Food Freezing: Emerging Techniques For Improving Quality and Process Efficiency A Comprehensive Review

3.
03 Food Freezing: Emerging Techniques for Improving Quality and Process

Efficiency a Comprehensive Review
Suresh G Sutariyaa,b and Venkateswarlu Sunkesulab, a Agropur, Appleton, WI, United States; and b Dairy and Food Science
Department, South Dakota State University, Brookings, SD, United States
© 2021 Elsevier Inc. All rights reserved.
3.03.1 Introduction 36
3.03.2 Basics of Freezing Fundamental 37
3.03.3 Impingement Freezing 38
3.03.4 Hydro-Fluidization 39
3.03.5 High Pressure Assisted Freezing 41
3.03.6 Ultrasonic Assisted Freezing 43
3.03.7 Freezing Assisted by Magnetic Field 46
3.03.8 Electric Field Assisted Freezing 47
3.03.8.1 Static Electric Field Assisted Freezing 47
3.03.8.2 Fluctuating Electric Field Assisted Freezing 50
3.03.9 Microwave Assisted Freezing 52
3.03.10 Radio-Frequency Assisted Freezing 54
3.03.11 Freezing Assisted Biosubstances Capable of Regulating Freezing Point Depression 55
3.03.11.1 Antifreeze Proteins 55
3.03.11.2 Ice-Nucleating Proteins (INPs) 55
3.03.11.3 Natural Deep Eutectic Solvents 55
3.03.12 Conclusions 58
References 59
3.03.1 Introduction
In history of humankind, we learned to control and use fire to cook food about a couple of million years ago. However, learning to
harness ice beyond the chilling winter months to preserve the food by freezing took much longer. Based on documented history, the
Chinese were the first to use the power of ice to freeze and preserve food by storing it in ice cellars circa 1000 BC. The Greeks and
Romans also learned to store food in insulated cellars along with compressed snow. The Egyptians and Indians knew all about rapid
evaporation through porous walls of clay pot and keeping food cool by storing in it, and also producing ice crystals in them. These were
all cradles of human civilization but modern man took a while to freeze and transport food at commercial level (William et al., 2005).
For food preservation, freezing is one of the oldest and most widely used method. Food preserved by freezing helps maintain
better taste, appearance and nutritional value than any other method. Freezing of food slows chemical reactions, arrest the micro-
organism growth and reduces cellular metabolic reactions (Delgado and Sun, 2001; George, 1993). Early inventors such as Enoch
Piper, William Davis, and Daniel E. Somes are considered as pioneers in developing mechanical methods for freezing of food.
However, Clarence Birdseye is credited with inventing as many as 168 patents, which enabled the production of the type of frozen
foods that we know today. These patents were focused on rapid freezing of foods to prevent large ice crystals formation and protect
food cell wall against rupture by such large ice crystals, which was responsible for damaging food structure and hence affecting it
acceptability. These patents also include packaging, type of paper used, and related innovations to support the rapid freezing
processes. This was the beginning of modern rapid freezing and now in the modern age of globalization there are various advances
made in the field of innovative freezing technologies.
The growing demand for minimally processed, additive-free and natural food products has brought back the good opportunity
for frozen food market and it’s one of the factors that is driving the positive growth of the frozen food market. The global frozen
food market size was estimated at USD 280.08 billion in 2018 and is projected to expand at a CAGR of 4.3% from 2019 to 2025
(Research Grand View, 2019). Frozen food market size in USA was estimated to be USD 56.7 billion with 2.6% growth in 2018
(Foodnavigator, 2019). Frozen food market growth is accelerating compared to other packaged foods as the consumer perception
of the category changes. Consumers are now beginning to see freezing as a way to preserve food in its most natural from, in contrast
to other preservation technologies based on external additives or extensive processing. Competing with new technologies of
minimal processing of foods, industrial freezing is still the most satisfactory method for preserving quality of food in its most
natural from during long storage periods (Arthey, 1993). The growing trend of the frozen food industry has also fueled the need
for new technologies for improving freezing process efficiency and its cost, incorporation of new technologies along with freezing
to assist in reducing the food structure damage, retaining its quality and improving its microbial quality. In this chapter we have
tried to provide a comprehensive review on the recent developments in emerging food freezing technologies.
36 Innovative Food Processing Technologies, Volume 3 https://doi.org/10.1016/B978-0-08-100596-5.23035-7

Food Freezing: Emerging Techniques for Improving Quality and Process Efficiency a Comprehensive Review 37
3.03.2 Basics of Freezing Fundamental
The process of freezing involves 3 key steps: (i) precooling, (ii) phase transition, and (iii) tempering. During precooling step (A and B
in Fig. 1), sensible heat is removed from the product to lower its temperature. Once the freezing point (TF) is reached, phase transition
is not usually triggered immediately, but cooling continues. Therefore, at the end of the precooling step, the product still remains in
unfrozen state (supercooled state) below its freezing point for certain period. At a certain degree of supercooling (DT), ice nucleation
suddenly occurs. This results in rapid increase in product temperature due to release of latent heat (B and C in Fig. 1). Ice nucleation
step is followed by phase transition, also known as freezing plateau (C and D in Fig. 1), and during this step product temperature
remains almost constant at TF (Fig. 1), whereas the latent heat of crystallization is removed, and ice crystals grow in the product.
The larger degree of supercooling (difference between freezing and nucleation temperatures) results in instantaneous formation of
larger amount of ice nucleation and, therefore, the shorter the phase transition time (Otero and Sanz, 2000, 2006; Le Bail et al.,
1997). Once most of the water has frozen into ice, sensible heat is removed during the tempering step (D and E in Fig. 1) during
the product cooling at freezer temperature. The final shape, size, and distribution of the ice crystals formed throughout a product
depend on the rates of ice nucleation and subsequent crystal growth. The larger rates of ice nucleation and subsequent crystal growth
promotes generation of smaller, the rounder, and the more homogeneously distributed the ice crystals (Petzold and Aguilera, 2009;
Kiani and Sun, 2011). One of the key factor controlling the ice nucleation is supercooling and, according to Burke et al. (1975), every
degree of supercooling increases the rate of ice nucleation roughly 10-fold. In pure water, for homogeneous nucleation a very large
supercooling is required. Whereas, supercooling is needed to initiate nucleation in foods, it is generally significantly lower because
of the presence of numerous solid particles, solutes, and surfaces which act as nucleating agents. Moreover, it is important to note
that, in food freezing, large thermal gradients are usually established between the outer side and center of the product. When this
occurs, supercooling and nucleation only take place at the product surface in contact with the refrigerant. The temperature rise caused
by the crystallization of ice generally impedes any subsequent nucleation at the center of the product. Crystal growth takes place only
after nucleation has occurred, through addition of water molecules to the nuclei already formed, and its rate mainly depends on the
efficiency of latent heat removal (Reid, 1983; Petzold and Aguilera, 2009; Kiani and Sun, 2011; Otero et al., 2016).
Existing modern freezing technologies include air-blast freezer, tunnel freezer, belt freezer, fluidized bed freezer, contact freezer,
immersion freezer, indirect contact freezer, plate freezer, cryogenic freezer, liquid nitrogen freezer and liquid carbon dioxide freezer.
The newer emerging methods are aimed at increasing the heat transfer efficiency to achieve rapid freezing and controlling ice crystal
formation process to produce smaller ice crystals for minimizing product tissue damage and improve product quality. The methods
aimed at improving the heat transfer efficiency to achieve rapid freezing are discussed in this review article. The most common
approach opted to control ice crystal size is by varying the cooling rate during the freezing of a food product. In general, lower cool-
ing rates will result in the formation of larger ice crystals in the food product which can damage the food tissue and affect its texture.
On the contrary, higher cooling rates would yield smaller size of ice crystals reducing the tissue damage and negative impact on
texture (Jha et al., 2017). In recent years, several new approaches have been proposed for controlling the ice nucleation. The
following table (Table 1) summarizes the existing modern freezing technologies, approaches for innovation in freezing technolo-
gies and new developments in innovative freezing technologies. The new developments in innovative freezing technologies are
described and discussed in subsequent sections.
Figure 1 Typical freezing curve. T0, Initial temperature; TF, Freezing temperature; TN, Nucleation temperature; DT, Degree of supercooling (difference
between TF and TN). From Otero et al. (2016).
38 Food Freezing: Emerging Techniques for Improving Quality and Process Efficiency a Comprehensive Review
Table 1 Summary of approaches for innovation in freezing technologies and new developments in innovative freezing
technologies.
Approaches for innovation in freezing technology New developments in innovative freezing technology
Improvements of existing methods Impingement freezing

