LWT - Food Science and Technology 103 (2019) 131–138

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LWT - Food Science and Technology

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Effects of sodium carboxymethyl cellulose on rheological properties and T

gelation behaviors of sodium alginate induced by calcium ions
Jiong Zhenga,b,∗, Ruiqi Zenga, Fusheng Zhanga,b, Jianquan Kana,b
a
College of Food Science, Southwest University, Chongqing, 400715, China
b
Chongqing Engineering Research Center of Regional Food, Chongqing, 400715, China

ARTICLE INFO ABSTRACT

Keywords: Different concentrations of sodium carboxymethyl cellulose (CMC) were added into 1.0 g/100 g sodium alginate
Sodium alginate to investigate the rheological properties and gelation behaviors of the composite gel. Gluconic acid-δ-lactone
CMC (GDL) was used to release Ca2+ ions to induce uniform gel formation by sodium alginate. The effects of CMC on
Rheological properties critical gelation behavior during sodium alginate gelation were discussed. The sodium alginate/CMC composite
Gelation behavior
gel is still a shear thinning fluid, and its viscosity is positively related to CMC content. When CMC content is
Critical exponent
higher than 0.4 g/100 g, the composite viscosity (η*) differs from the apparent viscosity (η), and η* remains at
higher level than η. When CMC content is lower than 0.2 g/100 g, the gelation of sodium alginate accelerates,
and the gelation strength increases. However, when CMC content is higher than 0.4 g/100 g, the gelation ac-
celerates, but the gelation strength decreases with increasing CMC. The gel point of sodium alginate (ƒgel) is
delayed with increasing CMC. The critical exponent differs greatly when CMC content is higher than 0.2 g/100 g,
and the system loses self-similarity at the gel point. The fractal dimension of the composite gel increases initially
and then decreases with increasing CMC. The system develops the densest structure at 0.4 g/100 g CMC content.

1. Introduction Mixing two or more hydrophilic colloids according to production

Sodium alginate is a natural polysaccharide extracted from brown
alga (Laminariales, Phaeophyta). It is widely used in the food industry
because of its high stability, thickening property, solidification, and
ability to prevent food drying; these properties also allow it to be ap-
plied in bioengineering or pharmaceuticals industries as a high-polymer
material (Bhat & Aminabhavi, 2007; Grant, Morris, Rees, Smith, &
Thom, 1973; Yu, Wang, Chen, Li, & Wang, 2018). Sodium alginate is an
anionic polyelectrolyte. The molecule is a linear alginic acid segmented
copolymer formed by β-D-mannuronic acid (M (or G) unit) through 1–4
glucosidic bonds (Gombotz & Wee, 1998; Grasdalen, Larsen, &
Smidsrod, 1981). Alginate gelation is triggered in the presence of bi-
valent cations (Ca2+), wherein chains establish junction zones called
egg-box structure (Grant, Morris, Rees, Smith, & Thom, 1973). How-
ever, the gel formed by adding Ca2+ into sodium alginate solution has
poor uniformity and instability. A uniform gel can be achieved by the in
situ release of cations (Bellich, Borgogna, Cok, & Cesaro, 2011; Li, Hu,
Du, Xiao, & McClements, 2011). Currently, many scholars use the
gluconic acid-δ-lactone (GDL) as an acidifier to prepare sodium alginate
gel (Kalaf, Flores, Bledsoe, & Sell, 2016; Mession et al., 2013; Sadeghi-
Mehr, Raudsepp, Bruggemann, Lautenschlaeger, & Drusch, 2018).
demands can offset shortages of one colloid or enhance some proper-
ties. Currently, studies on sodium alginate in admixture with hydro-
philic colloids mainly concentrate on the formulation of sodium algi-
nate, xanthan gum, and pectin (Braccini & Perez, 2001; da Silva,
Bierhalz, & Kieckbusch, 2009; Kondakci, Ang, & Zhou, 2015). A pre-
vious study found that in the presence of Ca2+, the gel formed after
sodium alginate reacts with high methoxyl pectin has high gel strength,
and the gelation accelerates (Walkenstrom, Kidman, Hermansson,
Rasmussen, & Hoegh, 2003). Another study also discovered that the
mechanical energy of the gel created from a combination of pectin and
sodium alginate increased and that the molecular network structure
was changed, thereby restricting molecular movement (Gohil, 2011).
Sodium carboxymethyl cellulose (CMC) is the main representative
product of ionic cellulose gum and is utilized by food industries for its
bulking, thickening, water absorption, stability, and gelation abilities
(Du et al., 2009). The blending of CMC and other hydrophilic colloids
can have a considerable enhancing effect on foods. For example, the
blending of CMC and gelatin can increase the water-retaining property
of foods (Duhoranimana et al., 2017). The mixture of CMC and gelatin
reportedly results in enhanced water-retaining property in foods. CMC
and carrageenan mixture or guar gum can increase the melting

