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Article history: This paper presents the development of a new 3D printing food constructs based on fish surimi gel
Received 29 September 2016 system. This study investigated the influence of NaCl addition on rheological property, gel strength,
Received in revised form water holding capacity (WHC), water distribution and microstructure of surimi gel to be used as a
22 February 2017
material for 3D printing. The obtained results from rheological studies showed that the surimi gels made
Accepted 27 February 2017
Available online 27 March 2017
with 1.5 g NaCl/100 g surimi mixture can be used for 3D printing. NaCl addition is helpful for the slurry to
flow out from the nozzle in time and then get viscous post-deposition for holding its shape. Moreover,
the effects of the printing parameters on the geometrical accuracy and dimension of the printed surimi
Keywords:
3D gel-printing
gel were also studied. In this particular printing system, the 2.0 mm nozzle diameter, 5.0 mm nozzle
Surimi gelation height, 28 mm/s nozzle moving speed and 0.003 cm3/s extrusion rate were the optimal parameters to
Additive manufacturing print 3D samples with fine resolution, better matching with the target geometry, fewer point defects and
Rheological properties no compressed deformation. The overall results suggested that the 3D printing based on surimi gel
Printing parameters system is a promising method for producing complexed-shape food patterns.
© 2017 Published by Elsevier Ltd.
http://dx.doi.org/10.1016/j.jfoodeng.2017.02.029
0260-8774/© 2017 Published by Elsevier Ltd.
102 L. Wang et al. / Journal of Food Engineering 220 (2018) 101e108
properties for extrusion as well as can support its structure during cylinder measuring probe (P/0.5) attached to a TA. TX2 texture
and after printing process (Godoi et al., 2016). In a multicomponent analyzer (TA-XT plus, Stable Micro Systems, Ltd., Surrey, UK) at a
system, the change of proteins, carbohydrates, fat/oil and water will constant probe speed of 1.0 mm/min at room temperature
affect the melting behavior and plasticization of the food-materials (25 ± 1 C). The gel strength is defined as the initial force required
during 3D printing processes. The plasticization lowers the glass to disrupt the gels. Experiments were conducted in triplicate for
transition temperature of food polymers, such as starch, proteins each type of sample.
and carbohydrates (Bhandari and Roos, 2003) making them a
viscous printable material. 2.2.3. Water holding capacity (WHC)
Surimi is a typical intermediate fish product. Gelation of surimi WHC values of the surimi gels were determined according to the
is induced by the denaturation of protein and the subsequent ag- method of Zhang et al. (2015) with slight modifications. Samples
gregation of the unfolding protein (Cando et al., 2015; Jin et al., (3 g) were centrifuged at 8,000 g for 30 min at 4 C and the WHC (%)
2011). New textures can be created via surimi gelation mecha- was expressed as the final weight of the centrifugate as a per-
nism with gelatin, alginate and other polysaccharides governed by centage of the weight before centrifugation.
both partical based-gelation and hydrogel-forming mechanisms
(Tahergorabi and Jaczynski, 2012). Sodium chloride is commonly 2.2.4. Microstructure
used to solubilize the myofibrillar proteins and to induce the pro- Scanning electron microscopy (SEM) was performed to examine
tein unfolding. The final gels exhibited different rheological prop- the structural characteristics of surimi gels (Quanta-200, FEI Ltd.,
erties as the different amount of NaCl added (Cando et al., 2015). Netherlands) according to the method described by Liu et al. (2008)
The surimi is a viscous food gel system and that can be a with slight modifications. Gel samples (3 3 3 mm3) were fixed
promising food material for developing various 3D constructs. The in 0.1 M phosphate buffer (pH 7.0) containing 2.5% glutaraldehyde
main aim of this work is exploring the opportunity of 3D printing of for 24 h at 4 C, and then post-fixed in the buffer containing 1%
a surimi mixture. In this work, the effects of nozzle diameter size osmium tetraoxide for 5 h at 4 C. Samples were washed 3 times
(0.8, 1.5, 2.0 mm), nozzle height (5, 10, 15, 20 mm), nozzle moving with 0.1 M phosphate buffer, dehydrated in graded ethanol series of
speed (20, 24, 28, 32 mm/s), extrusion rate (0.002, 0.003, 0.004, 50, 70, 80, 90and 100% (v/v), and then vacuum-freeze-dried.