Hydro-fluidization
Adjunct technology to existing methods that assist in High-pressure assisted freezing
controlling ice formation Ultrasound-assisted freezing
Freezing assisted by Magnetic field
Electric field assisted freezing
Microwave assisted freezing
Radio frequency assisted freezing
Freezing assisted by biosubstance capable of regulating
freezing point depression
3.03.3 Impingement Freezing
Impingement freezing technology involves striking high velocity air jet (10–100 m/s) against food product to be frozen (Singh and
Singh, 2008). The high velocity cold air disrupts the stagnant insulating boundary layer surrounding food surface and increase the
heat transfer coefficient. The impinging jet flow patterns can be categorized into three characteristic regions: (i) the free jet region,
(ii) impingement or stagnation flow region and (iii) wall jet region. The free jet region is further classified into three sub-regions:
(a) the potential core region, (b) developing flow region, and (c) developed flow region. Maximum heat transfer between the flow
and the surface is experienced in the stagnation region. The slowest cooling zones are found to lie off-center in the wall jet region.
Fig. 2 shows the schematic diagram of a typical flow structure of an impinging jet on an object surface (Marazani et al., 2017). This
technology helps in considerably reducing freezing time close to those achieved by cryogenic equipment. In addition, operating
costs with this technology are similar to those of traditional mechanical equipment (Salvadori and Mascheroni, 2002). When using
optimum treatment conditions the surface heat transfer coefficient during impingement can even reach as high as that for food
being fried in oil (Ovadia and Walker, 1998). It is used widely in industrial cooling of textile, electronics components, paper
pulp and food applications. In the food industry, impingement is applied in baking, drying, cooling, and to accelerate freezing
and thawing (Borquez et al., 1999). The technology is widely used for preservation of various food products such as sticky cookie
dough, thin bakery products, sandwich egg patties, chewing gums, confectionery products, shrimp, fish fillets, potato products, meat
Figure 2 Schematic diagram of the typical flow structure of an impinging jet on an object surface. From Marazani et al. (2017).
patties, poultry parts and fillets (Marazani et al., 2017). Fig. 2 shows the schematic diagram of a typical impingement freezing setup
used in industrial refrigeration (Greiciunas et al., 2019).
The efficiency of an air-impingement technology depends on various factors, such as orifice shape, orifice arrangements (Katti
and Prabhu, 2008; Wen et al., 2018) and spacing ratio (Erdogdu et al., 2005; Ingole and Sundaram, 2016; Singh and Singh, 2008;
Vinze et al., 2016), freezing air temperature and velocity (Sarkar and Singh, 2004), geometry of food slab, its dimensions, food
product water content; specific heat for unfrozen and frozen food, thermal conductivity, food density, food initial and final freezing
target temperature, latent heat of fusion, conductivity of packing material, convective heat transfer coefficient (Wickramasinghe,
2014; Anderson and Singh, 2006), design of the injections, orientation of the impinging air to the target surface (Yang et al.,
1999), reynolds number (Lakshmi Prasad et al., 2013; Lawal et al., 2015; Erdogdu et al., 2007), and type, size and shape of nozzles
(Khazaei et al., 2008; Zuckerman and Lior, 2005, 2006).
Salvadori and Mascheroni (2002) reported that, high heat transfer coefficients of around 400 Wm2 K1 at high air velocities of
40 m/s provided a noticeable reduction in freezing time with minimum possible product weight loss. The authors also suggested the
removal of unbound water, excessive internal diffusion and as a result surface dehydration especially in thicker product could cause
product degradation. Because of this reason Impingement freezing was said to be mainly effective for freezing thin products.
Erdogdu et al. (2005) reported that increase of heat transfer coefficient (h-value) using higher air velocity plays a pivotal role in
reducing the impingement freezing or cooling time of food products. Rapid cooling is important in preventing micro-organism
growth to enhance food safety, improving product quality, preventing overcooking and destruction of nutrients with the potential
of reducing evaporative weight losses. Jet distance/nozzle diameter (H/D) is an important factor in air-impingement freezing of
cylindrical objects (Singh and Singh, 2008). With increase in H/D, the impact of air velocity decreases, and the turbulence effect
on food contact surface decreases simultaneously. Therefore, optimum H/D ratio is important in maximizing the heat transfer at
product surface (Singh and Singh, 2008). Erdogdu et al. (2005) suggested optimum H/D ratio of 6–8, whereas Jafari and Alavi
(2008) studied the effect of nozzle to slab shaped foods distance under two impinging jets and suggested H/D ¼ 10–12 to obtain
the maximum heat transfer rate. Erdogdu et al. (2007) reported that the H/D ratio of 3 was an optimum value for cooling cylindrical
shaped products such as eggs. The use of nozzle configuration where multiple arrays of nozzles from both the top and bottom of the
food product reported to enhance heat transfer, reduce freezing time and yield quality frozen food products with extended shelf life
(Salvadori and Mascheroni, 2002; Kaale et al., 2011). Erdogdu et al. (2007) suggested the use of jets from top and bottom of the
product or an impingement tunnel where the eggs rolling might improve the cooling time in this industrial application. Salvadori
and Mascheroni (2002) reported that heat transfer coefficient is also the function of shape of the nozzle and shape of the food
product. Both these factors affect the impingement performance as they have great influence on air flow. Jafari and Alavi (2008)
used two slot impinging jest to study the effect of jet-to-jet spacing, nozzle to food distance and air velocity on freezing time of
slab shaped food. They reported poor heat flux in case of too large space between jets as a result of many single jets. If jets are
too close, they interfere with each other’s flow velocity through fountain effect between two jets and reduced heat transfer as a result.
Increasing air velocity decreased the freezing time and no significant reduction in freezing time beyond critical point in velocity was
reported (Kaale et al., 2011; Jafari and Alavi, 2008). The air velocity beyond critical point can causes the flow field disorder, espe-
cially when the frozen goods are spherical or cylindrical and this results in decrease in heat exchange efficiency (Yang et al., 2019).
Nozzle to food distance affected the flow field and heat transfer. Heat transfer decreased with increase in food-to-nozzle distance
due to wide expansion in shear layer. Lower freezing time was obtained by decreasing food-to-nozzle distance. Kaale et al. (2011) in
their study, on super-chilling of food discovered that ice content and the percentage of the water in a product that is in solid form are
another important factor in food freezing by this method as ice crystal growth that can cause food tissue damage. Sarkar and Singh
(2004) reported that single free jets with longer nozzles (larger length/diameter ratios) had a narrower spread which resulted in less
viscous dissipation in the free jet regions and manufacturing defects (surface roughness) and minor nozzle internal constrictions
could potentially cause uneven flow patterns as a result of deflection of flow. Longer jets also present a challenge of difficulty in
cleaning and potential risk of blockage and unhygienic conditions in food applications. They also supported the recommendation
of Erdogdu et al. (2005) using H/D in the range of 6–8 and reported that shorter H/D ratios were found to cause confinement,
which resulted in disturbance to the main jet streams. Cryogenic impingement is another emerging technology which combines
the power of high air velocity (Impingement) and very low cryogenic temperature to further improve the freezing efficiency.
3.03.4 Hydro-Fluidization
Hydro Fluidization (HF) freezing is essentially a form of immersion freezing. It can also be considered analogous to liquid impinge-
ment freezing. In HF freezing system, the agitating jet of cold freezing liquid medium is pumped through orifices or nozzles from
bottom side in a freezing chamber or fluidized bed. The highly turbulent cold liquid along with moving product in fluidized bed
provide extremely high surface heat transfer coefficients that enable rapid freezing (Fikiin, 2003). For rapid freezing of foods the HF
method was suggested and patented to overcome the drawbacks and to bring together the advantages of both immersion (higher
uptake of cooling medium solute by food) and air fluidization techniques (lower hear transfer coefficient compared to immersion,
moisture loss from product surface, comparatively high energy consumption) (Fikiin, 1985, 1992, 1994). The key part of the HF
involves circulating system that pumps the refrigerating liquid upwards, through orifices or nozzles, in a refrigerating vessel, thereby
creating agitating jets. These form a fluidized bed of highly turbulent liquid and moving products, and thus evoke extremely high
surface heat transfer coefficients. Basic process flow of HF system is illustrated in Fig. 3 (Fikiin and Fikiin, 1998).
Figure 3 General arrangement of a HF-based freezing system combining the advantages of both air fluidization and immersion food freezing tech-
niques: (1) Charging funnel; (2) Sprinkling tubular system; (3) Refrigerating cylinder; (4) Perforated screw; (5) Double bottom; (6) Perforated grate
for draining; (8) Sprinkling device for glazing; (7 and 9) Netlike conveyor belt; (10 and 11) Collector vats; (12) Pump; (13 and 14) Rough and fine
filters; (15) Cooler of refrigerating medium; (16) Refrigeration plant. From Fikiin and Fikiin (1998).
Foods such as peas, sweetcorn, cauliflower florets, brussel sprouts, cut parsley, parsley tops, cut celery, asparagus, dill, cut leek,
sliced cucumbers, tomatoes, sliced and whole mushrooms, cut kohlrabi, cut broccoli and broccoli spears, cut carrots, baby carrots,
french fries, shrimps, meat dices, strawberries, raspberries, blackberries, redcurrants, blackcurrants, plums, peaches, paprika, goose-
berries, grapes, sweet cherries, sour cherries, apricots, sliced apples, pineapple segments and whole potatoes can be frozen by the HF
technique. Efficiency of HF depends on several operative and geometric configuration factors such as freezing medium flow rate, the
fluid velocity at the jet exit, refrigerant temperature, number of orifices, orifice-sample distance, orifice arrangement, orifice-orifice
distance and sample-sample distance (Peralta et al., 2012; Belis et al., 2012, 2013, 2014, 2015). Orona et al. (2018) demonstrated
that, heat transfer between cooling fluid and product were mainly affected by product load, distance between orifices and velocity of
jets at the orifice. The mass loss is mainly affected by cooling fluid temperature. Fikiin and Fikiin (1998) patented a novel enhanced
HF method to overcome the few drawbacks of both air fluidization and immersion food freezing techniques by employing two-
phase ice slurry as fluidizing media (Fig. 4). Two main innovative aspects of method are combination of (i) employment of unfreez-
able liquids as fluidizing agents and (ii) use of pumpable ice slurries as fluidizing media to provides an extremely high heat transfer
Figure 4 Schematic diagram of an ice-slurry based hydro fluidization system (HyFloFreeze®). From Fikiin and Fikiin (1998).
rate, short freezing times, great throughput and better product quality at refrigerating temperatures maintained by a single-stage
refrigeration machine. This novel HF method is claimed to require nearly two times lower investments and power costs compared
with the popular individual quick-freezing methods. The HF freezing with ice slurries can achieve a process rate close to that of the
cryogenic flash freezing modes. When an ice-slurry at a temperature of 25 C and a heat transfer coefficient of 1000 Wm2K1
employed; apricot, strawberries, and plums were frozen from 25 C down to an average final temperature of - 18 C within 8–
9 min; cherries, raspberries, and morellos within 1.5–3 min; and green peas, cranberries and blueberries within about 1 min
only. The general layout of an ice-slurry-based system for HF freezing is shown in Fig. 4.
Peralta et al. (2009) studied the heat transfer on a stationary copper sphere (of different diameter – D) impinged by a liquid jet
(solution of NaCl–water as refrigerant) generated by the pilot scale HF system with 3 mm (d) diameter orifice. Re (Reynolds
number), Pr (Prandtle number), the orifice-sphere distance (H/d), and the curvature of the sphere surface (d/D) were considered
in a correlation for Nusselt number for the HF system and the ranges studied were: 15,000 # Re # 115,000; 9.2 # Pr # 11.5; 1.66
# H/d # 16.66; and 0.15 # d/D # 0.30. They reported that the Nusselt number range was 70–400 and it increased when Re and Pr
increased, it had a maximum for 3 < H/d < 10, and it decreased when d/D increased. HF freezing compared to other IQF techniques
showed a much higher freezing rate for products such as small fish and some vegetables (Fikiin, 1992, 1994). The HF technology
provides the rapid water crystallization in the product, which generates fine ice crystal structure in food and minimize the cellular
tissue damage. Also, the product surface freezes rapidly in a solid crust and minimize the osmotic transfer and provide better
product appearance. The mass loss in HF are close to zero as compared to 2%–3% in air freezing tunnel. The HF system incur
less physical damage, provides better product shelf life and it is more environmental friendly compared to air fluidization system
(Fikiin and Fikiin, 1998). In HF technology the maximal surface heat transfer coefficient achieved higher than 900 W m2 K1 as
compared to 378 W m2 K1 in the case of immersion in running liquid and 432 W m2 K1 in case of sprinkling and
475 W m2 K1 for immersion with bubbling through freezing technique. Even at a slight or moderate jet agitation and a compar-
atively high refrigerating medium temperature of about 16 C, in HF based freezer the scad fish were frozen from 25 C down
to 10 C in the center in 6–7 min, sprat fish and green beans in 3–4 min and green peas within 1–2 min (Fikiin and Fikiin,
1998, Fikiin et al., 2002). The HF treatment time and product temperature histories during HF freezing of scad and sprat fish, green
beans and peppers are illustrated in Fig. 5 (Fikiin and Fikiin, 1998).
3.03.5 High Pressure Assisted Freezing
In the field of novel freezing technologies, the quick-freezing technologies such as cryogenic freezing, immersion freezing, and fluid-
ized bed freezing are based on removing heat from the product through thermal conduction or convection. However, the heat
removal flow in these technologies is from inside to outside of the product. Thus, the freezing rate is inevitably slower inside
the food than near its surface resulting in comparatively larger ice-crystal in center and higher food product tissue damage (Kim
et al., 2014). Hence, there is a need for technology which can provide uniform ice-crystallization throughout the food.
Figure 5 The HF treatment time and product temperature histories during HF freezing of scad and sprat fish (A); HF freezing of green beans and
peppers (B) when using sodium chloride as a freezing agent. From Fikiin and Fikiin (1998).
During the past decade, high-pressure freezing has gained its reputation as a promising freezing method by the food industry in
various freezing application (Fuchigami et al., 2002; Koch et al., 1996; Lévy et al., 1999; Sanz and Otero, 2000; Schlüter et al., 1998).
According to the phase diagram of water, mainly 3 types of high-pressure freezing techniques are identified based on their phase
transition characteristics. These are (i) high-pressure assisted freezing (PAF), (ii) high-pressure shift freezing (PSF) and (iii) high-
pressure induced freezing (PIF) (Fernández et al., 2006). In case of Pressure-assisted freezing the phase transition occur under
constant pressure, in case of pressure shift freezing the phase transition occur due to a pressure release whereas in case of pressure
induced freezing the phase transition occur at a pressure increase and continued at constant pressure (Knorr et al., 1998; Fernández
et al., 2006). High-pressure induced freezing process is considerable new and very little study has been done on it so far (Benet et al.,
2004).
High pressure assisted freezing and in particular “pressure shift freezing” (PSF), has gained considerable scientific interest in
recent years since it can provide uniform ice-crystallization throughout the food (Fikiin, 2003; LeBail et al., 2002; Li and Sun,
2002b; Cheftel et al., 2000; Sanz, 2004). High-pressure assisted freezing Fig. 6A involves freezing food to below its corresponding
freezing point (point 3) while food is kept under constant pressure (step 2–4). Finally the pressures is released once the freezing
plateau is complete and product reaches the final temperature (point 4 in Fig. 6A) (Fernández et al., 2006). The basic principle
behind this process is that, water can remain in liquid state down up to 22 C under high pressure up to 200 MPa. This property
of water under high pressure allow rapid freezing through supercooling and promote rapid ice nucleation. However, freezing in this
process proceeds from the surface to the center and as a result the majority of ice nucleation occurs in the outermost part of the
product, it causes ice crystals which are large, needle-shaped, radially oriented and presenting a marked size gradient from the sam-
ple surface to the center (Fuchigami and Teramoto, 1997; Lévy et al., 1999). In high-pressure shift freezing (Fig. 6B,C), the under-
pressure cooling of sample occurs at less than 0 C and food remains in non-frozen state (steps 2–3). When the desired product
temperature is achieved (point 3), pressure is released. This pressure release step induces uniform supercooling throughout the
sample (point 4) resulting in formation of uniform nuclei throughout the sample (regardless of its shape and size). At this stage
Figure 6 Different high-pressure freezing processes represented over the phase diagram of pure water. (A) High-pressure assisted freezing [1–2:
compression; 2–4: pre-cooling þ phase change þ tempering under constant pressure; 4–5: pressure release]. (B) High-pressure shift freezing with
phase transition at atmospheric conditions. (C) High-pressure shift freezing with phase transition under pressure [1–2: compression; 2–3: pre-
cooling (sample is over the melting curve, therefore it is unfrozen); 3–4: pressure release; 4: sample is highly supercooled (no latent heat has been
yet released); 4–5: latent heat is released and sample temperature increases up to the corresponding freezing point at atmospheric conditions (B) or
under pressure (C); 5–6: tempering (at point 6, freezing is complete); 6–7: pressure release to atmospheric conditions (only in c)]. From Fernández
et al. (2006).
the latent heat is released, causing a rise in sample temperature to the corresponding freezing point (point 5). After this stage
freezing is completed at constant pressure (steps 5–6), usually at atmospheric conditions (Fig. 6B) (Fernández et al., 2006). This
process displays formation of uniform ice nucleation throughout the product and the ice crystals that formed are granular in shape
with no specific orientation (Martino et al., 1998; Thiebaud et al., 2002; Zhu et al., 2005). In PSF technology, food cooled to well
below its normal freezing point under the application of high pressure and up to 20 C supercooling may be obtained, in contrast
to just a few degrees under atmospheric pressure. When the pressure is released, very fine ice crystals spontaneously forms
throughout the food. Ice-crystal formed by this technique are much smaller than normal freezing which helps reduce food tissue
damage and improve frozen food quality.
Various researchers in their study, reported a better textural and microstructure properties of different foods frozen using PSF
technology compared to traditional freezing methods (Koch et al., 1996; Fuchigami et al., 1997; Fuchigami and Kato, 1998). Cheva-
lier et al. (2000a) in their study, on freezing on Norway lobster with PSF (200 MPa, 18 C) treatment reported decrease in salt
soluble protein extractability and increase in toughness. Also PSF yielded smaller ice crystals compared to air-blast freezing as dis-
played by scanning electron micrographs. Chevalier et al. (2000b) in another study, on turbot fillet treated with PSF
(140 MPa, 14 C) reported about 10 times smaller ice crystal and less thawing drip as compared to air blast freezing. Urrutia-
Benet et al. (2007) in their study, on freezing potato with PSF and PIT reported better quality-related parameters (texture, micro-
structure, color and drip loss) compared to atmospheric freezing and thawing. Otero et al. (2000) reported that, peach and mango
samples treated with PSF (200 MPa, 20 C) had a uniform and rapid ice nucleation, which helped maintained the original tissue
structure to a great extent. Martino et al. (1998) reported that, pork frozen by PSF showed similar, small-sized ice crystals at the
surface and at the central zones,.This technique is particularly useful for freezing large pieces of food when uniform ice crystal sizes
are required. Choi et al. (2016) in their separate research work on pork studied the effect of various PSF treatment conditions (0.1–
200 MPa) on the quality characteristics (pH, water-binding properties, shear force, histological change and color) of pork. The PSF
treatment greater than 150 MPa pressure resulted in high moisture loss and discoloration, while the PSF at 50 MPa offered no
advantageous effect on pork quality compared to atmospheric freezing (0.1 MPa). The PSF treatment at 100 MPa displayed best
results, where the pork quality did not differ from an unfrozen control after thawing. Studies are underway to investigate the effects
of PSF on the physical attributes of protein-based foods such as tofu, meat, and model foods (Chevalier et al., 2000a; Fuchigami and
Teramoto, 2003; Kanda et al., 1992). Koch et al. (1996) in the their study, reported that PSF treated potato maintained its texture
with higher bursting strength, minimum color change and lower dissolved concentration matter in the potato drip compared to
potato frozen with air blast freezer. Similarly Otero et al. (1998) reported a reduced drip in eggplants treated with PSF relative
to conventional freezing. Luscher et al. (2004) examined the impact of subzero temperatures and pressures up to 400 MPa on inac-
tivation of Listeria innocua BGA 3532 in buffer solution. Under liquid condition the pressure holding showed progressively rapid
inactivation, whereas under ice phase condition, extended pressure holding times had comparatively little effect on inactivation.
Inactivation of 3 log cycles was reported during transient phase change of ice I to other ice polymorphs (ice II or ice III) with pressure
cycles above 200 MPa. This could be due to mechanical stress associated with the phase transition and it was independent of the
applied pressure holding time. Bulut (2014) in his study, reported a 3.8 log reduction in E. coli for the milk sample treated with PSF
for 30 s at 3 C.
While various researchers have shown great potential of pressure shift freezing in producing smaller more widely distributed ice
crystals in many products, it remains to be established whether this technology can be applicable at commercial level due to its
current batch processing nature. Also, the capital cost of equipment is another obstacle in holding back further development of pres-
sure shift freezing in commercial application, as is the inherent batch nature of the current process and the long precooling step
required before nucleation. However, the penetration of other high-pressure processes into the food industry indicates potential
to overcome these problems in the near future.
3.03.6 Ultrasonic Assisted Freezing
Ultra-sonication (US) based technologies are gaining popularity in various food processing application either by replacing tradi-
tional technologies or assisting traditional technologies in improving their efficiency. Ultra-sonication had been applied to enhance
efficiencies of various food processing technologies namely freezing, thawing, extraction. oxidation, brining, filtration and drying
(Tao and Sun, 2015). US induced cavitation in the unfrozen liquid phase is one of the most important phenomena provoked by the
action of the acoustic energy. Cavitation induced microstreaming help to enhance the heat and mass transfer accompanying
the freezing process. Cavitation also assist in initiating the formation of ice-nucleation and increasing the rate of nucleation as
the gas bubbles produced can act as nucleating agents. Crystal fragmentation is another significant acoustic phenomenon which
can lead to crystal size reduction; an important aspect for better freezing processes to maintain quality of food. Power ultrasound
with its beneficial acoustic effects has proved itself to be an effective method in assisting food freezing, and its benefits are wide-
ranging. US-assisted freezing can be utilized to induce nucleation and to control crystal size distribution in the frozen products
during freezing of fluid food. If it is applied to the process of freezing fresh foodstuffs, it not only can increase the freezing rate
but also can improve the quality of the frozen products. Application of power ultrasound can also help to reduce incrustation
on the freezing surface. The ability of power ultrasound in performing these functions is affected by a wide range of parameters,
such as the duration, intensity, or frequency of ultrasonic waves (Zheng and Sun, 2005).
Figure 7 Schematic diagrams of ultrasound-assisted freezing devices. (A) Full-immersion type, (B) half-immersion type, and (C) non-immersion
type. From Xu et al. (2017).
Xu et al. (2017) in their book chapter on food freezing assisted with ultrasound described the three different types of US assisted
freezing devices: (i) full-immersion type, (ii) half-immersion type, and (iii) non-immersion type. As these are shown in Fig. 7; (i)
Full-immersion system consists of four basic component: ultrasonic system, refrigeration system, coolant circulation system and
temperature detection system (Fig. 7A) (ii) Half-immersion type of US assisted freezing devices consist of the ultrasound transducer
horn tightly bonded to an aluminum plate and connected to an ultrasound generator to obtain an adequate resonance frequency on
the plate (Fig. 7B). (iii) Non-immersion type of device consists of ultrasonic system added on a conventional refrigeration machine.
Several piezoelectric ultrasonic transducers are evenly attached to the bottom of the stainless-steel freezing tank and connected to
a generator (Fig. 7C).
US-assisted freezing has been studied by various researchers and its application in enhancing freezing efficiencies of various
foods has been summarized here. Sound waves generated during US treatment cause cavitation and a sponge effect, both of which
impact the freezing rate and properties of the frozen products. The application of ultrasound in the freezing process helps to inac-
tivate enzymes and microbes and enhances the ice crystal nucleation process. The advantages of ultrasound-assisted freezing over
conventional freezing includes high freezing rate, faster crystallization, uniform distribution of ice crystals, better microstructure,
and good product quality (Islam et al., 2017). High-intensity ultrasound has an ability to influence the ice-crystallization process
by controlling the ice-nucleation development and the formation of small crystals (Luque De Castro and Priego-Capote, 2007;
Zheng and Sun, 2006). US-assisted freezing has a potential in reducing the ice-crystal generation time and providing a better homo-
geneity, and preserving product textural property by minimizing tissue cell damage (Zheng and Sun, 2006). US induced cavitation
can help enhance ice-nucleation by minimizing ice encrustation on the ice-cream freezer wall, and microstreaming can improve
heat and mass transfer. Mortazavi and Tabatabaie (2008) investigated the effect of ultrasound (20 kHz) on ice-cream freezing
process time. Results were shown that ultrasound can shorten the freezing process time for ice-cream by about 65% compared
to conventional freezing method. Also, it can contribute to improve quality of ice cream e.g., reducing crystal size and preventing
incrustation of freezing surface. The US induced acoustic stress also promote ice crystals fracture to create smaller ice-crystals (Zheng
and Sun, 2006). Delgado et al. (2009) studied the effect of US treatment (40 kHz frequency, power level of 131.3 W, 0.23 Wcm2). In
this study, ultrasound was applied intermittently for different times from temperatures below and close to the initial freezing point
on apple cylinders freezing under immersed condition. Results showed that, US assisted freezing (ultrasound application at 0 C
or 1 C for 120 s in total, with 30 s intervals) significantly improved the freezing rate represented by the characteristic freezing
time up to 8% (P < 0.05), compared to immersion freezing without ultrasound. Results of the effect of ultrasound waves applied
on radial or tangential cut samples sonicated for 120 sec from 1 C and/or 0 C indicated that at the power level considered there
were no significant differences among the ultrasonic radial or tangential irradiated samples of these treatments, though the freezing
rates were enhanced and were different (P < 0.05) from the control treatment. They also observed some evidence of the influence of
ultrasound to induce primary nucleation. Islam et al. (2014) studied the application of US assistance during immersion freezing of
mushrooms. Their finding suggests Ultrasound at 0.39 W cm2 (20 kHz) reduced nucleation time by 24%, 53% and 34% in Len-
tinula edodes, Agaricus bisporus and Pleurotus eryngii respectively. About 10% less drip losses were found during the thawing
process compared to control samples. Increase in whiteness index was also reported when ultrasound intensity was higher than
0.27 W cm2 (20 kHz) in L. edodes and P. eryngii whereas, ultrasound at 0.39 W cm2 (20 kHz) showed the highest chroma value
with lower yellowness and browning indices. Highest textural hardness values were reported with ultrasound at 0.39 W cm2
(20 kHz). Polyphenol oxidase and peroxidase enzyme activities were also significantly reduced with the increase in ultrasound
power during ultrasound-assisted freezing. In a study, by Comandini et al. (2013), US treatment (35 kHz) combined with immer-
sion freezing of potato (< 0.1 temperature in the geometrical center) was able to induce nucleation in the center of potato cubes,
interrupting the super-cooling process. Also a reduction in freezing time was observed when ultrasound was applied at 2.0 C
compared to non-US treated sample. Li and Sun (2002a) investigated the immersion freezing of potatoes with the aid of power
ultrasound. Ultrasound power, exposure time and the freezing phase to which ultrasound was applied had an effect on freezing
rate. The higher ultrasound power and longer exposure time resulted in greater sonication action. However, care should be taken
in choosing the ultrasound power and exposure time to avoid thermal effect of ultrasound. The greater improvement in freezing rate
was noted when 15.85 W ultrasound power was applied for 2 min and when ultrasound was applied to the phase change period
during freezing process. Kiani et al. (2015) suggested that, since ultrasound irradiation increased the heat transfer coefficient but
simultaneously generated heat at the surface of the samples, an optimum duty cycle (DC) was needed for the shortest freezing
time which in their study, found in the range of 30%–70% DC. DCs higher than 70% increased the freezing time. DCs lower
than 30% did not provide significant effects on the freezing time compared to the control sample. The numerical model predicted
the characteristic freezing time in accordance with the experimental results. Kiani et al. (2012) studied the US-assisted (25 kHz; 0,
120, 190, 450, 890, 1800, 2800, 3400 and 4100 W m2, ethylene glycol-water mixture at 10 C) freezing of a sphere (0.01 m in
diameter) placed at different positions (0.02, 0.04 and 0.06 m) above the transducer surface. In their study, they demonstrated
a significant increase in the rate of heat transfer and considerably shorter cooling times as a result of US treatment. The higher cool-
ing rates, and increased Nu (Nusselt number) values (from about 23–27 to 25–108) were reported as the US intensity increased.
Based on their visual observation it was indicated that both cavitation and acoustic streaming were important for improved heat
transfer. Higher cooling rates were reported as the sphere got closer to the transducer surface. On the other hand, the enhancement
in heat transfer was also reported despite the longer distance of the sphere from the transducer but it’s closer location to the gas-
liquid interface. US application in this study showed promising effect for the enhancement of convective heat transfer rate during
immersion cooling. However, high intensities also acted as a limiting factor in achieving the lowest final temperature due to the
generation of heat at the surface of the sphere. Cavitation clouds at the surface of the sphere were suggested as primary cause of
the heating effect.
Cheng et al. (2014) investigated the effect of US temperature and intensity on the freezing and nucleation in strawberry samples.
They reported that, the application of US at different temperatures was able to induce nucleation at lower degree of supercooling
compared to the control samples. The achieved degree of supercooling in the US treated strawberries was linearly correlated to the
US temperature. At the US temperature of 1.6 C, the freezing time was significantly shorter than that in the control sample. The
application of US at higher intensities was found to effectively shorten the freezing time. The degree of supercooling in ultrasound
irradiated samples was not linearly correlated to ultrasound intensity. Xu et al. (2015) reported that ultrasound application can
decrease freezing time and drip loss of red radish. Ultrasound-assisted freezing showed better retention on firmness and color,
improved retention of anthocyanins, vitamin C and phenolic content and better microstructure of frozen radish. Aromatic profile
of red radish was deeply affected by the freezing/thawing process (Xu et al., 2015). Xu et al. (2014) studied the nucleation by US assis-
ted immersion freezing of radish cylinders. They reported a good linear relationship between nucleation temperature and ultrasound
application onset temperature. Power ultrasound facilitated the nucleation effectively and ultrasound treatment (0.5 C, 7 s,
0.26 W cm2) was the optimal conditions for the nucleation of radish cylinders. Xin et al. (2014) studied the freezing time and quality
of US assisted frozen broccoli. They reported a decreased freezing time and microstructure of broccoli was better preserved. The firm-
ness of broccoli was better preserved and the drip loss was reduced by the application of US assisted freezing (Xin et al., 2014).
Cheng et al. (2015) provided an overview of recent developments related to the application of ultrasound in low temperature
and closely related processes such as freezing, thawing, freeze concentration and freeze drying. The applications of high intensity
ultrasound to improve the efficiency of freezing process, to control the size and size distribution of ice crystals and to improve
the quality of frozen foods have been discussed in considerable detail. The use of low intensity ultrasound in monitoring the ice
content and to monitor the progress of freezing process has also been highlighted. Zhang et al. (2018) provides latest overview
on recent researches of power ultrasound technique to accelerate the food freezing processes and illustrates the main principles
of power US assisted freezing. The effects of US treatment on liquid food, model solid food as well as fruit and vegetables are dis-
cussed, respectively, from the aspects of increasing freezing rate with assistance of US treatment. It is shown that US assisted freezing
can effectively improve the freezing efficiency and promote the formation of small and evenly distributed ice crystals, resulting in
better food quality. The effectiveness of ultrasound application and optimum ultrasound parameters depend on the nature of the
samples and different inherent properties of food samples. Islam et al. (2017) in their comprehensive review of the literature covers
recent advances in structure and working principles of common and US assisted freezers. The impact of the fast and slow freezing
processes on the characteristics of frozen fruits and vegetables have been reviewed. The mathematical modeling and quantification
aspects of the freezing and thawing process have also been reviewed. The structure–function aspects of power ultrasound, including
the associated transducers and design aspects of different ultrasound-assisted freezing systems, have been reviewed in considerable
detail.
Various research studies have shown great potential for application of US assisted freezing on certain types of food products,
however efforts are still needed for scaling up of equipment and process of US assisted freezing from laboratory to industrial scale
(Zhang et al., 2018; Islam et al., 2017).
3.03.7 Freezing Assisted by Magnetic Field
The Magnetic fields (MF) assisted freezing is an emerging research field and various researchers are investigating the role of MF in
food freezing. MF can influence the properties of water (Pang and Deng, 2008a,b). Various Researchers have studied the effect of MF
and effect of different parameters (MF strength) on supercooling and crystallization properties of water during freezing (Aleksan-
drov et al., 2000; Zhou et al., 2012; Inaba et al., 2004; Zhang et al., 2010a; Mok et al., 2015). Similarly, Many studies demonstrating
effect of Oscillating magnetic field (OMF) and its different parameters (strength, frequency) on supercooling and crystallization
properties of water during freezing are available in literature (Semikhina and Kiselev, 1988; Mihara et al., 2012; Niino et al.,
2012; James et al., 2015; Naito et al., 2012).
Under the application of unidirectional MF, the electron spin’s magnetic moment is aligned in one direction, and thus, the influ-
ence of the electron spin on the thermal vibration cannot be mutually canceled. As a result, the thermal vibration induced by elec-
tron spin is strengthened and increased. Therefore, when the temperature is dropped below the freezing temperature of water, the
vibration of the free water molecules are still too large to freeze water, and the free water is brought into a supercooled state for
longer time instead. When supercooling continues for extended period of time, a heat quantity, equivalent to the latent heat
required for solidification, is taken away. At this stage, by a sudden lowering of the vibration level either by reducing the temperature
to a certain extent, or, by relieving the magnetic field instantaneously, permits the molecules to get rearranged according to the
hydrogen bond, and rapid freezing can be achieved. MF application has a potential to delay the formation of ice crystals, and as
a result, most of the ice crystals form at the same time producing numerous and smaller ice crystals. Moreover, MF application
breaks water cluster (aggregations of free water molecules) into smaller groups. These smaller water clusters form hydrogen bonds
with the polar groups of a tertiary structure of proteins that face outwards from the outer surface, and thus, the free water is turned
into bound water. The decrease in amount of free water indirectly restrains free water crystals from growing too large (Owada and
Kurita, 2001; Owada and Saito, 2010). Oscillating electromagnetic fields interact with water, perturb and even disrupt hydrogen
bonds, which in turn are thought to increase the degree of supercooling and to generate numerous fine ice crystals. Based on the
literature, it seems that the frequency has an influence on the above-mentioned phenomena (Jha et al., 2017).
Recently, Application of MF assisted freezing has been reported in various food applications. The chicken and tuna samples
treated with OMF (0.5–0.7 mT, 50 Hz) combined with or without MF (1 mT) displayed 20% to 50% less time to cool the central
temperature from 0 C to 20 C. Also the thawed sample hardly showed any evidence of cell damage, while the color, flavor, and
taste were found similar to raw food (Owada, 2007). Sato and Fujita (2008) patented MF technology equipped freezer comprising
of a freezer main body, a cluster fragmenting device (MF-generator) for fragmenting the water clusters contained in the matrix,
a loading part, a heat exchanger, and a cold gas supply device attached with a dehumidifier. They froze different food matrices under
various test conditions using MF assisted freezing and they stored them in the freezer at 50 C for a certain period of time prior to
quality evaluation (storage period of Chinese noodles was three months, while spinach, packed pasta, lumps of pork, and tofu
blocks were stored up to 150 days). The food frozen in their freezer under the oscillating MF (MF of 200–300 mT at frequencies
60–100 Hz) and a cold atmosphere with low water vapor content satisfactorily maintained their quality attributes (e.g., good flavor,
appearance, fragrance, no or little change to texture and less drip loss, etc.) of the product upon thawing compared to products
frozen in the same freezer at a similar freezing condition but without MF and dehumidifying devices. The inventors suggested
that the fluctuating MF breaks the hydrogen bonds between the water molecules and thereby fragments the water cluster efficiently
resulting in small size ice crystals. Owada and Kurita (2001) in another patent applied the combined influence of SMF (10 mT),
OMF (0.5 mT, 50 Hz), SEF (static electric field) (6 105 V/m) and sound waves (20–2000 Hz) to freeze tuna, sardine, pork, juices,
wines, oranges, and cakes. They claimed lower freezing time to achieve the target temperature of 50 C and better quality (less loss
on thawing, drip loss, discoloration and off flavor) upon thawing compared to the conventional freezing method. Furthermore,
freezing under MFs combined with electric field and sound waves reduced the number of bacteria in the frozen product compared
to the conventional method. Suzuki et al. (2011) using their specially designed freezer coupled with a magnetic field generator
investigated the effect of weak MF (about 0.5 mT) on freezing process of several kinds of foods. They reported no significant effect
of the weak MF on the time-temperature history during freezing and on the quality (drip loss, color and texture, microstructure, and
sensory evaluation) of frozen foods compared with no MF experimental conditions. In contrast, James et al. (2015) reported a minor
increase of the degree of supercooling of garlic bulbs under the oscillating MF conditions in comparison to freezing under the same
conditions without oscillating MF. In this work the degree of supercooling of garlic bulb was studied using the effect of freezing with
CAS (Cell Alive Systems) conditions in ABI freezer (Cell Alive Systems commercial freezers manufactured by ABI Corporation,
Japan; 4 CAS conditions: off, 0%, 50% and 100% at frequencies 50 Hz were studied), compared to freezing under the same condi-
tions without CAS. For instance, when the samples were frozen from an ambient state (21 1 C), the degree of supercooling at
50% CAS condition was 4.0 C compared to 2.7 C and 3.1 C in the case of 0% CAS condition and conventional freezer, respec-
tively. Moreover, the time before nucleation (i.e., the time period till which the product remained under the supercooled state) was
longest when the freezing was performed under 50% CAS condition. Choi et al. (2015) investigated the changes in quality attributes
and microstructure during storage period (at 20 C for 8 months) of beef sample frozen by ABI freezer (ABI Co. Japan) using CAS
technology (Cell Alive System) and air blast freezer to 55 C and 45 C, respectively. They reported that, beef sample frozen with
MF application had small size ice crystals and their rate of size increase during the storage period was lower compared to those of an
air blast frozen sample. Also, a significant lower drip loss and protein denaturation (in terms of water holding capacity) was
observed for samples frozen under MF than compared to the air blast frozen samples on 8-month storage. Moreover, their sensory
evaluation results revealed that the beef samples stored after MF assisted freezing did not show the difference until 4 months, and it
showed higher acceptability in comparison with the beef sample stored after the air blast freezing. At this point, it has to be
mentioned that the freezing temperature for MF assisted freezing was 10 C lower than the air blast freezing; therefore it is difficult
to say whether observed effects were because of the MF or due to the reduced temperature. Yamamoto et al. (2005) compared the
quality of frozen chicken breasts in an ABI freezer (B ¼ 1.5 to 2 mT at 20, 30 and 40 Hz, maintained at 45 C) with the product
frozen in conventional rapid freezer (CRF; 45 C) and a slow freezer (SF; 20 C). They reported no significant difference in drip
loss and fracture properties among the samples that were frozen by these three different freezing methods (MF, SF and CRF) and
stored for one week. The rupture stress of meat frozen under MF was lower than those with SF and CRF and did not change in frozen
storage from one week to six months, while significantly higher rupture stress values were reported for the samples frozen with SF
and CRF and stored for six months than those stored for one week. Hence, the MF application during freezing prevented an increase
in the firmness of the samples during storage period. Moreover, the microscopic observations revealed large space in the muscle
fibers after six months of storage for the meat frozen with CRF, while these spaces were small and scattered throughout the muscle
fibers for samples frozen under MF and stored for six months. The researchers suggested that, the observed change in CFR-frozen
sample might have been caused by protein denaturation during freezing and storage (Yamamoto et al., 2005). Owada and Kurita
(2001) also suggested the use MF technology for reducing the population of unwanted bacteria in food products. MF induced
changes in magnetic flux and an electromagnetic induction occur during food freezing. Thus, the induced electromotive force caused
by the electromagnetic induction generates free electrons within the food. These free electrons can interact with water molecules
present in food matrix and produce hydroxyl-radicals capable of destroying the cell membranes of microbes.
Otero et al. (2016) in their extensive review on “Effects of magnetic fields on freezing and application to biological products”
covered the effects of MFs on water, patents on magnetic freezing, experimental data about the effects of MFs on freezing, freezing of
food products and freezing of biological specimens such as cells, tissues, organs, and organisms. They provided the summary of
experimental data about the effects of magnetic fields on freezing of food products which is presented in Table 2. They suggested
that the experimental data compiled in this review failed to back up the claims reported in various patents on magnetic freezing with
evidence. Also, some research papers reveal positive results, whereas others show no effect of MF application. Many difficulties asso-
ciated to both MFs and freezing hamper the reproducibility and replicability of the results. Moreover, although there exist a number
of reports on the effects of magnetic freezing, it is important to note that many of them have not been peer-reviewed and, as a conse-
quence, the quality of these papers is sometimes questionable. They concluded that, although it has been more than 10 years since
magnetic freezers were introduced in the market, evidence of the efficacy of MFs in improving the quality of frozen products has not
yet been well established. Data in the literature are frequently confusing and apparently contradictory and, therefore, much more
research is needed to confirm the potential benefits of MFs on freezing. After examining the magnetic properties of water, the low
strength of the MFs applied in ABI freezers (usually lower than 1 mT) casts doubt on the effects that these extremely weak MFs can
have on water crystallization, but other mechanisms could be affected. Many doubts also arise concerning the working principles
(The combination of static MFs with electromagnetic waves at the Larmor frequency) of Proton freezers (IFP, Ltd). Although the
scientific community has frequently questioned the science behind magnetic freezers, it sounds strange that manufacturers have
not yet presented conclusive evidence to dissipate any doubt as far as their efficacy is concerned. In any case, investigations on
magnetic freezing should cover not only MF strengths and frequencies currently used in commercial freezers but also much
more wide ranges to have a complete view of the potential effects of MFs on freezing of biological products. Only after finding posi-
tive results, mechanisms involved in such results should be investigated. Although patents on magnetic freezing claim that MFs
mainly affect water supercooling, the role of other molecules and different mechanisms should not be neglected. Overall MF assis-
ted freezing is still an emerging technology and more studies are required to understand the different aspects of this technology in
food freezing application.
3.03.8 Electric Field Assisted Freezing
Several novel freezing methods are gaining attention in recent times which provides better energy saving and/or quality preservation
to a greater extent upon thawing of frozen foods. Some of these novel technologies are summarized above. Electric field assisted
freezing is again a novel technique gaining momentum among electro-freezing technique; it offers less energy intensive freezing
conditions (higher set point ambient temperature, lower air velocity), and allows better quality retention (Jha et al., 2018b). Electric
field assisted freezing are generally divided into two main categories (i) static electric field (SEF) and (ii) fluctuating electric field
(FEF) (Jha et al., 2017).
3.03.8.1 Static Electric Field Assisted Freezing