∗
Corresponding author. College of Food Science, Southwest University, Tiansheng Road 1, Chongqing, 400715, PR China.
E-mail address: zhengjiong_swu@126.com (J. Zheng).

https://doi.org/10.1016/j.lwt.2018.12.081
Received 29 September 2018; Received in revised form 27 December 2018; Accepted 31 December 2018
Available online 03 January 2019
0023-6438/ © 2019 Elsevier Ltd. All rights reserved.
J. Zheng et al.
resistance of foods and improve their taste (Hayati, Ching, & Rozaini,
2016; Regand & Goff, 2003). The blending of CMC and xanthan gum
can replace pectin in the saccharose-organic acid model system (Ozgur,
Dogan, & Karaman, 2017).
The composition of CMC and sodium alginate exhibits large changes
in both of their functional properties because of their interaction.
However, associated studies have been rarely reported. The interaction
between sodium alginate and CMC was studied in this paper. CMC was
added into sodium alginate and GDL was used for releasing Ca2+ which
induce gelation of sodium alginate. Changes in apparent viscosity,
composite viscosity, and dynamic modulus of the composite gel are
investigated by rheological means. Microstructural changes in the
composite gel were observed by scanning electron microscope (SEM).
Winter-Chambon criterion was used to analyze the effect of CMC on the
critical gel behaviors of sodium alginate. Fractal structural changes of
sodium alginate were assessed by calculating the fractal dimension.
2. Materials and methods
2.1. Materials
The following were used: food level sodium alginate (Qingdao
Bright Moon Seaweed Group Co., Ltd, China), CMC (food level,
Qingdao Bright Moon Seaweed Group Co., Ltd, China), EDTA (analy-
tical pure = 99%, Aladdin Reagent (Shanghai) Co., Ltd, China), CaCl2
(analytical pure, Aladdin Reagent (Shanghai) Co., Ltd, China), gluconic
acid-δ-lactone (GDL) (food level, China Jiangxi New Yellow River
Pharmaceutical Food Chemical Co. Ltd.), and NaOH (analytical pure,
Aladdin Reagent (Shanghai) Co., Ltd, China). The viscosity of 3 g/100 g
sodium alginate aqueous solution at 20 °C is 500 mPa s, Mn = 357,475,
Mn/Mw = 1.392; whereas the viscosity of 1 g/100 g CMC aqueous so-
lution at 20 °C is 300–800 mPa s, Mw = 700,000, Mn/Mw = 1.429, and
the degree of substitution is 0.9).
2.2. Generation of Ca2+ releasing curve
EDTA solution (25 mL of 0.06 mol/L) and CaCl2 solution (25 mL of
0.06 mol/L) were mixed, with the pH adjusted to 7.0 using NaOH. The
mixture was dissolved to a constant volume in a 100 mL volumetric
flask whereas the concentration of EDTA-Ca solution was controlled at
0.015 mol/L. R was defined as the molar concentration ratio between
GDL and EDTA-Ca, or R = [GDL]/[ EDTA-Ca]. Different volumes of
GDL were added into the prepared 0.015 mol/L EDTA-Ca solution,
which was stirred evenly to assure complete reaction. The mixture was
left to stand for 3 h to test the pH. The pH test values served as the y-
axis and R values served as the x-axis in plotting the Ca2+ release curve.
Based on the Ca2+ release curve, the relationship between pH and R
can be drawn: y = 0.0328x4 – 0.2954x3 + 1.0224x2 – 1.832x +
5.5924. From this equation, a pH of 4.0 reached at equilibrium and R
value of 2.86 after 3 h is computed. The GDL mass fraction which has to
be added is 0.764 g.
The ƒ value is the molar concentration ratio between Ca2+ in
composite gel and carboxyl in sodium alginate. Given the fixed sodium
alginate concentration, Ca2+ content in the system is expressed by the ƒ
value. The ƒ value is expressed as:
[Ca2 +]
f=
[COO ] (1)
2.3. Preparation of composite gel
A control group (CG) of single sodium alginate solution was pre-
pared by dissolving 0.5 g of sodium alginate into 50 mL deionized
water. After full dissolution, 0.05, 0.2, 0.4, 0.8 and 1.0 g/100 g CMC
