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Food Structure 18 (2018) 1–13

Contents lists available at ScienceDirect

Food Structure
journal homepage: www.elsevier.com/locate/foostr

Effects of filler ingredients on the structure and texture of starchy, extruded T


snacks

R.G.M. van der Smana, , H.M. Vollebregta, M.B.J. Meindersa, A. Berib
a
Wageningen Food Biobased Research, Wageningen University & Research, Netherlands
b
PepsiCo R&D, Leicester, UK

A R T I C LE I N FO A B S T R A C T

Keywords: Several starchy snacks differing in filler ingredients have been analysed regarding (1) the fate of filler ingredients
Expanded snacks during processing, and (2) the role of filler ingredients with respect to texture and structure. The structure has
Crispiness been characterized with X-ray tomography, and the texture has been evaluated via acoustic emissions from snack
Filler ingredients compression using a texture analyzer, which is assumed to be representative for crispiness. Our study shows that
one has to distinguish hard and soft fillers. The absence of any filler or the presence of many hard fillers lead to a
snack with a hard, coarse and non-crispy texture. However, if a significant amount of soft fillers is used then one
attains a fine, and crispy texture.

1. Introduction vital role in the expansion process (van der Sman & Broeze, 2014).
Lubricants like oil and emulsifiers are intended to lower the friction
Potato-based snacks have often been developed in an artisanal way between dough and extruder, but they can also complexate free amy-
without much knowledge of ingredient functionality (van der Sman & lose (van der Sman & Broeze, 2013). If filler ingredients are sufficiently
Broeze, 2013). This lack of knowledge poses problems for industry small, and at volume fraction lower than 5% they can also act as nu-
when developing snacks for upcoming markets where potato-based cleation agents (Guy, 1994; van der Sman, 2016). Both nucleation and
ingredients are rarely locally available. For cost-effective manu- bubble expansion can be enhanced by inorganic leavening agents like
facturing of similar snacks one needs to replace potato-based in- sodium bicarbonate. Leavening agents are often added in crystalline
gredients with local available starch resources. This requires good form and thus can act as nucleation site too.
knowledge on the functionality of potato-based ingredients. Studies on Another classification of particular potato-based snacks is given in
how starches sources can be substituted with others are rare. We know our earlier review paper (van der Sman & Broeze, 2013). There, we
of a single study on starch substitution in fish crackers (keropok) have distinguished the following classes of starchy ingredients: (a) na-
(Saeleaw & Schleining, 2010). tive starches, (b) potato cells, and (c) gel formers. These three basic
An initial study towards ingredient functionality in extruded food ingredients with water make an cohesive dough that can be extruded
materials is by Guy (1994), where the following classes of ingredients and formed. The cohesiveness is provided by the gel former, which
are distinguished: (a) structure forming ingredients like starches and forms a network with native or (partially) gelatinized starch granules
potato granules, (b) dispersed filler ingredients like proteins and fibers, and potato cells embedded. In the trade the potato cells are also called
(c) plasticizers like water or sugars, (d) lubricants like oil or emulsifiers, potato dehydrates, which can be (a) potato granules, being cooked, and
(e) nucleation agents like small fillers and leavening agents, and (f) mashed potatoes – but with intact cells walls, and (b) potato flakes,
colouring and flavouring ingredients. The main matrix is build up using being cooked and drum dried potato cells – but with the integrity of the
ingredients from class (a) with possibly several ingredients dispersed cell wall lost due to the drum drying. Note that both type of potato cells
into it from class (b). If ingredients from class (b) like proteins exceed a comprise of a mixture of pre-gelatinized potato starch and cell wall
certain threshold of about 15% they can form a network resisting ex- material. The presence of potato cells is thought to be essential for the
pansion (Chanvrier, Colonna, Della Valle, & Lourdin, 2005; Zeng, crunchiness/crispiness of potato-based snacks (van der Sman & Broeze,
Huang, Lu, Fan, & Lourdin, 2011). Plasticizers like water, sugars or 2013). Potato flakes are often used to provide the gel former too, which
polyols lower the glass transition of the starchy matrix, which plays a is free amylose leached from the broken cell. The native potato starches


Corresponding author.
E-mail address: ruud.vandersman@wur.nl (R.G.M. van der Sman).