0.005 cm3/s) and material properties of surimi slurry induced by
different concentrations of NaCl (0, 0.5, 1.0, 1.5 g/100 g) on the 2.2.5. Low frequency-NMR relaxation measurements
extrusion behavior and final qualities of the 3D constructs were The 1H NMR measurements were carried out using a NMR
investigated. spectrometer (PQ001, Niumag Electric Corporation, Shanghai,
China) at 100 KHz, connected with an external circulating cryostat
2. Materials and methods bath to control the sample temperature in the magnet chamber.
Surimi sample was tightly packed up to 6 cm into a NMR sample
2.1. Surimi sample preparation tube with diameter of 10 mm, and put into the chamber. Transverse
(T2) relaxation was measured using the Carr-Purcell-Meiboom-Gill
Fresh silver carp fillet was purchased at a local market in Wuxi pulse sequence (CPMG) with 4 scans, 3000 echoes, 13.8 s between
city, China. The fish fillet was minced using a mechanical mincer scans, and 200 ms between pulses of 90 and 180 . The data were
(Model UM 5, Stephan Machinery Co., Hameln, Germany) with an analyzed by applying multi-exponential fitting of T2 relaxation data
orifice diameter of 4 mm. The minced fish was then washed with with the MultiExp Inv Analysis 4.09 (Niumag Electric Corporation,
cold water (4 C) using a mince/water ratio of 1:3 (v/w). Washing Shanghai, China).
was performed twice, and the washed mince was centrifuged at
700 g for 15 min at 4 C. Surimi moisture and pH were 82% and 6.8, 2.3. Printing process
respectively. Surimi mince was mixed with NaCl at different levels
(0, 0.5, 1.0, 1.5, 2.0% w/w) in a mixer HSN-29 (Wuzhe Food Machine The 3D printing system composed of the following three major
Co., Ltd, Wuzhe Town, Guangdong, China). The temperature of the parts: (i) feed hopper with auger mixer and conveyor, (ii) an
mixture was kept below 5 C during mixing. extrusion system, (iii) and a X-Y-Z positioning system using stepper
motors. The nozzle height (5, 10, 15, 20 mm) from the printing bed
2.2. Testing of material properties was achieved by adjusting the whole feeding device. The pressure
exerted on the surimi was applied via the extruder conveying
2.2.1. Rheological characterization screw. The surimi samples were extruded onto a polished trans-
The rheological properties of the mixed surimi slurry at different parent plastic polymer plate using nozzles of circular shape with
NaCl levels were characterized using a AR-G2 Rheometer (AR-1000, diameters of 0.8, 1.5 and 2.0 mm. The printing process was con-
Co. TA, USA) with a parallel plate (diameter ¼ 20 mm), at 25 C. The ductued at rome temperature (25 C). The motion and positioning
gap between two plates was set to 2.0 mm. For determination of control were provided by a computer with a specifically designed
steady shear viscositie, shear rate was ramped from 0.1 to 100 s1. Java program and micro controller.
Shear stress, shear rate, and steady shear (apparent) viscosity (h) To assess the effects on the extrudate geometry, line tests were
were recorded by a RheoWin 4 Data Manager (Rheology Software, used. Lines of surimi gel were extruded at varying extrusion rates,
Thermo Fisher Scientific, Waltham, MA). for different movement rates and the diameter of these lines was
Dynamic viscoelastic properties were characterized using small- then measured (Fig. 9). The line test samples were then cut to a
amplitude oscillatory frequency sweep mode. The frequency was known length and weighed.
oscillated from 0.1 to 100 rad/s, and all measurements were per-
formed within the identified linear viscoelastic region and made at 2.4. Statistical analysis
0.4% strain. The elastic modulus (G0 ), loss modulus (G00 ), and loss
tangent (tan d) were recorded. All tests were repeated three times. Analysis of variance was performed and mean comparisons
were run by Duncan’s multiple-range test using the SAS system for
2.2.2. Gel strength Windows 9.0 (SAS Institute, Cary, NC). Significant differences
The gel strength of the surimi gels was measured using a (p < 0.05) between mean values of samples were determined.