were added and dissolved by heating. After the sodium alginate and
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LWT - Food Science and Technology 103 (2019) 131–138
CMC were dissolved completely, a transparent composite gel solution
was formed and used to prepare two groups of composite gel solutions.
One group was used to test apparent viscosity and composite viscosity.
The other group was used for dynamic rheological test. Different
amounts of EDTA-Ca were added in dynamic rheological test samples
and mixed completely. 0.764 g GDL was added and mixed evenly. The
mixture was left to stand for 24 h to test the dynamic rheological
characteristics of the composite gel.
2.4. Test of apparent viscosity and composite viscosity
A few samples were placed in the panel of rheometer (DHR-1, TA
Instruments, New Castle, USA) and the plate measuring system was
used. The plate diameter and space were set 40 mm and 1.0 mm, re-
spectively. The surface was coated with silicone oil to prevent water
evaporation. All samples were reached equilibrium for 5 min before the
test to achieve constant temperature of 25 °C.
Apparent viscosity test: the temperature was set 25 °C. The shear
rate was increased gradually from 0 to 100 s−1 and then decreased from
100 to 0 s−1. Variations in apparent viscosity (η) and shear stress (τ)
with the shear rate (γ) were recorded. The regression fitting of static
shear data points was carried out by the Power-law model shown
below.
=K n
(2)
−1
where τ is the shear stress (Pa), γ is the shear rate (s ), n is the flow
behavior index, and K is the consistency coefficient (Pa•sn).
Composite viscosity test: temperature was set 25 °C. The scanning
strain was determined to be 5% by testing the linear viscoelasticity in a
preliminary experiment. Composite viscosity (η*) values with angular
frequency (ω) between 0.1 and 100 rad/s were tested.
2.5. Dynamic rheological test
Samples were collected based on apparent viscosity test methods for
dynamic viscoelasticity test. The temperature was set to 25 °C and the
linear viscoelastic region was tested in the preliminary experiment. The
scanning strain was determined to be 5%. Variations of storage mod-
ulus (G′) and loss modulus (G″) with ω between 0.1 and 100 rad/s were
tested.
Relaxation modulus test: a fixed shear strain (20 Pa) was applied
and the variations of the relaxation modulus (G(t)) with time were
tested. The relaxation time was set to 20 s.
Dynamic time scanning: an equal volume of EDTA-Ca solution was
added to the composite gel system. After 0.764 g GDL was added, the
mixture was stirred magnetically for 1 min and the samples were ap-
plied onto the rheometer quickly to begin the test. The gelation process
of each composite gel was monitored by small-amplitude dynamic time
scanning. The experimental frequency, scanning strain, and scanning
time were set 1 Hz, 5%, and 3 h, respectively. A total of 720 data
sampling points was set.
2.6. SEM observation
The composite gel system was poured into the culture dish and then
frozen for 24 h. After the water was frozen completely, the samples
were placed in a freeze dryer (SCIENTZ-10ND, Ningbo Xinzhi
Biotechnology Co., Ltd., China). The samples were processed by va-
cuum freeze drying at −55 °C for 72 h to complete drying. All dried
samples were put on an aluminum sheet which is conductive on both
surfaces and coated with polarium. The conductivity of the samples was
measured by an ion splashing machine. The samples were observed and
photos were taken by a tungsten filament SEM (JSM-6510LV, Japan
Electronics Corporation) with an acceleration voltage of 15 Kv and an
amplification of 2 k–6 k×.
J. Zheng et al. LWT - Food Science and Technology 103 (2019) 131–138