The freezing assisted by static electric field permits to induce nucleation at a reduced supercooling of water. The application of SEF
assisted freezing of water has been reported to have a beneficial effect on nucleus formation by inducing nucleation at relatively high
Summary of experimental data on the effects of magnetic fields on freezing of food products.
48
Table 2
Intensity Frequency
DT
Food Freezing: Emerging Techniques for Improving Quality and Process Efficiency a Comprehensive Review
Field applied (mT) (Hz) Device Sample Freezing kinetics Ice crystals Quality Author/document
Static 0.36 Lab prototype Carps No effect No effect on precooling time. – – Lou and others (2013)
magnetic 0.72 Shorter freezing plateau. Research paper
Field 1.08 Shorter empering and total
freezing times
Oscillating 100 107 Patented by Sweet potatoes – – Smaller Color, taste, aroma, Ino and others (2005)
magnetic Kansho smoothness, and hardness Patent
field Riyo Gijutsu similar to those of raw potato
Kenkyusho: KK
0.5–0.7 50 Patented by ABI Chicken and tuna – Time for lowering the core – Cells were hardly destroyed. Owada (2007) Patent
Co. Ltd temperature from 0 C to Color, flavor, and taste similar
20 C was 20%–50% to those of the original raw
reduced food
200–300 60–100 Patented by Packed Chinese noodles, – – – Quality satisfactory maintained Sato and Fujita (2008)
Shounan spinaches, packed pasta, after thawing Patent
Jitsugyou Co. lumps of pork, and tofu blocks
0.5 50 Lab prototype Radish, tuna, sweet potato, No effect No effect No effect No effect Suzuki and others (2009);
yellow tail fish, and agar gel Watanabe and others (2011)
Research paper
Pulsed 500 1 Lab prototype Potato starch gels – – – Larger exudates. Miura and others (2005)
magnetic Lower rupture stress Patent
field (55
ms)
Static 1.5–2 20,30 and Commercial Chicken breasts – Longer freezing – No effect on drip and cooking Yamamoto et al. (2005)
magnetic 40 freezer designed Plateau losses. Research paper
field þ by ABI Softer texture after 6 months of
oscillating Co., Ltd. frozen
magnetic Storage
field
1 0.6 50 Patented by ABI Chicken and tuna – Time for lowering the core – Cells were hardly destroyed. Owada (2007)
Co., Ltd. temperature Color, Patent
from 0 C to 20 C flavor, and taste
was 20% to 50% similar to those of the original
reduced raw
food
20 0.12 1 106 Lab prototype Tuna and agar gel No effect No effect No effect No effect Suzuki and others (2009);
Watanabe and others (2011)
Research paper
n.r. n.r. Commercial Beef (loin and round) – – – Lower drip losses. Kim et al. (2013)
freezer designed Larger water holding capacity. Research paper
by ABI No effect on sensory evaluation
Co., Ltd.
n.r n.r Commercial Beef (loin and round), pork – Shorter total freezing – Effects on drip and cooking Kim et al. (2013)
freezer designed (belly and ham), and chicken Time losses, Research paper
by ABI (breast and leg) water holding
Co., Ltd. capacity, and composition
Food Freezing: Emerging Techniques for Improving Quality and Process Efficiency a Comprehensive Review
depend on the
product
n.r n.r Commercial Pork (belly and ham) – – – Effects on drip and cooking Ku and others (2014)
freezer designed losses, Research paper
by ABI water holding
Co., Ltd. capacity, and moisture
content
depend on the pork
cut. No effect on sensory
evaluation
0.098 50 Commercial Garlic bulbs No effect – – – James et al. (2015)
0.155 freezer designed Research paper
0.418 by ABI
Co., Ltd.
n.r n.r Commercial Beef (loin and round) – – Smaller Larger water holding capacity. Choi et al. (2015)
freezer designed Better Research paper
by ABI overall
Co., Ltd. acceptability after sensory
evaluation.
Better flavor and Taste
Oscillating 0.5* EF: 50* EF: 50* Patented by Chicken and tuna – Time for lowering the core – Cells were not ruptured, color, Owada (2007) Patent
MF þ 15 kV/m 50 Hz– ABI Co., Ltd. temperature from 0 C to flavor, and taste are the same
electric 5 MHz 20 C was 50% more as the original raw food
field reduced
Static MF þ 10 0.5* 50* Patented by ABI Tuna, sardine, pork, juices, – No effect on precooling time. – Lower drip losses, color and Owada and Kurita (2001)
oscillating EF: 600 EF: n.r. Co., Ltd. wines, Shorter freezing plateau. odor changes, Patent
MF þ kV/m oranges, cakes Shorter and microbial
electric total freezing time counts. No phase
Field separations
1 0.5 * 50* Patented by ABI Chicken and tuna – Time for lowering the core – Cells were not ruptured. Color, Owada (2007)
EF: 15 kV/ EF: 50 Hz– Co., Ltd. temperature flavor, and taste are Patent
m 5 MHz from 0 C to 20 C the same as the
was 50% or more original raw food
reduced
1 0.5 * 50* Patented by ABI Mackerel and lobster – – – Improved microstructure after Owada and Saito (2010)
EF: 100– EF: n. r. Co., Ltd. thawing Patent
1000 kV/m
–, Not studied; n.r., Not reported; *EF, Electric field.