https://doi.org/10.1016/j.foostr.2018.10.001
Received 13 April 2018; Received in revised form 27 July 2018; Accepted 15 October 2018
Available online 21 October 2018
2213-3291/ © 2018 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/BY-NC-ND/4.0/).
R.G.M. van der Sman et al. Food Structure 18 (2018) 1–13

are thought to be nucleation sites for bubble formation, and water with a texture analyser. Earlier studies have shown that these two
sinks. If starch granules gelatinize during expansion, they will im- methods renders information about (1) the structure, in terms of bubble
mediately bring the starchy matrix in the glassy state. size distribution and bubble wall thickness (Babin, Della Valle,
More recently, we have reviewed filler functionality in starchy Dendievel, Lourdin, & Salvo, 2007; Horvat, Guthausen, Tepper, Falco, &
snacks in general (van der Sman, 2016). The filler particles applied in Schuchmann, 2014; Robin et al., 2010; Trater, Alavi, & Rizvi, 2005),
edible starch foams can be assigned the following functionality: (a) and (2) the crispiness as related to fracture events as recorded by si-
increase of mechanical strength of the matrix, (b) promotion of bubble multaneous acoustic emission and texture analysis (AETA) measure-
nucleation, (c) promotion of opening of the expanding bubble wall. ments (Arimi, Duggan, O’Sullivan, Lyng, & O’Riordan, 2010; Chanvrier,
Types of fillers applied in snacks are: (a) fibers, (b) proteins, (c) native Jakubczyk, Gondek, & Gumy, 2014; Jakubczyk, Gondek, & Tryzno,
starch granules, (d) whole grains or flour particles. Note that these 2017; Luyten & van Vliet, 2006; Roudaut et al., 1998; Saeleaw,
fillers are not inert, as they are all hygroscopic, and thus interact with Dürrschmid, & Schleining, 2012; Saeleaw & Schleining, 2011; Salvador,
other ingredients via thermodynamics, and thus determine the boiling Varela, Sanz, & Fiszman, 2009). The combination of both XRT and
point. The boiling of water present in the matrix drives the expansion of AETA methods in a single study is just a recent trend in food science
the foam bubbles. literature (Chanvrier et al., 2014; Herremans et al., 2013; Primo-Martín
The above formulated hypotheses on ingredient functionality in et al., 2010; Rizzolo et al., 2014), but which can give good insight how
potato-based snacks are largely based on claims in patent literature, and microstructure is influencing crispiness.
translation of empirical findings for cereal-based snacks, which are Our paper is organized as follows. First, we describe the materials
manufactured via hot-extrusion where the native starch will be gelati- and experimental methods used. Subsequently, the results of the in-
nized. The classification of Guy (1994) has been used only in a single dividual methods are presented. However, due to space constraints we
thesis study to develop novel cereal snacks via hot extrusion (Xiao, have moved many of the details to Supplementary materials. Via mul-
2015). For potato-based snacks experimental validation of hypotheses tivariate analysis (cross-correlation analysis, principle component
is still lacking. Hence, with this study we aim for experimental in- analysis and partial least squares) we investigate if there are any cor-
vestigation of the validity and fine tuning of our earlier hypotheses (van relations between pellet ingredient formulations and the experimental
der Sman, 2016; van der Sman & Broeze, 2013). Furthermore, we are results of all our methods.
interested in their role in the eating quality of the potato-based snacks,
which is dominated by crispiness. 2. Materials and methods
In our investigation we will use an array of experimental methods,
such that we can monitor the fate of ingredients during the individual The composition of the used snack pellets are listed in Table 1. The
processing steps, i.e. the extrusion and frying. Extrusion (with sub- snack pellets have been anonymized as Pi. P1 is the reference snack
sequent drying) renders shelf-stable intermediate half products, which pellet high in potato ingredients, whose texture can be viewed as de-
are called pellets in the trade (Moraru & Kokini, 2003). For our ex- sired. The starchy ingredients have been given abbreviations for con-
periments we have obtained pellets with known composition from the venient reference. The entries in Table 1 must be read as percentage of
commercial market. Expanded snacks are produced from these pellets the total dry matter. The pellets are discussed in more detail in the
via frying them in oil, under standard conditions. These expanded Supplementary materials.
snacks are called indirectly expanded snacks, in contrast to directly We have applied a series of experimental methods to individual
expanded snacks – which expand on exit of (hot) extrusion. ingredients, pellets, and the expanded snacks. The list of applied
The fate of ingredients during processing is evaluated with methods, methods are:
that are used traditionally to screen starch resources for their physi-
cochemical properties (Singh, Singh, Kaur, Sodhi, & Gill, 2003), • Water activity (WA), as moisture content is one of the determining
namely: (1) X-ray diffraction (XRD) for detection of the presence of factors in crispiness.
crystalline starches, (2) particle size distribution (PSD) measurement • Differential scanning calorimetry (DSC) for determining degree of
for detection of filler ingredients, (3) differential scanning calorimetry gelatinization.
(DSC) for detection of the degree of gelatinization, (4) rapid viscometer • X-ray diffraction (XRD) for detection of crystalline ingredients
analysis (RVA) for detection of effect of filler ingredients on rheology, • Rapid viscometry analysis (RVA) for fingerprinting of pellets and
and (5) water activity and moisture content of pellets and expanded expanded snacks.
snacks, to assess amount and state of water as plasticizer, because it has • Particle size distribution after enzymatic hydrolysis (PSD) for de-
significant effect on both the expansion and the crispiness (Roudaut, tection of filler ingredients.
Dacremont, & Le Meste, 1998; van der Sman & Broeze, 2014). • X-ray tomography (XRT) for determining structure characteristics.
RVA is also measured because it has proven to be a good method for • Acoustic emission and texture analysis (AETA) for determining
finger printing starch resources for use in expanded snacks (Saeleaw & crispiness.
Schleining, 2010). For manufacturing of cereal-based pellets using hot
extrusion RVA is a commonly used tool to screen ingredients (Saeleaw Table 1
& Schleining, 2010; Xiao, 2015). RVA has also been used to screen Starchy ingredient in the selected group of pellet snacks.
starch resources for fish crackers (keropok) (Saeleaw & Schleining,
Ingredient P1 P2 P3 P4 P5 P6 P7
2010), whose production has large similarity with indirectly expanded
potato-based snacks manufactured via cold extrusion. Structure- Potato granules (PPG) 44 – – – – 40 25
forming ingredients should well gelatinize and swell during hot-extru- Potato flakes (PFL) – – 26 24 70 40 25
sion, and show high peak viscosity. Often they also provide the gel Native potato starch (NPS) 40 – 52 – 11 20 40
Native tapioca starch (NTS) – – 7 30 – – –
former via leached amylose. Their presence is indicated via a high
Native rice flour (NRF) 8 – 8 6 12 – –
setback of viscosity during cooling. Good correlations have been found Native wheat flour (NWF) – – – 29 – – –
with physical parameters relevant for crispiness. However, because Native corn flour (NCF) – – – 6 6 – –
RVA profiles can be related to various factors, it has not been possible to Nix. corn flour (NNCF) – 96 – – – – –
assign differences in crispiness to starch properties. Because of the in- Crosslinked potato starch (XPS) – – – – – – 8
Fine grind – – 5 3 – – –
terest in factors determining crispiness, we have given special emphasis
Methyl celluclose (MC) – – 0.4 0.4 – – –
to experimental investigation of textural properties via X-ray tomo- Pre-gelled potato starch (GPS) 5 – – – – – –
graphy (XRT) and via acoustic emissions during compression of snacks