Fig. 1. Relationship curve between shear stress (τ) and shear rate (γ) of the Fig. 2. Comparison between apparent viscosity, η (open symbol) and composite
composite gel system. Solid symbols as the uplink line (the curve of the shear viscosity, η* (solid symbol) of sodium alginate under different CMC content.
force applied to the sample when the shear rate varies from small to large),
open symbols as the downlink line (the curve of the shear force applied to the The Cox-Merz criterion states that, considering equivalence, η and
sample when the shear rate varies from large to small). η* are equal (Vernon-Carter, Avila-de la Rosa, Carrillo-Navas, Carrera,
& Alvarez-Ramirez, 2016). Comparisons between η and η* of sodium
2.7. Data processing alginate under different CMC content are shown in Fig. 2. There is a
small gap between η and η* for the single sodium alginate solution,
Tests were repeated three times. Relevant diagraphs were drawn indicating that the sodium alginate meets the Cox-Merz criterion. In-
using Origin 9.0. Analysis of variance was carried out using SPSS 11.5. creasing the CMC contents gradually increases both viscosity indexes of
Difference of means was tested using Duncan's method (p < 0.05). the composite gel system. However, the gap between η and η* of the
composite gel system increases after adding 0.05 g/100 g CMC. In the
3. Results and discussions low-frequency region (0.1 < ω < 1), η > η*, which reflected that the
structure is disrupted during the frequency sweep test by small ampli-
3.1. Effects of CMC on the viscosity of sodium alginate tude rheology than that due to the shear thinning (Augusto, Ibarz, &
Cristianini, 2013). When the CMC content is 0.2 g/100 g, the η* of the
The relation curve between shear stress of the composite gel system composite gel system begins to increase and becomes significantly
and shear rate is shown in Fig. 1. With the gradual increase of shear higher than η of the solution. At 0.8 g/100 g CMC content, η* is still
rate, the shear stress of the composite gel system increases con- higher than η. At this concentration, η* and η deviate from the Cox-
tinuously. In the increasing and the decreasing stages of the shear rate Merz criterion. CMC may induce change in interaction between alginate
sweep measurements, the relation curves of shear stress almost overlap chains in solution, thereby changing the solution behaviors (Augusto,
completely. This demonstrates that the composite gel system has good Falguera, Cristianini, & Ibarz, 2013).
recovery performance under the effect of external forces. Increasing the
CMC content gradually increases the shear stress of the composite gel. 3.2. Gelation process of the sodium alginate
Compared with the CG system, the shear stress of composite gel with
CMC is higher, which might be caused by high viscosity of CMC (Cho, Changes of G′ and G″ with time upon releasing in situ Ca2+, indu-
Choi, & You, 2009). cing gelation of the system, are shown in Fig. 3. In the beginning of
The Power-law model was used to fit the data points on the com- gelation, G′ and G″ of the sodium alginate have been in the smooth
posite gel system curve (Table 1). The fitting accuracy reached 0.98, state. G′ and G″ of the CG begin to present a sharp increase at nearly
indicating that the Power-law model can be applied to the composite 2 h. In this case, sodium alginate combines with Ca2+ slowly and the
gel system. The n value of the composite gel mixture is smaller than that gelation speed is relatively low. G′ is always lower than G″ and the
of CG. With the increase of CMC content, the n value of the composite viscosity property is dominant. By increasing the CMC content, the
gel mixture declines gradually, indicating the gradual enhancing gelation of composite system occurs earlier than in the case of CG so-
pseudoplasticity of the composite gel system. The n value of the com- lution. In particular, the sharp growth of G′ of the composite system
posite gel system is lower than 1, indicating that this system has typical with 0.4 g/100 g CMC content occurs 120 s after the gel point and
pseudoplasticity. Adding CMC in the studied concentration range fails G′ > G′′. Elastic component begins to take the dominant position in the
to change the fluid property of sodium alginate. The consistency coef- system. In this case, Ca2+ cations and alginate chains interact to each
ficient presents an increasing trend. The system is a type of shear other, so that they could establish a network that strengthened owing to
thinning fluid with the increase of viscosity. molecular rearrangements. Increasing the CMC content within compo-
site gel system resulted in lowering of both moduli at plateau value.
Table 1
Although the gelation point of the composite system occurred earlier
Power-law parameters of the sodium alginate/CMC composite gel system.
than that for CG, the gel strength decreased. This might be because
Sample (g/100 g CMC) Upward curve Downward curve CMC and sodium alginate compete for Ca2+, thereby weakening the
n 2
ability of sodium alginate to combine with Ca2+. The number of cross-
K(Pa•s ) n R K(Pa•sn) n R2
links decrease, which declines the gel strength of the composite system
CG 1.5000 0.7294 0.9975 1.5471 0.7229 0.9975 (Karaca, Erdem, & Ak, 2018; Nakauma et al., 2016).
0.05 2.7547 0.6964 0.9962 3.5507 0.6416 0.9958 The microstructure of the composite gel system is shown in Fig. 4.
0.2 4.4855 0.6455 0.9953 5.5748 0.5911 0.9947 Single sodium alginate combines with Ca2+ into a uniform gel with few
0.4 7.9889 0.5753 0.9932 9.0213 0.5490 0.9933
large pores on the surface. After CMC is added, a network structure is
0.8 24.3114 0.4843 0.9894 25.7705 0.4718 0.9890
1.0 45.0754 0.4339 0.9856 44.9635 0.4335 0.9859 formed on the composite gel surface, which appears rougher than that
for single sodium alginate. At 0.05 g/100 g CMC content, regular