L. Wang et al. / Journal of Food Engineering 220 (2018) 101e108 103
3. Results and discussion myofibrillar protein and thus the increased interaction between
protein molecules as affected by NaCl addition (Tahergorabi and
3.1. The rheological behavior of the surimi gel Jaczynski, 2012). This enhanced gel strength could successfully
support its own weight during 3D printing and form the strong gel
The apparent viscosity curve of the surimi slurry is shown in patterned into three-dimensional structures.
Fig. 1A. The viscosity decreased significantly with the increased The water holding capacity (WHC) in surimi gels depends pri-
shear rate. This indicated that the surimi gels are pseudoplastic marily on the kind and number of protein-water interaction sites in
fluids and shear-thinning. Furthermore, increased NaCl concen- the gels. As shown in Fig. 2B, the WHC of surimi gels significantly
tration led to a general decrease in viscosity, which will be helpful increased with the increased NaCl addition, indicating an enhanced
for the slurry to flow out from the nozzle and then get viscous post- capacity of the gel network to hold water. This is consistent with
deposition for holding its shape. In light of surimi viscoelastic the reports that chloride ions bind to myofibrillar proteins and raise
properties, the storage modulus (G0 ) was higher than the loss the electrostatic repulsion between filaments, thus increasing the
modulus (G00 ) in the linear viscoelastic region (Fig. 1B and C), sug- protein’s affinity for water (Qin et al., 2015). This could result in a
gesting its potential to form elastic gel or gel-like structure. The G0 better gel network formation, causing a higher elasticity with
and G00 both progressively increased as a function of increasing strong water-holding capacity in the gel matrix. Meanwhile, WHC
oscillatory frequency, leading to the increased internal friction of could reflect the coarseness of surimi gel structure, as discussed
the material, as the losses (tand) are defined by G’/G’’. Besides, at below.
any oscillatory frequency, G0 and G00 continuously and significantly
decreased with increasing NaCl concentration from 0 to 1.5 g/100 g.
3.3. LF-NMR spin-spin relaxation times (T2) of surimi gels
This decrease might have been due to the denaturation of the
myosin tail (light meromyosin), which induced the redistribution of
NMR analysis showed the distributions of different types of
inter- and intra-molecular forces. In this way, the elastic compo-
water in surimi gel, which is related to its microstructure and
nent of the pre-gel structure was weakened and the fluidity of
physiochemical properties (Ahmad et al., 2007). It can be observed
surimi increased (Tahergorabi and Jaczynski, 2012). An ideal surimi
from Fig. 4 that there were four peaks in each sample, indicating
slurry should be able to keep the shape of extrudate as well as be
that the surimi proteins restricted the water mobility with different
mixable and printable below the maximum extrusion pressure of
magnitudes. Four relaxation populations of surimi gels were
the printer and capable of fusing with earlier printed layers. The
centered at approximately 0e1 ms (T2b), 7e20 ms (T21), 60e200 ms
decreased G0 and G00 of salted surimi slurry will be helpful for the
(T22), and 600e1000 ms (T23). Sanchez-Alonso et al. (2014) also
slurry to flow out from the nozzle.
reported that a typical NMR T2 signal for hake fish muscle proteins
exhibited four components, which were assigned to the bound,
3.2. Gel strength and WHC immobilized, partially immobilized, and free water, respectively.
As illustrated in Fig. 3, the water population that was tightly
Gel strength is one of the most important functional properties bound to macromolecules (T2b and T21) was not observed to have
of surimi gels (Lin et al., 2015). Results from Fig. 2A shows that significant differences in the four treatments. However, the T22
increasing addition of NaCl enhanced the gel strength. At the began to increase markedly with the increased NaCl addition,
highest concentration of NaCl (1.5 g/100 g), the gel strength indicating an alteration of water-protein interaction. Besides, the
reached to 7.20 N, representing an increase of about 2.0 times relaxation components T23 disappeared with the further addition of
compared with that of control. This is mainly due to the swelling of NaCl (above 0.5 g/100 g), which was believed to be associated with
A B
C D
Fig. 1. Rheological behavior (A. Apparent viscosity, B. G0 , C. G00 and D. tand) of the surimi gel at three NaCl level (0.5, 1.0 and 1.5% (w/w)).