2
R.G.M. van der Sman et al. Food Structure 18 (2018) 1–13

As most of these methods are quite standard we have moved the 3.2. RVA
detailed description of the methods towards the Supplementary
Materials. Also, we have indicated there to which samples these The RVA profiles of the pellets and expanded snacks are given in
methods have been applied. Fig. 2. The characteristics of the RVA profiles are listed in SM Table B.2.
They comprise of the following: the pasting temperature Tpaste, where
the peak viscosity ηpeak, the hold viscosity ηhold, and the final viscosity
3. Results
ηfinal. Not all relevant data can be extracted from the profiles, due to
uncommon profiles, lacking a peak for example.
Full account of the direct experimental results of the various applied
The pasting temperatures are a bit in line with the gelatinization
measurements techniques one finds in the Supplementary materials,
temperatures (SM Table B.1), except for the strong deviations for P4,
where they are presented in the form of tables and figures. These data
which has quite a complex composition. The pasting temperature would
will be the basis of the multivariate analysis, as discussed in the next
be determined by the weakest starch, while the gelatinization tem-
section. In this section, we discuss some of the important direct ex-
perature in the DSC is determined by the starch component with the
perimental results. Tables or figures present in the supplementary ma-
largest amount of crystalline starch. Furthermore, it has a low peak
terials will be indicated by (SM).
viscosity, making it difficult to determine the pasting temperature. The
differences in viscosities will be interpreted when we discuss the fate of
3.1. XRD the filler ingredients given the results of the multivariate analysis.