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J. Zheng et al. LWT - Food Science and Technology 103 (2019) 131–138

Fig. 3. Variation curves of storage modulus, G′ (solid symbol) and loss modulus, G′′ (open symbol) of the composite system with time.

network structures are formed on the composite gel surface. At 0.2 g/
100 g CMC content, the network structure is enhanced. As CMC content
increases to 0.4 g/100 g, there is hardly an open region in composite gel
system and the gel surface is smooth (Loren et al., 2009). The gel net-
work in this system is dense and runs through the whole system. With
the further increase of CMC content, the structure of the composite gel
begins to collapse. The structure is more discontinuous by increasing
CMC content at grate higher than 0.4 g/100 g, with coarse strands en-
trapping large pores. At 1.0 g/100 g CMC content, the smooth surface of
composite gel disappears and the network structure decreases. The
strands appeared coarser, their connectivity may be more random, in-
dicating that CMC content weakens the structure of the composite gel
system (Shi, Wei, Luo, Tan, & Cao, 2018).
3.3. Dynamic viscoelasticity of the sodium alginate/CMC composite gel
The variation curves of G′ and G″ moduli of the composite gel
system with angular frequency under different f values (Eq. (1)) are
shown in Fig. 5. Change in the viscoelasticity of the composite gel
system are reflected by these curves. The transformation of the state of

Fig. 4. Microstructure of the sodium alginate/CMC composite gel system.

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J. Zheng et al.
Fig. 5. Variation curves of storage modulus, G′ (solid symbol) and loss modulus, G′′ (open symbol) of the composite gel system with angular frequency (ω) under
different f values.
a single sodium alginate from sol to gel induced by Ca2+ is shown in
Fig. 5a. When the ƒ value is 0.67, G′ < G'′ for the sodium alginate in the
whole test range, and the system remains liquid. In the low-frequency
region, G′ of sodium alginate is far lower than G′′. However, the gap
between them narrows with increasing angular frequency. In the high-
frequency range, G′ and G″ curves of sodium alginate tend to overlap,
but G′ is still lower than G′′. This implies that highest amount of energy
in the test goes to viscosity flow, thereby showing fluid-like viscoelas-
ticity characteristics (Maa, Lin, Chen, Zhao, & Zhang, 2014). When ƒ
value increases to 0.84, G′ of the sodium alginate begins to exceed G″,
and their curves keep a parallel state in the whole test range of angular
frequency. The system mainly develops elasticity features, which means
that the sodium alginate system has achieved gel transformation.
After the addition of CMC, significant changes are detected in the
relationship between the viscoelasticity of the composite gel system and
Ca2+ content. At 0.05 g/100 g CMC content, the viscoelasticity char-
acteristics of the system are close to those of CG system. Nevertheless,
with increasing Ca2+ content, the composite gel shows typical elasticity
behavior gradually. It can be seen from Fig. 5b that the ƒ value of
composite gel with 0.05 g/100 g CMC is 0.84 and G′ and G″ almost
overlap completely. The system is viscoelastic, and then it transforms
into a gel state. When the ƒ value continues to increase 1.0, the elastic
component of the system improves. In the whole test range, G′ is always
slightly higher than G″, and the system presents weak gel behaviors.
When ƒ value increases to 1.67, G′ begins to be significantly larger than
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LWT - Food Science and Technology 103 (2019) 131–138
G′′. A space-filling network results from crosslinking of alginate chains
via calcium cations. At this moment, the elastic component increases
more rapidly than the viscous one (Fang, Takahashi, & Nishinari,
2004).
When the CMC content is ≤ 0.2 g/100 g (Fig. 5c), G′ and G″ almost
intersects when ƒ value is 0.67. Upon further increase of CMC content,
the intersection between G′ and G″ occurs, while the Ca2+ content in-
creases. When the CMC content is 0.4 g/100 g (Fig. 5d) and ƒ value is
0.84, the system presents an apparent intersection between G′ and G′′.
The ƒ value has to be 1.0 to develop a weak gel. Further increasing the
CMC content continuously increases Ca2+ needed for the gelation
process. When the CMC content is 0.8 g/100 g (Fig. 5e), the ƒ value
corresponding to the necessary Ca2+ content for gelation is 1.20, and
the elastic gel can only be formed when the ƒ value is 1.67. At 1.0 g/
100 g CMC content (Fig. 5f), the ƒ value for the system to form an elastic
gel is higher than 1.67. To a certain extent, adding CMC favors the
formation of an elastic gel by sodium alginate. However, when the CMC
content exceeds 0.4 g/100 g it will hinder the gelation behavior of so-
dium alginate (Karaca et al., 2018).
3.4. Critical gelation behavior of the composite system
Critical gelation uses gel strength (S) and critical exponent (n) as the
characteristics (Eq. (3)). The relaxation modulus G(t) and n at the cri-
tical gel point present the Power-law relationship (Winter & Chambon,
J. Zheng et al. LWT - Food Science and Technology 103 (2019) 131–138