104 L. Wang et al. / Journal of Food Engineering 220 (2018) 101e108
Fig. 2. Gel strength (A) and water holding capacity (B) of 3D printed surimi gels at three levels (0,0.5,1.0,1.5 g/100 g) of added NaCl.
the profusely swelling of myofibrillar proteins resulted in certain shapes exhibiting some spread in pore size and protein aggregates
level of the free water shifting to immobile water, and reduced the (Fig. 4A). Partially compact structure was also observed but the
abundance of water in surimi gels (Wang et al., 2016). The moisture entire product did not exhibit an obvious three-dimensional gel
status of the gel is closely related to its texture. So the corre- network. With NaCl addition, the micrographs of surimi gels
sponding gel strength was well improved. revealed a more aggregated structure compared with control gels
that exhibited a more regularly ordered structure, indicating that
NaCl addition caused cross-links of myofibrillar protein via bonding
3.4. Microstructure of surimi gels free amino acids to proteins, reducing the empty spaces and
changing the aggregate gel structure into a fine-stranded gel
The three-dimensional network structure is an important network to some extent. Nevertheless, at high NaCl concentrations
determinant of the functional properties of surimi gel, such as (above 1.0 g/100 g), there was no significant change observed,
WHC, strength, and rheology (Rawdkuen et al., 2009). Fig. 4 shows suggesting that the cross-link of surimi protein with 1.0 g/100 g of
the microstructures of surimi gels at different NaCl levels, signifi- the NaCl reached a saturation level. The improved gel structure was
cant differences in texture was observed between control gels and well consistent with the gel strength and WHC observations
the composite gels. The control surimi gels appeared uneven
L. Wang et al. / Journal of Food Engineering 220 (2018) 101e108 105
A B
C D
Fig. 4. Scanning electron microscope micrographs (magnification1: 200) of 3D printed surimi gels manufactured by NaCl addition. (A ¼ Control, B ¼ 0.5 g/100 g, C ¼ 1.0 g/100 g,
D ¼ 1.5 g/100 g).
previously described. The microstructure of surimi gels plays an nozzle height (hc) can be estimated using the following equation
important role in the 3D printing process, because a well-defined (Wang and Shaw, 2005):
network has excellent shape retention property, which is benefi-
cial to stabilizing the shape of surimi gels after printing. hc ¼ Vd =vn Dn (1)
A B
C D
Fig. 5. Different geometrical shapes of 3D printed surimi gel samples by the addition of three different levels of NaCl (A ¼ Control, B ¼ 0.5 g/100 g, C ¼ 1.0 g/100 g, D ¼ 1.5 g/100 g).
Extrusion parameters are nozzle diameter 2.0 mm, nozzle height 5.0 mm, nozzle moving speed 28 mm/s and extrusion rate 0.003 cm3/s.
A B C D
Fig. 6. Geometry shape of 3D printed surimi gel (NaCl content 1.5 g/100 g) samples using four different nozzle heights (A ¼ 20, B ¼ 15, C ¼ 10 and D ¼ 5 mm). Other extrusion
parameters are nozzle diameter 2.0 mm, nozzle moving speed 28 mm/s and extrusion rate 0.003 cm3/s.
leading to massively inaccurate sections (Hao et al., 2010). Ac- printing process in order to establish dynamic working range of a
cording to Equation (1), the critical nozzle height would be: 3D printer, which was expected to print a pattern that was com-
parable to that of the original design. The moving speed available
0:003 for printing was limited by the printer motors (from 1 to 40 mm/s).