The XRD spectra of the ingredients (SM Fig. B.1) show that PFL and
3.3. PSD
GPS are fully gelatinized, while in PPG the gelatinization is almost
completed as indicated by the presence of small peaks, at similar angles
From the particle size distribution (PSD) of fillers present in the
as the B-type spectrum. In PPG the swelling and gelatinization of starch
various pellets and expanded snacks (SM Fig. B.4) one can clearly see
granules may be restricted due to the hindrance of the intact potato cell
that the various pellets and snacks are quite distinctive. For the fate of
walls. NPS shows strong peaks at the expected positions.
the ingredients during extrusion, it is more instructive to compare the
Cereals and tapioca adhere well to the expected A-type spectrum,
PSD of the pellets with that of the snacks. Hence, in Fig. 3 the PSD for
while there is definitely differences in the height of the peaks between
pellets and snacks are plotted in a single graph for each formulation
different ingredients. Tapioca (NTS) is showing strong peaks, while
separately. We observe that P2 is characterized by the absence of large
nixtamalatized corn starch (NNCF) shows small peaks. The latter in-
filler particles, while it is particular rich in small particles. We expect
dicates that the alkaline pretreatment has affected the degree of crys-
that those small particles are protein aggregates, due to the lime pre-
tallinity of corn starch.
treatment. In other formulations most of the fillers are large, and par-
In Fig. 1 we have shown the spectra of pellets. Again the results are
ticularly formulations with a large amount of potato dehydrates (PPG
divided over two groups: (1) with predominantly native potato starch
and PFL) display a large peak of around 200 μm, as shown by P1, P6 and
(NPS) in the formulation, and (2) with a significant amount of cereal
P7.
starches in the formulation. In the left figure we have indicated the
In Fig. 3 we observe that for most of the formulations there is only a
expected B-spectrum, while in the right figure we have indicated both A
slight change in the PSD before and after expansion. If the formulation
and B spectrum, because P5 has both cereal and potato based in-
contains potato granules or flakes (PPG or PFL) one often observes a
gredients.
significant decrease of the larger peak, and a growth of the smaller
Except for P5 the pellets with NPS show strong peaks corresponding
peak. It is likely that some of the potato granules (PPG) are ruptured
with the spectra of native B-type starches. The peaks in P5 are less
during extrusion, leading to a decrease of the peak at 200 μm and an
strong because of the lower amount of NPS (11%). The spectra of pellets
increase of the peak at about 80 μm.
containing cereal starches do not show strong peaks, except for P2. The
We have analysed the PSD also quantitatively in terms of (1) the
peaks for P2 are not at angles corresponding with native cereal starches.
DeBroukere mean diameter (D43) of the PSD, and (2) the height of the
We expect that the starch in P2 has retrogradated, as some of the peaks
peak for particles larger than 100 μm (SM Table B.3).
are at angles found for V-type starch (as found in retrogradated amy-
lose). Also P4 is showing small peaks at the angles for V-type starch, and
thus it has partly retrogradated. P5 is showing peaks at angles of both B- 3.4. XRT
type and A-type starches, which is expected as the formulation has
equal amounts of potato and cereal starches. The peaks are small, be- In the Supplementary Materials we show (a) examples of the pro-
cause of the low amounts of native starches and possible gelatinization jection of 3D voxel data (SM Fig. B.6), cross sections of (b) the pellets
during extrusion. (SM Fig. B.7) and (c) expanded snacks. The latter we have reproduced

Fig. 1. X-ray diffraction (XRD) spectra of several pellets, with


(1) having predominantly potato starches (left pane), and (2)
having significant amount of cereal starches (right pane). The
dashed lines indicate the spectra of B-type starches (black), A-
type starches (red). (For interpretation of the references to
color in this figure legend, the reader is referred to the web
version of the article.)

3
R.G.M. van der Sman et al. Food Structure 18 (2018) 1–13

Fig. 2. RVA profiles of pellets (left panel) and expanded snacks (right panel). The temperature profile is indicated with the dashed line.

in Fig. 4. On the 3D data sets we have also performed quantitative numbers of sound events (peaks), (2) the mean sound energy E as
analysis, and computed the porosity and pore sizes of both pellets and computed via Eq. (2), and (3) the sound intensity I (SM Fig. B.10) From
expanded snacks, and pore size distribution and the mean bubble wall the force–displacement data we have extracted the following data: (1)
thickness for the expanded snacks (SM Table B.4). the number of force drops, (2) the mean slope, and (3) the maximum
The results for the pellets show that there are air inclusions present force (SM Fig. B.11). From analysis follows that the energy released per
in the unexpanded pellets. Especially, the volume fraction of air in- fracture is an important characteristic for crispiness. These values we
clusions for the P1 is high. One might think that the air inclusions can be have displayed in Fig. 6.
a major nucleation site for bubbles to grow. However, observing the
expanded snacks shows that P1 does not stand out in a significantly 4. Discussion
higher number of bubbles. With respect to its structure P1 is comparable
to the majority of snacks. It is rather that P2 and P4, which stand out in The objective of this study is to correlate physical properties of
the collection of expanded snacks. These snack types show a different pellets to textural properties of snacks as measured via AETA and XRT.
texture consisting of a large number of big cells, and a few small cells - Hence, in order to perform such quantitative analysis we have to
while the other snacks show a large number of small cells, and a few characterize the pellets in a number of physical quantities. These
moderately large cells. numbers will be obtained from the experimental data, as described in
This difference in texture is also evident from the pore size dis- previous section and detailed in SM. The correlation between these
tribution of the expanded snacks, as shown in Fig. 5. The shape of the physical quantities and the AETA/XRT results will be determined via
pore size distributions is similar for all samples, except that for snacks the multivariate analysis. Finally, we will discuss the found correlations
with higher mean diameter it is shifted towards higher pore sizes. Three and we will draw some hypotheses. In the discussion of the char-
clusters can be observed: (a) P2 and P4 with very large pores, (b) P3 and acterization of pellets and snack samples we can refer to raw data
P7 with very small pores, and (c) P1, P5, and P6 with an intermediate presented in the Supplemented materials.
pore sizes. A similar clustering can also be observed if one compares the
mean bubble wall thickness (SM Table B.4).
4.1. Characterization of pellets