Table 2
Parameters at the gel critical point for the sodium alginate/CMC composite gel
system.
Sample (g/100 g CMC) ƒ n1 n2

CG 0.8428 0.386 0.387

0.05 0.8375 0.287 0.286
0.2 0.9264 0.324 0.335
0.4 0.9231 0.365 0.340
0.8 1.0024 0.260 0.258
1.0 1.3241 0.250 0.254

Table 3
Fractal dimension for critical gelatinization of the sodium alginate/CMC com-
Fig. 6. Curves of relaxation modulus (G(t)) of the composite gelatinization posite gel system.
system at the critical gel point. Sample (g/100 g CMC) dƒ1 dƒ2 dƒ1′ dƒ2′

CG 5.77 5.75 2.13 2.14

1986). Winter-Chambon method is often used to determine the critical 0.05 7.45 8.49 2.15 2.18
gel point. In Fig. 6, the relaxation modulus of the composite gelation 0.2 6.26 6.96 2.19 2.18
system close to the critical gel point and time has a linear relationship 0.4 5.22 6.82 2.27 2.26
0.8 8.54 9.63 2.26 2.27
in the double logarithmic coordinate system, thereby indicating that the
1.0 9.00 9.81 2.24 2.24
critical gelation of the composite system upon gelation is in agreement
with the relaxation modulus equation (Muthukumar, 1989):
G (t ) = St n
(3)

Fig. 7. Relationship curve between loss tangent (tanδ) of the composite gel and ƒ at the critical gel point.