From Otero et al. (2016).
49
temperatures. Under the effect of external SEF, the alignments of water molecule dipoles changes from its native random direction
to the direction of the electric field vector. This realignment of water molecule dipoles strengthens the hydrogen bond between the
water molecules in the direction of the electric field. As a result the structure of water clusters can be reordered, which in turn may aid
in the nucleation process (Wei et al., 2008; Shevkunov and Vegiri, 2002; Sun et al., 2006a; Vegiri, 2004; Vegiri and Schevkunov,
2001). SEF application can induce ice nucleation at a desired degree of supercooling which is a function of strength of SEF and
the nucleation temperature (Orlowska et al., 2009).
Dufour (1862) is believed to be the first researcher to study the freezing of supercooled water assisted by SEF. Since then several
laboratory scale studies have been conducted to learn about SEF assisted freezing. SEF has been investigated in both model and real
food systems and summary of which is provided in Table 3. In food system studies on investigating the effect of SEF assisted freezing
on food quality parameters such as texture, microstructure, color, drip loss on thawing and water holding capacity has been con-
ducted by various researchers. SEF application during freezing assist in producing numerous small sized ice crystals in frozen
matrices, and thus, minimizes the cell disruption, reduce the drip loss, lessen the protein denaturation, and preserve the texture
of the fresh food to a greater extent after thawing (Orlowska et al., 2009; Xanthakis et al., 2013; Wei et al., 2008; Jia et al., 2017;
Dalvi-Isfahan et al., 2016; Carpenter and Bahadur, 2015).
3.03.8.2 Fluctuating Electric Field Assisted Freezing