3.5. AETA First we investigate the WSI (SM Table B.3), which gives an estimate
of mechanical degradation during extrusion. We note that the WSI is
From the measured sound emissions we have quantified (1) the considerably high for all pellets. Most notable is that for P2, but it is

Fig. 3. Changes in the particle size distribution before and after expansion for six different formulations. PSD of P5 show little change, and is not presented.

4
R.G.M. van der Sman et al. Food Structure 18 (2018) 1–13

Fig. 4. Cross sections of all expanded snacks. The colors indicate the size of individual bubbles, ranging up to 1 mm. Especially the P2 and AMA chip stand out in their
larger number of big cells, and very few small cells. Other snack types show a mixture of many small cells and a few large cells.

mechanical energy to gelatinize the NWF (extrusion is done at 80 °C as


compared to 60 °C for most other pellets, while P2 is extruded at
140 °C). Consequently, the NTS from P4 will be more degraded than it
would during the milder extrusion conditions at 60 °C. If we exclude P2
and P4, we have pellets with similar extrusion conditions and com-
parable formulation as they have for more than 85% potato-based in-
gredients.
The degree of gelatinization in the pellets is determined from the
enthalpy ΔHm from the DSC measurements of the hydrated pellets (SM
Table B.1). For native potato starch the typical melting enthalpy is
ΔHm,0 18 J/g (Ratnayake & Jackson, 2007; Singh et al., 2003). We can
estimate the degree of gelatinization DG via:

ΔHm
DG = 1 −
ΔHm,0 × NS (1)

with NS the fraction native starches in the formulation. Here, we do not


regard NNCF as a native starch, as it has lost its crystallinity already as
Fig. 5. Pore size distribution for the expanded snacks, as obtained from gran- raw ingredient via the nixtamalization, as shown by the XRD results on
ulometry applied to XRT images. NNCF.
We have plotted ΔHm against NS in Fig. 7, with the dashed line
indicating DG = 0 (i.e. the amount of enthalpy released if all starches
have gelatinized). We note that P6 is above this line, which might in-
dicate that some of the starch in the potato dehydrates have not fully
gelatinized. We observe that P4, P7 and P5 are below the line of DG = 0.
P4 has the highest DG, which is expected from the higher required ex-
trusion temperature for NWF, which would gelatinize NTS fully.
Hence, we can infer that the native starches in pellets with en-
thalpies near the dashed line in Fig. 7 are still ungelatinized. Pellets that

Fig. 6. Acoustic and mechanical energy per pulse for all snacks.

known that these pellets are manufactured via hot extrusion. Hence,
significant starch degradation can be expected. In other pellets the WSI
value is due to (1) leached starches from PFL or PPG, and (2) gelati-
nized and degraded starch via the mechanical action of the extruder.
Observing WSI from literature (Bhatnagar & Hanna, 1996) shows that
the WSI for native potato starch is higher than for tapioca, wheat and
rice starch (More specifically NPS > NTS > NRF > NWF > NCS).
Potato starch is thus most vulnerable to degradation in the extruder.
Given this order of the strength of native starches, it is surprising that P4
Fig. 7. Relation between relative amount of native starch (NS) in the for-
has a higher value of WSI than other pellets high in NPS. However, mulation and the released enthalpy during gelatinization of a hydrated pellet
because P4 is rich is NWF it requires a higher extrusion temperature or during a DSC scan. The dashed line is based on the assumption that DG = 0.