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Winter and Chambon (1986) discovered that G′ and G″ close to the
gel point have the same Power-law dependence to the angular fre-
quency (ω) (Eq. (4)). In Fig. 5, G′ and G″ values of the composite system
are almost parallel in the double logarithmic coordinate system. This
reflects that G′ and G″ values of the system show the same Power-law
dependence to the angular frequency (ω).
n (4)
G G
By combining the universal relaxation modulus equation and the
dependence of G′ and G″ on angular frequency (ω), the loss factor be-
comes unrelated with angular frequency (Eq. (5)). This method can
determine the gel point of the system quickly.
G n
tan = = tan (0 < n < 1)
G 2 (5)
The relationship curve between tanδ of the composite gel and ƒ is
shown in Fig. 7. While adding different Ca2+ concentrations, tanδ of the
composite gel system loses angular frequency dependence at the critical
gel point and converges at one point, whereas tanδ is unrelated to ω.
With little or no CMC content in the system, the system begins to
transform from sol to gel when ƒ value is about 0.84. With the con-
tinuous increase of CMC content, the Ca2+ content needed to develop
the critical gel point is gradually increased.
The critical exponent can be calculated from the straight slope
(Fig. 6). The critical exponent at this point is recorded as n1. However,
tanδ intersects at one point under the critical gel point, and does not
show dependence on angular frequency (Eq. (5)). The corresponding
critical exponent is n2. The critical gel parameters of the composite
system are listed in Table 2. In the CG and 0.05 g/100 g CMC system,
the critical exponent values are similar, indicating that the composite
gel system has structural self-similarity at the critical gel point. When
the CMC content is higher than 0.2 g/100 g, there is a large gap be-
tween n1 and n2, indicating that the gel system has no self-similarity. It
might be that the heterogeneous structure is formed in the system with
the increase of CMC content, which hinders the random crosslinking in
the gelation process and thereby destroys the formation of self-simi-
larity in the molecular structure (Mours & Winter 1996).
3.5. Fractal structure of critical gelation in the composite system
Muthukumar (1989) and Winter and Chambon (1986) studied the
relationship between critical exponent (n) and fractal dimension (dƒ)
when the repulsive volume is shielded completely during the gelation
process of a polydispersion gel system. They further discussed the in-
teraction of gel crosslinking based on the percolation theory and found
that when the fluid dynamics is shielded completely, and the repulsive
volume is considered, the relationship between n and dƒ becomes Eq.
(6), where d is the spatial dimension (set 3 in this experiment).
d and its modified membranes - a review. Separation and Purification Reviews, 36(3–4),
n=
df + 2 (6)
When the fluid dynamics and repulsive volume are shielded com-
pletely, the relationship between n and dƒ´ is:
d d (d + 2 2d f )
n= = Coacervates characterization, stabilization and formation mechanism. Food
df + 2 2(d + 2 df ) (7)
The fractal dimension number for the critical gelation of the com-
posite gel system is shown in Table 3. When the repulsive volume be-
comes dominant because of shielded fluid dynamics, the fractal di-
mension numbers calculated by n1 and n2 are higher than 3, which are
higher than selected values in other studies. Thus, it is unreasonable to
calculate the fractal dimension number from the Eq. (6). Therefore,
repulsive volume cannot be viewed as the dominant factor. When fluid
dynamics and repulsive volume are shielded completely, the fractal
dimension numbers calculated by n1 and n2 are smaller than 3, and the
difference between dƒ1′ and dƒ2′ is smaller. With increasing CMC
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LWT - Food Science and Technology 103 (2019) 131–138
content, dƒ increases initially then decreases. When the CMC content is
higher than 0.2 g/100 g, the growth amplitude of dƒ′ is high. When the
CMC content is 0.4 g/100 g, the composite gel has the largest dƒ1′, which
is reflected as a denser and ordered structure of the composite gel
system. Low CMC content (≤0.4 g/100 g) might increase the con-
centration of sodium alginate, which leads to the dense structure of the
system at the critical gel point (Liu et al., 2004). When CMC content
exceeds 0.4 g/100 g, dƒ1′ is decreased slightly, and the system structure
is slightly loosened. When the CMC content increases to 0.8 g/100 g,
CMC becomes dominant in the system and combines with the abundant
Ca2+, thereby forming a weak gel with loose structure (Liu et al.,
2004).
4. Conclusions
CMC can substantially affect the rheological properties and critical
gelation behaviors of sodium alginate induced by Ca2+. The viscosity of
sodium alginate is positively related with CMC content. When the CMC
content is higher than 0.4 g/100 g, the composite viscosity differs from
the apparent viscosity. GDL acidification is used to release Ca2+ to form
the uniform gel. The gel point occurred earlier in presence of CMC in
the content of 0.05–0.2 g/100 g than that for CG. The gelation speed of
sodium alginate and the gel strength are increased. However, the gel
strength is decreased after 0.8 g/100 g. With the gradual increase in
CMC content, the ƒgel point of the composite gel system is delayed. At
the same time, a significant gap in the critical exponent occurs, and the
self-similarity of the composite gel disappears when the CMC content is
higher than 0.2 g/100 g. The system develops the densest structure at
0.4 g/100 g CMC content. Studying the effect of CMC on sodium algi-
nate brings widens the application of sodium alginate, which suits it
better to the application demands of food, biological fields, and medi-
cine.
Acknowledgements
This work was supported by the Fundamental Research Funds for
the Central Universities (XDJK2016B035; SWU115051) National
Natural Science Foundation of China (Grant No. 31701617).
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