The fluctuating electric field (FEF) application in assisting with freezing to retain better food quality is a very new and emerging
technology getting attention by various researchers. The mechanism of action is yet to be completely understood, but few hypoth-
eses have been proposed by different researchers. One of such hypotheses is that, the FEF is generated in the inner space of a freezer.
This gives vibration to the water molecules and ions of water contained in the material placed in the inner space, thereby the mate-
rial is supercooled below the normal icing temperature while suppressing the freezing of the water, and subsequently when the
generation or the fluctuation of the magnetic field or the electric field is terminated, the material is instantaneously frozen at
a low temperature (Hiroshi et al., 1999). Another hypothesis proposed that, the FEF induced torque can increase the number of
isomeric configurations and displace water molecules from the equilibrium state in a cluster, thereby reducing the chance of config-
uration of cluster of molecules which is well suited to integrate into a crystal lattice. As a result, the crystal growth rate will decrease
considerably (Sun et al., 2006b; Woo and Mujumdar, 2010; Dalvi-Isfahan et al., 2017b).
The FEF can interfere with both the steps of crystallization: the nucleation of ice crystal in the supercooled water and the subse-
quent ice crystal growth from the existing nuclei. They also suggested that the FEF induced crystallization process is a function of FEF
frequency and intensity applied to the system (Sun et al., 2006b,c; Stan et al., 2010). The effect of FEF and its operating parameters
(frequency and intensity) on freezing of water, change in vibration frequency of the H2O dipole freezing time, ice morphology, ice
nucleation rate and crystal size distribution are investigated by various researchers (Mok et al., 2015; Sun et al., 2006b; Salt, 1961;
Bartlett et al., 1963). Based on thermodynamic models, it was proposed that FEF strength ranging from 107–108 V/m fields and the
frequency of 100 kHz might cause an evident increase in the rate of ice nucleation (Stan et al., 2010).
The peer-reviewed research articles related to FEF assisted food freezing are very scarce when it comes to freezing of real food
matrix under FEF. However, there are some recent patents claiming better food preservation by freezing under FEF. A patent by
Owada (2007) claimed that the freezing of chicken and tuna under the influence of FEF at 1.5 104 V/m and the frequency in
the range from 50 Hz to 5 MHz reduced the time for lowering the core temperature of the samples from 0 C to 20 C
and 40 C by 20% to 50% respectively. Their highly-efficient freezing apparatus is capable of producing a good quality frozen
product with minimal damage to their cells and thus, the color, flavor, and taste were retained. The inventor suggested that, the
fluctuating electric field with variable frequency can eliminate the growth of ice crystal nuclei, and thus, a high degree of supercool-
ing can be achieved. The suppression of the ice crystallization prevents the surface of the objects from freezing and therefore,
increases the heat transfer from inside of the object to the surrounding cooling medium. Thus, the cooling rate of the objects
can be remarkably increased.
Owada (2007) also proposed hybrid method combining FEF and MF (either SMF or OMF or both was applied simultaneously)
for the freezing of food products. They claimed that the hybrid method, such as: (a) freezing under the influence of FEF (E ¼ 1.5
104 V/m at frequency in the range from 50 Hz to 5 MHz), SMF (1 mT), and OMF (0.5–0.7 mT, 50 Hz), and (b) freezing under FEF
(E ¼ 1.5 104 V/m, 50 Hz to 5 MHz) and OMF (0.5–0.7 mT, 50 Hz) reduced the time for cooling the central temperature of prod-
ucts from 0 C to 20 C or 40 C by 50% or more. When FEF was applied simultaneously with the OMF, the free water in the
food matrix interacted with proteins and carbohydrates and turned into bound water forming molecules of hydrated higher order
structures. According to them, this reduction in the amount of free water decreased the probability of ice crystallization and conse-
quently led to a higher cooling rate. Moreover, it was claimed that the minimum cell damage helps retaining maximum quality of
the product like color, flavor, and taste. Another inventor, Kim et al. (2013) patented a non-freezing refrigerator claiming that it can
maintain the contents in a non-frozen state by applying an FEF generated by a radio frequency voltage when it is supercooled at
temperatures in the range of 0 to 5.8 C. The inventors proposed that the torques exerted by FEF would continuously rotate
and vibrate the water molecules to inhibit the ice crystal formation and keep water in the product in the supercooled state. Accord-
ing to the inventors, their invention can keep the food products (meat, fish, fruits and vegetables) in highly fresh state for a longer
period of time as the product would be kept below the freezing temperature and with minimum chances for the microstructure to be
damaged due to ice crystal formation. The claims made in this patent are encouraging, but they are not supported by research
studies.
Table 3 Key published studies on the use of SEF assisted freezing for model and real food systems.
Sample Conditions Observations References
Water drops of a few millimeters in 2–6 106 V/m, Electric field was • Freezing of water drops initiated in the presence Rau (1951)
diameters applied once the water got of electric field than compared to without field
supercooled to a temperature conditions.
between 4 to 7 C
Distilled Water and water with organic 6 105 V/m • The SEF up to 6 105 V/m had no intrinsic effect Doolittle and Vali
nuclei on the heterogeneous freezing process (1975)
Interfacial water 106 V/m, at a room temperature • The researchers were able to freeze interfacial Choi et al. (2005)
water at room temperature by using a weak
electric field (106 V/m).
Distilled water (1 mL) Sample was cooled from 5 C to • Application of electric field induced nucleation at Wei et al. (2008)
30 C in the presence of electric higher temperature compared to no field.
field varying from 1.0 103–1.0 • (SEF application led to a lower supercooling
105 V/m degree)-SEF greater than 1.0 104 V/m was
required to have a significant effect on water
freezing process.
Distilled water (1.6 mL) The SEF equivalent of 0–6.0 106 V/m • SEF influenced water freezing process: the Orlowska et al.
was applied when distilled water degree of supercooling decreased, and the phase (2009)
sample was cooled from 1 to 16 C transition time increased with increasing
strength of the SEF (For e.g., SEF strength of
6.0 106 V/m decreased the supercooling
degree approximately by 52% than compared to
zero field condition. While at same SEF strength
crystallization time increased by 22%).
• Controlled ice nucleation at a small degree of
supercooling (DT ¼ 4 C) with a probability of
100% was possible by using higher SEF strength
of 6.0 106 V/m.
Pork tenderloin(1 g) 0–12 kV, sample was cooled from 1 to • Lower supercooling under DC voltage was Xanthakis et al.
20 C with a cooling rate of 1 C/ observed. (2013)
min • Ice crystal size reduced under DC voltage
conditions (For instance, the average ice crystal
size obtained at 12 kV was around 44% lower
than that obtained at zero field condition).
Water (5 mL) Up to 8 107 V/m • Freezing temperature significantly increased by Carpenter and
15 C with the increase in strength of the SEF Bahadur (2015)
with a saturation at 2.0 107 V/m.
• Also, current passing through the water droplets
elevated the freezing temperature.
Deionized water droplets 4.28 0.13 105 V/m, cooling rate of • Ice nucleation was promoted under a 105 V/m Zhang et al. (2016a)
1.0 0.2 K/min electric field and was independent of the field
direction.
• The ice nucleation rates were found to be higher
under an electric field.
Lamb meat (2.3–2.5 g), (Ø ¼ 0–5.8 104 V/m, sample was cooled • Ice crystal size reduced with increasing Dalvi-Isfahan et al.
10 mm, H ¼ 10 mm) to 20 C magnitude of SEF. (2016)
• Freezing under SEF reduced the drip loss,
meanwhile, it kept hardness and microstructure
of lamb meat on thawing.
Deionized water and Pork tenderloin: DC voltage of magnitude 0–10 kV was • Freezing of deionized water under DC voltage Jia et al. (2017)
fresh meat was cut into cuboids applied at the same time upon resulted in lower supercooling.
(50 50 10 mm3) initiation of cooling the samples to • Freezing in combination with exposure to a 10 kV
less than 15 C led to smaller ice crystals in the meat samples
than ordinary freezing treatments. Moreover, the
meat quality indicators, such as color, pH, and
water holding capacity of sample frozen under
10 kV treatment were closer to those of fresh
pork tenderloin, while freezing without DC
voltage gave inferior quality product.
Agar gel (Ø ¼ 20 mm, H ¼ 10 mm) Agar gels were frozen under SEF 0– • SEF aided in production of smaller size ice Dalvi-Isfahan et al.
5.8 104 V/m at 20 C crystals, but did not cause any obvious change in (2017a)
syneresis and texture of the samples.
(Continued)
Table 3 Key published studies on the use of SEF assisted freezing for model and real food systems.dcont'd
Sample Conditions Observations References
Distilled water, NaCl solutions, SEF intensities of 0.0–9.6 105 V/m • The pure water had the highest freezing Fallah-Joshaqani
mushroom extract and mushroom during freezing at 30 1 C temperature, supercooling degree and shortest et al. (2019)
phase transition period in the absence of electric
field. By applying the electric field, the nucleation
temperature and phase transition period of the
samples increased.
• The highest nucleation temperature was
observed in the pure water under 6.4 105 V/m
electric field
• The nucleation temperature of the other samples
showed an optimum value in the intensity of
3.2 105 V/m
Agarose gel High-voltage electric field (HVEF) • HVEF combined with a low freezing rate Wang et al. (2019)
produced by an improved electrode significantly reduced the supercooling degree,
system enhanced the average freezing rate in particular
the nucleation rate, and higher internal electric
field intensity showed a better microstructure
with smaller ice crystals in frozen samples.
• Study suggested that HVEF-assisted freezing
was able to reduce the size of ice crystals formed
in semi-solid model foods, and the integration of
a dielectric spacer with high permittivity to the
electrode could be used as a potential method to
solve the electrical discharge problem.
Ø ¼ Diameter, H ¼ Height.
From Jha et al. (2017).
Jha et al. (2018b) in their recent review covered the latest summary of advances of electro-freezing in food processing. So far, SEF
for model and real food systems has been performed at a laboratory scale on small sample size whereas FEF research studies are very
rare but few recent patents are available. These technique needs further studies, tailored optimization of parameters and conditions,
and scale up in order to compete with the existing freezing techniques at an industrial level.
3.03.9 Microwave Assisted Freezing
The potential of microwave assisted freezing (MAF) has been investigated by a few researchers. MAF have shown promises to
produce smaller ice crystal with less intensive energy requirements (Hanyu et al., 1992; Anese et al., 2012; Xanthakis et al.,
2014; Jackson et al., 1997). MAF is a novel and innovative technology that it is based on electromagnetic perturbations during
the crystallization process of a matrix (Xanthakis et al., 2018). Two hypotheses have been proposed to explain the mechanism of
MAF: (i) Water molecules rotations due to microwaves interference with Hydrogen bond network, which could be a crystalline
structure precursor (Hanyu et al., 1992); (ii) Microwave heating induces a partial melting of ice crystals. The small temperature
rise induced by microwaves pulses is followed by a rapid temperature decrease. The partial melting due to these temperature
oscillations could induce a secondary nucleation (Xanthakis et al., 2014). Sadot et al. (2017) worked on numerical modeling
of an innovative microwave assisted freezing process and reported that the freezing front location and the reflection at air-
product interfaces have a large impact on microwave behavior in the product, especially on hot-spot displacement. As in
some experimental work, the temperature oscillations were observed. It is shown that their amplitude is related to the pulse
duration. These results will help in designing experimental procedures to study the application of low energy pulsed microwaves
during freezing. Xanthakis et al. (2014) in their investigation reported 62% reduction in the size of ice crystal for the pork meat
frozen under higher microwave irradiation power. Xanthakis et al. (2018) reported promising results regarding the microstruc-
ture of meat and fish sample frozen under the influence of MAF. They reported that the application of constant microwave power
during freezing can lead to the elimination of the intracellular crystals in fish samples. Xanthakis et al. (2015) Investigated the
effect of microwave assisted freezing on pork tenderloin freezing temperature profiles at different power level of 40%, 50% and
60% (Fig. 8). In their pre-study they learned that at lower levels no influence appeared on the ice crystal sizes while higher power
was restricted due to heat transfer limitations. As shown in Fig. 8 conventional food freezing temperature curves were smooth,
while MAF sample freezing temperature curves appeared to decrease in steps. A significant decrease of the freezing rate at three
levels of microwave power was reported compared to the conventional freezing. There was also a reduction in degree of super-
cooling when a power level of 40% microwave radiation was applied. The degree of supercooling was further decreased when
Figure 8 Real time – temperature plots obtained during conventional freezing (red curve) and under different power levels of microwave radiation
of pork tenderloin samples (40% - green curve, 50% - purple curve, 60% - blue curve). From Xanthakis et al. (2015).
the microwave power level was higher. The overall freezing time was longer in the MAF conditions as compared to the conven-
tional freezing and it increased in tandem with the increase in power level. Xanthakis et al. (2015) also performed the micro-
structure analysis of the frozen pork tenderloin and micrographs images (transversal cuts to the fiber direction) of samples after
freezing under different microwave power levels are presented in Fig. 9. Based on quantitative analysis of voids (white zones)
representing the location of the ice crystals, it was suggested that the damage to the tissues of the meat is higher with the conven-
tional freezing procedure (Fig. 9A) than with the application of MAF (Fig. 9B–D). Jha et al. (2019) investigated the effect of low
energy MAF (constant microwave power-167 W/kg and pulse microwave power-500 and 667 W/kg with 10 s pulse width and
Figure 9 Micrograph images of frozen pork tenderloin transversal cuts under different levels of microwave power radiation. (A) 0% (conventional
freezing), (B) 40%, (C) 50% and (D) 60%. The tissues of the pork tenderloin muscle are shown in red while the voids (white zones) represented the
location of the ice crystals that were formed in the microstructure during freezing. From Xanthakis et al. (2015).
20 s pulse interval resulting in an average power of 167 and 222 W/kg) on freezing time and quality attributes (microstructure,
texture, drip loss and color) of apple and potato. They reported that the freezing time was not affected by the MAF process and
less freeze damage in apple and potato compared to control sample. Jha et al. (2018a) investigated the impact of freezing under
low power MAF (2450 MHz) and reported no effect on the freezing time and the microstructure of the potatoes. They also re-
ported that the time taken by short pulse high power (SPHP), long pulse low power (LPLP) and constant microwave (MW)
freezing conditions were 37.53, 19.87 and 20.18 min respectively, while conventional freezing process to reach same temper-
ature (from 6 C to 10 C) was 13.95 min, which indicated shorter freezing time of conventional freezing method compared to
SPHP, LPLP and MW freezing conditions. Also the image analysis results suggested that the MAF produced better microstructure
in potato sample than the conventional freezing method. Chizoba Ekezie et al. (2017) in their comprehensive review summa-
rizes the recent developments in MAF in process efficiency and product quality.
So far very limited research work has been published by researchers in this field and further research is required to gain more
understanding on this technology so as to harness the benefit of this technology at commercial level.
3.03.10 Radio-Frequency Assisted Freezing
Radio-frequency assisted (RFA) freezing is again a new emerging technology to enhance freezing by producing instant and smaller
ice-crystal in food matrix to minimize tissue damage caused by large ice-crystals. RFA is interestingly based on its long and pene-
trating wavelengths, low investment costs, energy saving due to its high energy efficiency, and compatibility with automated produc-
tion in batch and/or continuous flow processing (Anese et al., 2012). This is the very latest technology and not a lot of research
literature is available on it.
Anese et al. (2012) in their experiment tried to utilize radio frequency induced water dipole rotation to control ice crystal size
during freezing of a pork meat. This experiment involved application of low voltage RF pulses to minimize heat generation and
a specially designed pilot scale RFA freezing equipment (Fig. 10). This equipment comprised of modified pilot-scale radiofrequency
(RF) equipment (3.5 kW, 27.12 MHz, Stalam Spa, Nove, Vicenza, Italy) with plate applicators as a source of low voltage RF energy
and a cryogenic fluid flowed in the chamber through three aligned nozzles (Mod. H1/8VV-6503, 6502, 6501, Spray Systems Co.,
Wheaton, IL, USA) placed at 3 cm distance from each other on a 7 cm diameter polytetrafluoroethylene (PTFE) pipe. Anese et al.
(2012) in their study, reported that the microstructure of meat frozen by low voltage pulse (2 kV) RF assisted freezing had a smaller
ice crystals, better cellular structure, less intercellular voids and cell disruption as compared to the control sample. The smaller ice
crystal formation was attributed to the ability of RF to depress the freezing point thus producing more nucleation sites. Hafezparast-
Moadab et al. (2018) investigated the RFA freezing application (three electrode gaps: 2, 3 and 4 cm) on rainbow trout fish to under-
stand freezing process and quality characteristics (drip loss, color, texture and microstructure) of fish after thawing as compared to
the conventional air blast freezing method. They reported a reduced drip loss, however no significant fish weight loss on freezing.
The color was not affected by RFA freezing. Textural analysis displayed similar hardness, gumminess and chewiness of RF treatments
compared to the fresh sample (unfrozen). The microstructure analysis of frozen fish indicated significantly reduced ice crystals
under RF-assisted freezing and at the minimum electrode gap it was about 75% of the size of the ice crystals of the control sample
frozen without RF.
As stated earlier the RFA freezing is relatively new technology and hence further investigations are required to understand the
effect of RFA freezing on different food matrices by combining different process variables including RF power, cooling media
and cooling parameters. Also, significant efforts will be required to apply this technology at industrial scale.
Figure 10 Schematic representation of the RF chamber modified to allow cryogenic freezing. From Anese et al. (2012).
3.03.11 Freezing Assisted Biosubstances Capable of Regulating Freezing Point Depression
Traditional methods of food freezing by regulation of freezing point mainly involves chemical regents, ion solutions and alcoholic
solutions (Castro et al., 2018; Day and Stacey, 2007). With recent consumer awareness and increasing demand of clean label foods,
the food industry is looking for alternative to this freezing point regulating chemicals. Recently, naturally sourced biosubstances are
showing some promises as chemical alternatives to freezing point regulator in water during freezing. These biosubstances can be clas-
sified in category of (i) ice-nucleating proteins (INPs) for increasing freezing point (Pandey et al., 2016), (ii) antifreeze proteins (AFPs)
and (iii) natural deep eutectic solvents (NADES) for suppressing freezing point (Gertrudes et al., 2017; He et al., 2018). Among these
biosubstances, both AFPs and INPs are considered as ice-binding proteins (IBPs) because of their ability to bind with the ice surface
(Duman, 2015), while NADES, as eutectic solvents present in nature, are a transparent liquid mixture of two or more natural products
(Liu et al., 2018c). Tian et al. (2020) provided the very comprehensive review of naturally sourced biosubstances for regulating freezing
points in food researches, their mechanisms, current applications and latest future application trends.
3.03.11.1 Antifreeze Proteins