5
R.G.M. van der Sman et al. Food Structure 18 (2018) 1–13

are below this line are: P4, P7 and P5. XRD results of the pellets as shown
in Fig. 1 indicate indeed that P2, P4, and P5 have little crystallinity,
which is in line with the estimated DG. The largest crystallinity is
shown by P1 and P3, which is in line with their value of
(1 − DG) × NS = ΔHm/ΔHm,0. XRD shows intermediate values of crys-
tallinity for P6 and P7.
The pellets below the dashed line in Fig. 7, whose native starches
have experienced some degree of gelatinization, also show higher level
of WSI (SM Table B.3). For P4, P5 and P7 it holds that WSI ≥ 50%.
Furthermore, we note that P2 does not show any melting enthalpy and
also has a high WSI. Due to its pretreatment and hot extrusion condi-
tions no crystalline starch has remained to provide a DSC signal. The
XRD of the main raw ingredient (NNCF) shows that it already has lost
much of its crystallinity. The XRD of the pellet of P2 does show a slight
peak, which is due to retrogradation.
Fig. 9. The volume fraction of the peak at 200 μm in the PSD of the pellets
It follows that (100% − Fillers) in the pellets is always larger than (Peak) versus the amount of potato dehydrates in the formulation PFL + PPG.
WSI (SM Table B.3). (100% − Fillers) is a measure of the amount of Solid line is obtained via linear regression with r2 = 0.83.
soluble starches after applying the enzymatic hydrolysis. Hence, the
difference between WSI and (100% − Fillers) shows that the enzyme
indeed hydrolyses some of the remaining gelatinized starches. (Recall
that the enzyme does not enter the ungelatinized native starch gran-
ules). Hence, Fillers is expected to indicate the amount of insoluble
(non-gelatinized) starches, and other particulate ingredients like the
potato dehydrates, except for P2 as these fillers are assumed to be
protein aggregates. In Fig. 8 we show the correlation between Filler and
(1 − DG) × NS + PFL + PPG. If we exclude P2 from the analysis, the
regression line nicely follows the experimental data. This conclusion is
also supported by the relation between the height of the largest peak in
the PSD of the pellets, Peak, and the amount of potato dehydrates (SM
Table B.3). The correlation between them is shown in Fig. 9. Linear
regression shows that the correlation is strong with r2 = 0.83.
With the DSC results and the composition of the pellets we have
made a rough estimate of the solubles (SOL) in the supernatant - which
expect to be comparable to WSI: Fig. 10. WSI versus the estimated solubles in the supernatant. Solid line is
obtained via linear regression, with r2 = 0.74.
SOL = DG × NS + 0.50(PFL + PPG) (2)

with NS the fraction of native starches in the formulation, DG the de-


gree of gelatinization. The factors in front of the potato dehydrates, PFL
and PPG, indicate how much soluble starch we expect to have leached
from these ingredients. In Fig. 10 we have compared the prediction of
SOL with WSI. It shows that there is a reasonable correlation with
r2 = 0.74.
The viscosity of the pellets as measured in the RVA is highly influ-
enced by the swelling of native starch granules upon their gelatiniza-
tion, which follows from the plotting of the RVA viscosities against the
amount of remaining native starch in the pellets, RNS = (1 − DG)NS -
as shown in Fig. 11. All RVA viscosities show a similar trend, albeit that

Fig. 11. The peak viscosity (red circles), hold viscosity (blue squares) and final
viscosity (black stars) as function of the remaining native starch,
(1 − DG) × NS.

there is one outlier for the peak viscosity. Up to (1 − DG) × NS < 0.2
the viscosity has a plateau value of about 1000 Pa s. For larger values
the viscosity rises steeply, after reaching a plateau value again. This
steep increase can be due to the fact that the swollen starch granules
become space filling. Pellets showing significant effect of swelling in the
viscosity (i.e. ηpeak > 1500 Pa s) are P6, P1 and P3, which are particu-
larly rich in native potato starch (NPS) or potato dehydrates (PFL and
PPG). The potato dehydrates also take part in the space filling network,
and contribute to the peak viscosity.
Fig. 8. The amount of particulate ingredients ((1 − DG)NS + PFL + PPG)
From the above analysis, we draw the following conclusions about
versus the amount of fillers measured after enzymatic hydrolysis. Solid line is
obtained via linear regression, with r2 = 0.75. the fate of starchy ingredients during extrusion. Depending on extrusion

6
R.G.M. van der Sman et al. Food Structure 18 (2018) 1–13

Table 2
Characterization of snack pellets.
Formulation DG RNS (%) PF (%) SOL (%)

P1 0 40 22 38
P2 100 0 0 100
P3 8 62 13 25
P4 77 17 12 71
P5 34 14 35 51
P6 0 20 40 40
P7 56 18 25 57

conditions and pretreatments, some of the native starches have gelati-


nized – which is determined via DSC measurement. The remaining
native starches retain their particulate structure, as shown by the peaks
Fig. 12. The amount of remaining cereal starches, RCS = (1 − DG)
at diameters of 10–100 μm in the PSD of the pellets. Gelatinized star-
(NWF + NRF), in pellets versus the melting enthalpy of expanded snacks ΔHm,x
ches are soluble and they will end up in the supernatant during cen-
Solid line is obtained with linear regression showing r2 = 0.85 if P5 is excluded.
trifugation of hydrated pellets, as measured by WSI. About half of the
potato dehydrates retain their integrity, and remain particulate.
Summarizing after extrusion the pellets can be characterized by
several factors:

