W . Sakai and Y . Iwakura:
0.493 of the saturated moisture content by means of the vapor “Modern Industrial Chemistry 22. Industrial Chemistry of
processing reported by Hellman [7] and Nara [9], resp. Nqtural Resources,” Asakura (Tokyo) 1967,pp. 135- 153.
Consequently, the water-saturated state of potato starch was [26]Sobue, H., and S . Fukuhara: J. Chem. SOC.Japan, Ind. Chem.
considered t o be obtained by the vapor Brocessing for 30 d and Sect. 60 (1957),32.
by centrifuging at p F 4.20, since the saturated moisture [27]Zobel, H . F., and R . Senti: “Program of 45th Annual Meeting
content of potato starch was given as 0.49. American Associtation of Cereal Chemistry 1960”,p. 40;2.
Nikuni: “Handbook of Starch,” Asakura (Tokyo)1961,p. 64.
[28]Brown, H . P . , A . J . Panshin and C . C . Forsaith: “Text Book of
Wood Technol. (2)”,Mc. Graw Hill, New York 1952,p. 26.

Address of authors: Prof. Dr. Shozo Nara and Dr. Takashi Komiya,
Mie University, Faculty of Agriculture, Tsu, Mie-ken, 514 Japan.

(Received : February 18, 1983)


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41 0 starch/stlfke 35 (1983)Nr. 12,S. 407-410