AFPs are naturally occurring cryoprotectants that retard the freezing point of water. Antifreeze proteins were first discovered in
Antarctic marine fishes preventing it from freezing in icy seawater (Devries and Wohlschlag, 1969) and after that they were gradually
isolated from other cold surviving organisms, such as bacteria, algae, fungi, plants, insects and polar fishes (Bredow and Walker,
2017; Ding et al., 2015; Hassas-Roudsari and Goff, 2012; Meister et al., 2015; Tomalty and Walker, 2014; Villarreal et al., 2018;
Wu et al., 2018; Tomalty et al., 2019). AFPs derived from different species with different cold adaptation and environment stress
possess different structures. AFPs with different structures are categorized in six categories, AFPs I, AFPs II, AFPs III, AFPs Ⅳ, hyper-
active AFPs and anti-freezing glycoprotein AFPs (Duman, 2015). The AFPs retards ice growth by the Gibbs–Thompson effect
through binding over the surface of seed ice crystals (Raymond and Devries, 1977). AFPs are capable of causing a depression of
the solution freezing point below the ice melting point, which is termed thermal hysteresis (TH), and led to the suggestion that
AFPs could be used to extend freeze protection to other fishes (Hew et al., 1999). The detailed mechanism of AFPs in freezing point
depression has been very well summarized by Tian et al. (2020). The AFPs with varying structure inhibit ice growth with different
activities (TH z 0–13 C), and hyper active AFPs mostly derived from insect exhibit excellent freezing point depressing ability,
achieving high TH values (>5 C) at low concentrations. As a result, hyperactive AFPs have gained much more attention in AFP
studies (Hudait et al., 2018a,b; Meister et al., 2015).
Since AFPs are commonly present in various human diet foods such as fish, shrimp, mussel, carrot and cabbage, it is thus consid-
ered that humans have ingested AFPs as a part of food for a long time and based on that it can be argued that AFPs in human diges-
tion and metabolism are safe. With the ability of AFPs to depress the freezing point and inhibit recrystallization, AFPs can also be
used as natural ice crystal formation regulators within the food. Table 4 lists recent studies on AFPs applications in food freezing.
3.03.11.2 Ice-Nucleating Proteins (INPs)