hc ¼ ¼ 5:357mm
28 2:0 Changing the moving speed would affect its critical nozzle height
From this result, it is clear that the ideal build height for this when all other parameters were kept constant. If the moving speed
surimi mixture was 5.0 mm. During the printing process it was was much higher, the nozzle height calculated would be closer to
observed that when the nozzle hight was 5 mm, the printed objects its actual nozzle height (5.0 mm) used in the experiment. This
achived desired uniform shape with highest fieldity (Fig. 6D). means that no obvious forced flow of the slurry was present with
the nozzle moving speed. Too high speed (32 mm/s) can cause
dragging of the extruded filaments of products causing breaking of
3.5.3. Optimisation of nozzle diameter size
the extruded slurry filaments (Fig. 8D). While at very low moving
The nozzle size mainly affected printing precision and surface
speeds, the flow instabilities of slurry occurred resulting in the
roughness of the products (Vogeler et al., 2013). Obviously, the
formation of coils as shown in Fig. 8A, suggesting that the nozzle
dimensional resolution and surface quality of the final sample were
moving speed (28 mm/s) was found to be suitable as they produced
enhanced with the decreasing size of nozzle. But the pressure of
a higher-resolution and accuracy matching with models and fewer
extrusion increased with the reduced size of nozzle. Fig. 7 showed
borken lines (Fig. 8C).
the effects of the nozzle diameters on the geometric quality of
extrudates. It was apparent that the optimal diameter of nozzle was
2.0 mm. By using diameters of 0.8 and 1.5 mm (7A and B), relatively 3.5.5. Optimisation of the extrusion rate
poor models occurred for the extruded surimi was inconsistent in As shown in Fig. 9B, there is a liner relationship between the
both diameter and length. While when the nozzle diameter was extrusion rate and the diameters of surimi slurry that are collected
2.0 mm (Fig. 7C), both of the dimensional resolution and surface from the line tests. When the extrusion rate was high (Vd ¼ 0.004
quality of the final printed sample were the best compared to other and 0.005 cm3/s), the diameter was larger than the critical nozzle
conditions. size (Fig. 9A), indicating that the slurry had spread along the sub-
strate surface before it was set. This is because the higher the
3.5.4. Optimisation of the nozzle moving speed extrusion rate is, the greater volume of surimi slurry is extruded to
We also investigated the effect of nozzle moving speed on the give a larger diameter. When the extrusion rate was very low
L. Wang et al. / Journal of Food Engineering 220 (2018) 101e108 107
A B C
Fig. 7. Geometry shape of printed surimi gel samples (NaCl content 1.5 g/100 g) with different nozzle diameter size (A ¼ 0.8, B ¼ 1.5, C ¼ 2.0 mm). Other extrusion parameters are
nozzle height 5.0 mm, nozzle moving speed 28 mm/s and extrusion rate 0.003 cm3/s. NaCl content 1.5 g/100 g.
A B C D
Fig. 8. Geometry shape of printed surimi gel samples (NaCl content 1.5 g/100 g) with different nozzle moving speed (A ¼ 20, B ¼ 24, C ¼ 28, D ¼ 32 mm/s). Other extrusion
parameters are nozzle diameter 2.0 mm, nozzle height 5.0 mm and extrusion rate 0.003 cm3/s. NaCl content 1.5 g/100 g.
A B
Fig. 9. Relationship between extrusion rate and resulting diameter of surimi slurry (NaCl content 1.5 g/100 g). A: Line test of extruded surimi gel samples at varying extrusion rates;
B: Relationship between extrusion rate and resulting diameter of surimi slurry. Other extrusion parameters are nozzle diameter 2.0 mm, nozzle height 5.0 mm and nozzle moving
speed 28 mm/s. NaCl content 1.5 g/100 g.
(Vd ¼ 0.002 cm3/s), the extrusion pressure decreased, leading to an speed and the extrusion rate are also critical parameters influ-
inconsistent surimi slurry. From this relationship, the extrusion rate encing the geometry accuracy of the 3D surimi printing. The
can be determined to be 0.0028 cm3/s in order to give a 2.0 mm 2.0 mm nozzle diameter and 5.0 mm nozzle height were the
diameter. As the extrusion rates in the software can only be input as optimal parameters to provide good bonding between layers to
integer values, thereby the optimal extrusion rate was determined maintain proper geometry.
0.003 cm3/s.
4. Conclusions