• the amount of remaining native starches, RNS = (1 − DG) × NS, as


measured via DSC,
• the amount of remaining fillers, that are based on potato dehydrates,
PF = 0.5(PPG + PFL) (PF = Potato Filler), and
• the amount of solubilized starch (SOL), which is measured via WSI.
From the correlation shown in Fig. 10 one can expect that 50% of
the potato dehydrates end up as filler in the pellet. The remainder is
probably fragmented during extrusion, and becomes part of the con-
tinuous matrix. In Table 2 we have listed these numbers for the pellets,
together with the degree of gelatinization DG. We have computed the Fig. 13. The RVA viscosities (peak and final) of the expanded pellets are linear
soluble starches from the mass balance SOL = 100 − RNS − PF. with RCS. Linear regression shows r2 = 0.63 for the ηpeak and r2 = 0.88 for ηfinal.
DG can be viewed as a measure for the conditions of extrusion. For
P1, P3 and P6 the extrusion has been very mild, similar to pasta – where
The PSD results of the expanded snacks, as shown in Fig. 3, indicate
there is little gelatinization or starch degradation. The pretreatment and
that potato-dehydrate fillers (PF) undergo some changes. The main
extrusion of P2 is relatively harsh, leaving little native starch remaining.
peak in the PSD (with diameter larger than 100 μm) shifts to smaller
P4 has also received quite some thermal and/or mechanical energy
diameters, and its volume fraction is reduced with about 1/3. Si-
during extrusion, which is probably required to gelatinize the wheat
multaneously, there is an increase of fillers at about 80 μm. This in-
flour (NWF). P5 and P7 have received a moderate amount of thermal
dicates that some of the potato fillers can be disrupted during expan-
and mechanical energy, rendering some moderate degree of gelatini-
sion.
zation of their native starches. The mild extrusion conditions for P1, P3
The change in the total amount of fillers during expansion can be
and P6 are reflected in their low values of WSI ∼ SOL. The harsh con-
inferred from the comparison of the fraction of fillers in pellets and
ditions of extrusion for P2 is reflected in its high value of WSI and SOL.
expanded snacks (SM Table B.3). We observe that for all pellets, except
P4, the amount of fillers is decreased due to expansion. As explained
4.2. Characterization of expanded snacks above, P4 is rich in cereal starches (NWF + NRF), which hardly gela-
tinize during expansion. Hence, its amount of fillers has remained at
From the DSC results of the expanded snacks (SM table B.1), we similar level. P2 still has some significant amount of fillers remaining,
observe that the measured melting enthalpy ΔHm,x is smaller than that while its formulation does not contain any potato dehydrates. As it is
of pellets. For most of the pellets holds that much of the native starches made from nixtamalatized corn flour, and the pellets are made via hot
have gelatinized during expansion. For some pellets we observe some extrusion conditions, it is probable that protein aggregates are formed.
residual starch remaining, and especially those pellets rich in cereal For the other pellets the decrease in the amount of fillers can be
starches. We have compared the amount of (remaining) native cereal explained by two phenomena: (1) the gelatinization of native starches
starches (RCS) with the recorded melting enthalpy. RCS is computed as: in the pellet (RNS), and (2) the rupture of some potato dehydrate-based
RCS = (1 − DG)(NWF + NRF) (3) fillers (PF). The former can be inferred from the melting enthalpy of the
expanded snacks. From the difference between RCS and the amount of
DG in the above formula is taken as the value of the pellet, as shown in fillers in the expanded snack, Fillerx (SM Table B.3) we can compute the
Table 2. The correlation between RCS and melting enthalpy of the ex- remaining potato fillers PFx:
panded snack ΔHm,x is shown in Fig. 12. If we exclude the outlier of P5,
we obtain a good correlation. PFx = Fillerx − RCS (4)
Similar to the pellets we observe a good correlation of the RVA
viscosity with the amount of remaining native starches. Fig. 13 shows These numbers do not correlate well with the amount of potato dehy-
that both the peak and final viscosity are linear with RCS. Due to the drates in the formulation of the pellets. This discrepancy can be due to
low amount of native starches remaining, there is no steep rise of the presence of protein aggregates. Snacks high in PFx are either rich in
viscosity – as seen in Fig. 11. PPG, or rich in cereal flour. PPG is assumed to be stronger than PFL and