Ice nucleation proteins are another class of biosubstances with their ability to initiate heterogeneous ice crystallization at high
subzero temperatures up to 2 C. These INPs are large and multimeric with subunits ranging from 120 to 150 kDa in size.
INPs are structurally homologous class of proteins and composed of three domains: (i) a N-terminal domain, (ii) a central repeating
domain with (RCD) varying amino acid sequence and sequence repetition in the CRD (CRD), and (iii) C terminal domain (Kawa-
hara, 2017). These large INPs through their ice binding sites provide an ice lattice template for the ordering of free water molecules
responsible for inducing ice crystal nuclei (Xu et al., 1998). These ice binding sites contains repeated amino acid sequences to
promote ice formation by generating ice nuclei (Tian et al., 2020). The detailed mechanism of INPs producing ice nucleation
and subsequent ice growth under high subzero temperatures has been very well summarized by Tian et al. (2020).
INPs capabilities in increasing freezing point and facilitating ice formation under high subzero temperatures has been investi-
gated by various researchers in different food freezing application. Table 5 provide the summary of recent applications of INPs in
the food freezing applications. Various research on application of INPs in to real foods or model foods, packaging, and in freeze
drying and freeze concentration is available in literature. However, applications of INPs in real foods are still not widespread, which
may be due to the cost and complexity of the crystallization mechanisms (Aichinger et al., 2017). Further research is required to gain
a better understanding of the INPs mechanisms, industrial applications and the safety of this particular material in the commercial
freezing of food products.
3.03.11.3 Natural Deep Eutectic Solvents

Natural deep eutectic solvents (NDES) are emerging novel natural biosubstances assisting with enhancing freezing efficiency of food
products (Choi et al., 2011) was the first one to report term NDES. The knowledge of NDES originated from the fact that some cold
tolerant species are capable of producing metabolites that can significantly reduce the crystallization temperature of water inside
their cells to balance osmolality of the tissues to avoid osmotic stress and allowing them to survive at extreme temperature ampli-
tude with a low death rate (Gertrudes et al., 2017). Some of this metabolites contains a mixture of organic acids, sugars, urea and
choline derivatives and are generally mixtures of glycerol as hydrogen bond donor and quaternary ammonium salts as hydrogen
Table 4 Summary of recent research for the applications of AFPs in the foods.
Field AFP sources Products Effects References
Food Yeast Glaciozyma sp. (recombinant AFPs) Korean Beef • Prolonged the shelf-life by delaying lipid peroxidation Lee et al. (2015)
freezing and microbial growth rates during cold storage.
• Improved antioxidative enzyme activities during cold
storage.
• Reduced thiobarbituric acid reactive substances.
Tenebrio molitor larvae Vegetables • Cryoprotective effect on onion, cucumber, carrot, Song et al. (2019)
zucchini texture retention at 4, 0, 2, and 20 C for
13 days.
• Higher breaking force measured.
Chinese privet (Ligustrum vulgare) leaves Frozen Gluten-water • Increased hydration of protein. Jia et al. (2014)
dough • Improved dynamic rheological properties.
Recombinantly produced fish type III and Ice cream • Improved shape preservation during melting. Kaleda et al. (2018)
winter rye • Improved frozen network of ice-crystal and ice-cream
mix.
Cold-Acclimated Oat (Avena sativa L.). Ice cream • Improved recrystallization and melting resistance of Zhang et al. (2016b)
ice cream
Increase in glass transition temperature.
Drimys angustifolia leaves Star fruit • Physicochemical properties unchanged. Provesi et al. (2019)
• Firmness was maintained on thawing after 60 days of
storage.
Pichia pastoris GS115 (recombinant Hydrated gluten • Alleviated GMP depolymerization, weakened the Liu et al. (2018a)
AFPs) damage of freeze-thawed cycles to disulfide bonds,
secondary structure, and microstructure of hydrated
gluten, and protected the rheological properties of
hydrated gluten during freeze-thawed cycles.
Pichia pastoris GS115 (recombinant Frozen dough, bread • Decrease in increment of freezable water content Liu et al. (2018b)
carrot AFPs) during freeze-thawed cycles, weakened the damage of
freeze-thawed cycles to fermentation capacity and
microstructure of frozen dough, and consequently
improved the specific volume and texture properties
of bread.
Purchased type III AFP Truffles • Reduction in quality degradation of freeze-thawed Derossi et al. (2015)
truffles.
• Increase in porosity fraction in treated truffles.
Lolium perenne Tomato lines • Elimination of chilling stress induced damage. Balamurugan et al.
• Increase in relative water content and reduction in (2018)
electrolyte leakage in transgenic tomato lines
compared to wild type lines.
Type I AFP (Fish) Strawberries • AFP impregnated strawberries showed no statistical Rosa et al. (2019)
differences with respect to the physicochemical
properties.
• Drip loss was statistically lower from the thawed
strawberries treated with the antifreeze protein.
• Less damage to the microstructure.
Modified from Tian et al. (2020).
acceptor in the food system, and such mixtures have a lower melting point than that of the individual compounds (Abbott et al.,
2004). The interactions between water and NDES are capable of maintaining water in liquid state even at 50 C (Dai et al., 2013;
Gertrudes et al., 2017). Consequently, NDES has shown potential as freezing point regulating agent for the food freezing applica-
tion. The detailed mechanism of NDES producing ice nucleation and subsequent ice growth under high subzero temperatures has
been very well summarized by (Tian et al., 2020).
The research related to NDES application in natural products extraction, biocatalysis, electrochemistry, protein thermostability
enhancement, CO2 capture and biomedicine are widely reported in literature (Paiva et al., 2014), however very little has been re-
ported on its application in food freezing. Table 6 provides the summary of recent applications of NDES in food freezing
applications.
With change in life style, increasing consumer awareness and demand for clean label, people increasingly prefer safer, more
natural and nutritional foods. Naturally sourced biosubstances generally meet these demands for the frozen food applications
as an alternative to chemical based cryoprotectant/freezing point regulators. These naturally sourced freezing point regulators
including INPs, AFPs and NDES are alternatives for improving frozen food quality, with advantages of greenness, nontoxicity,
Table 5 Summary of recent research for the applications of INPs in the foods.
Fields INP sources Products Effects References
Food Pseudomonas, Erwinia and Model food systems and real • Elevates nucleation temperatures. Review: Li and
freezing Xanthomonas foods, such as salmon, egg white • Reduces freezing times and improves the quality Lee (1995)
protein and cornstarch gels (e.g., the flavor and textural properties) of frozen
foods.
• Suggests that there may be profound potential
for energy savings and quality improvement in
the food industry.
Erwinia herbicola subsp. Ananas Fish actomyosin gel • Better retention of Ca2þ ATPase activity. Zhu and Lee
• Significantly reduces denaturation of AM protein (2007)
caused by FT cycling.
• Significant protective effect on gel-forming
capacity of fish and textural stability of fish AM
during FT cycling
Ice-nucleation active bacteria Solid model food • Freezing operations carried out at 20 C Zhang et al.
(INAB), Pseudomonas syringae pv. showed that the addition of INAB produced no (2010b)
Panici obvious change in the freezing time.
• The scanning electronic microscope (SEM)
observation of microstructure of the model food
indicated that the mean ice crystal size was
reduced from 25.7 mm to approximately 15 mm
by the addition of INAB.
Biogenic ice nucleators from Frozen dough • Hardening of bread crumb caused by three Shi et al.
Erwinia herbicola freeze/thaw cycles was alleviated by about 50% (2013b)
compared to the control.
• The mechanism of cryoprotective effects from
INPs was possibly that INPs helped in
preserving the viability of yeast cells during
freeze/thaw cycles.
• Study revealed the potential of ECINs as
a cryoprotectant for applications in the food and
biotechnology industries.
Extracellular Ice Nucleators from Magnetic Fe3O4/Chitosan • Increase of ice nucleation temperature for water, Zhou et al.
Erwinia herbicola Nanoparticles seawater and apple juice (6.83 0.18 C, 8.08 (2014)
0.50 C and 9.38 1.12 C).
• Promising applications for INPs in freeze
concentration industry fields
INPs Block freeze concentration • Improve efficiency of block freeze concentration Jin et al. (2017)
in a desalination model.
• Approximately 50% of the energy cost can be
saved by the inclusion of INPs in desalination
cycles while still meeting the EPA standard of
drinking water (<500 ppm).
• Promote the development of a lamellar
structured ice matrix with larger hydraulic
diameters, which facilitates brine drainage and
contains less brine entrapment as compared to
control samples.
• Great potential for applying INPs to develop an
energy-saving freeze concentration method via
the alteration of ice morphology.
INPs Freeze drying • X-ray CT image analysis provides new evidence Jin et al. (2018)
of 3D ice structures in frozen samples before
sublimation.
• The modification of ice morphology by INPs is
very likely to be the major reason for efficiency
improvement.
• The morphology study emphasizes the
importance of controlling the freezing step and
related ice morphology.
• Suggests significant energy savings.
(Continued)
Table 5 Summary of recent research for the applications of INPs in the foods.dcont'd
Fields INP sources Products Effects References
Food Zein-basedIce nucleation films Frozen bread dough • Increased the water ice nucleation temperature. Shi et al.
packaging (INFs) • Wrapping the INFs on frozen dough improved its (2013a)
baking qualities.
• INFs showed potential in reusability.
Erwinia herbicola Zein film • INPs-modified zein film elevated the ice Shi et al.
nucleation temperature of distilled water from (2013c)
15.5 C to 7.3 C.
Erwinia herbicola Low-density polyethylene (LDPE) • Up to 4–5 C increase in ice nucleation Gezgin et al.
films temperatures and an up to 10 min decrease in (2013)
freezing times were observed with high-purity
deionized water samples frozen in ECIN-coated
LDPE films.
• Films retained their ice nucleation activity up to
50 freeze–thaw cycles.
• Results suggests potential of using ECIN-coated
polymer films for frozen food application.
Modified from Tian et al. (2020).
Table 6 Summary of recent research for the applications of NDES in the foods.
Fields Products Effects References
Food Freezing Frozen Lactic acid bacteria culture • No adverse effect on cell membrane integration. Qiao et al. (2018a)
• Enhanced intracellular enzyme activity, confirming their
LAB viability preservation ability.
High freeze-thaw stable wheat gluten-based emulsions • Higher concentrations of NDES exhibited elastic gel-like Liu et al. (2020)
emulsions with smaller droplet size.
• Wheat gluten-based emulsions showed extraordinary
freeze-thaw stability against coalescence after 3 cycles of
freeze-thaw treatment (40 C, 24 h; 25 C, 2 h).
Freeze dried Streptococcus thermophilus • NDES formed by choline chloride and D-sorbitol Qiao et al. (2018b)
significantly increased S. thermophilus viability after
freeze-drying.
biodegradability and biocompatibility (Tian et al., 2020). The literature for applications of the naturally sourced freezing point
regulating biosubstances in the food researches are very limited, especially for INPs and NDES. The effect of natural freezing point
regulators on improving frozen food quality is encouraging and further investigation at the same time making sure they meet the
food safety requirements for food applications is required.
3.03.12 Conclusions
Freezing is a widely used method for food preservation which maintains its nutritional quality, sensory characteristics and textural
properties. Although freezing is used for food preservation for several decades, it is not suitable for all foods, and freezing can cause
physical and chemical changes in some foods that are perceived as reducing the quality of either the thawed material or the final
product. Moreover, food manufactures are also looking for improving food quality through production of smaller ice crystals (to
reduce damage caused by large ice crystals) and at the same time lower cost of freezing. Food manufacturers are also looking for
advanced freezing technologies to freeze foods which they cannot freeze previously without affecting its quality significantly. On
the consumer side with change in life style, increasing consumer awareness and demand for clean label, people increasingly prefer
safer, more natural and nutritional foods. The research in food freezing are advancing at very rapid pace to enhance shelf life, main-
tain product quality as close as to original unfrozen product, reduce cost of freezing and meet the changing consumer need and
perception. In this paper we reviewed the various novel innovative freezing technologies that are currently being researched and
developed throughout the world to improve freezing conditions and product quality. Some of the innovative freezing technologies
reviewed here (impingement and hydrofluidization) are essentially improvements of existing methods (air blast and immersion,
respectively) to produce far higher surface heat transfer rates than previous systems and thus improve product quality through rapid
freezing and lower the cost of freezing in some applications. The factors related to product or process affecting freezing efficiency are
also reviewed here. Other technologies (High-pressure assisted freezing, Ultrasound-assisted freezing, Freezing assisted by Magnetic
field, Electric field assisted freezing, Microwave assisted freezing, Radio frequency assisted freezing) are adjunct to existing freezing
systems that aim to improve product quality through controlling ice crystallization process in the food during freezing. Another
alternative is to change the properties of the food itself to control how ice is formed during freezing (Freezing assisted by bio-
substance capable of regulating freezing point) which also has a potential to satisfy clean label demand of the consumer.
Some the novel technologies such as natural deep eutectic solvents, ice-nucleating proteins and antifreeze proteins reported here are
well established on other types of food application. However for their application in food freezing they are still at very early stage of
development. Some of the challenges this new technologies are faced with are high capital cost, fitting them into continuous commer-
cial freezing operation as well as food safety regulations. These emerging novel technologies have shown great potential in research
studies and continued research efforts are required to address the challenges associated with their success at commercial level.
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3.

03 Food Freezing: Emerging Techniques for Improving Quality and Process

36 Innovative Food Processing Technologies, Volume 3 https://doi.org/10.1016/B978-0-08-100596-5.23035-7

3.03.2 Basics of Freezing Fundamental

Improvements of existing methods Impingement freezing

3.03.3 Impingement Freezing

3.03.5 High Pressure Assisted Freezing

3.03.6 Ultrasonic Assisted Freezing

3.03.7 Freezing Assisted by Magnetic Field

3.03.8 Electric Field Assisted Freezing

3.03.8.1 Static Electric Field Assisted Freezing

–, Not studied; n.r., Not reported; *EF, Electric ﬁeld.

3.03.8.2 Fluctuating Electric Field Assisted Freezing

Sample Conditions Observations References

Sample Conditions Observations References

3.03.9 Microwave Assisted Freezing

3.03.10 Radio-Frequency Assisted Freezing

3.03.11 Freezing Assisted Biosubstances Capable of Regulating Freezing Point Depression

3.03.11.1 Antifreeze Proteins

3.03.11.2 Ice-Nucleating Proteins (INPs)

3.03.11.3 Natural Deep Eutectic Solvents

Field AFP sources Products Effects References

Fields INP sources Products Effects References

Fields INP sources Products Effects References

Modiﬁed from Tian et al. (2020).

Fields Products Effects References

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