7
R.G.M. van der Sman et al. Food Structure 18 (2018) 1–13

Table 3 • Peakpellet, Peakexp, PotatoDehydrate, PF, TpasteExp


Characterization of expanded snack. • WSI, DG, SOL, etarawpellet
Formulation RCS (%) PFx (%) SOLx (%) • dHpellet, RNS, etaholdpellet, etafinpellet
• Fillerexp, PFx, SOLx
P1 5 14 81
• etafinexp, dHexp, RCS, D43exp
P2 0 20 80
• poroexp, Qx
• awexp, MCexp
P3 8 19 73
P4 8 16 76
P5 1 3 96
P6 2 19 79 From the above clusters only one parameter will be chosen for the
P7 2 0 98 PCA analysis. Furthermore, we have excluded MCpellet, TpastePellet,
and poropel from the PCA analysis, because they do not correlate with
any other parameter.
a reasonable amount of it might survive expansion. The amount of
The selected parameters for the PCA analysis are:
fillers (excluding remaining native starches RCS) present in the ex-
panded snacks will be based on PFx, and will be used in our further PFx , PF, SOL, RNS, PFx , RCS
analysis. These numbers are listed in Table 3. For completeness we have for the description of the composition of pellet and expanded snack,
also computed the amount of soluble starches in the expanded snacks
SOLx = 100% − RCS − PFx. Qx , awx , diax , Wwall

as descriptors of the microstructure, and

4.3. Multivariate analysis FnPulsesKramer, FmaxForceStartDropKramer, FworkInTimeSpan

SnPulsesKramer, SmaxIntensityKramer, STotalPulseEnergyKramer


Fig. 14 shows the cross-correlation matrix (CCM) of the measured
variables. The matrix is reordered using hierarchical clustering method. as descriptors of the crispiness and hardness. In Fig. 15 we have re-
The labels of the measured variables are explained in the Supplemen- plotted the cross correlation matrix (CCM), but now for the above se-
tary Materials. Note that several variables are not fully independent, as lected parameters. We will use that matrix together with the PCA plots,
for example SOL + PF + RNS = 100%. The size of the circles indicates Figs. 16 and 17, in our discussion.
the magnitude of the correlations, and the color indicates the sign of the From the PCA plot we observe that on the first two principal com-
correlation (with blue indicating a positive correlation, and red in- ponents explain together 75% of the variation amongst our measure-
dicating a negative correlation). We observe that several parameters are ments and samples, but PC2 and PC3 are about evenly strong. From the
strongly correlated, with several confirming relations already estab- PCA plot and cross-correlation matrix follows that the AETA parameters
lished in the previous two sections. can be divided in two clusters:
Based on their correlations and interdependencies, we have grouped
{FworkInTimeSpan, FmaxForceStartDropKramer}
several parameters together. From these groups we have selected only a
few characterizing parameters, which will be used further in the PCA {StotalpulseEnergyKramer, SmaxIntensityKramer}
analysis. The groups of parameters are: and

Fig. 14. Cross-correlation matrix of measured variables. Colors correspond to the correlation coefficient, as is indicated at the right.

8
R.G.M. van der Sman et al. Food Structure 18 (2018) 1–13

Fig. 15. Compact cross-correlation matrix of measured variables.

Fig. 16. Corresponding scores and loadings as a function of the PC1 and PC2,
resulting from PCA. Fig. 17. Corresponding scores and loadings as a function of the PC2 and PC3,
resulting from PCA.
{SnPulsesKramer, FnPulsesKramer}
as follows from both the CCM and the PCA plot. If the snack has higher
As follows from literature as discussed in the introduction the first water activity and larger bubble diameters, at comparable expansion
cluster relates to hardness of the snack, while the second cluster relates ratio, the starch matrix is less hard and less bubble walls have to be
to the crispiness. In our further discussion we will use these clusters of fractured. This will lead to less total energy required for fracturing.
AETA parameters as indicators of these sensory traits. The main interest of this paper is the correlation between snack
The crispiness is strongly dependent on structural properties and formulation and texture cq. crispiness. Hence, we now focus on the
water activity. Hence, we also investigate correlations amongst these correlations between snack formulation parameters and AETA and
properties. The most striking correlation is that between the water ac- structural parameters.
tivity of the expanded snacks awx, and the pore diameter diax. There is a The structural parameters {awx,diax,Wwall} are strongly correlated
somewhat less strong correlation of {awx,diax} with the wall thickness with the amount of soluble starch SOL in the pellet, and strongly ne-
Wwall. For the XRT images it follows indeed that snacks with large gatively correlated with the amount of potato fillers PF and RNS in the
diameters have thick bubble walls. However, both these structural pellet. Snacks with more soluble starch, i.e. less remaining native
parameters have little correlation with the expansion ratio Qx. Qx also starch, can hold more water in the matrix during expansion, leading to
has little correlation with the AETA parameters. The group a higher water activity. Together with the oil temperature the water
{awx,diax,Wwall} is negatively correlated with StotalPulseEnergyKramer,

9
R.G.M. van der Sman et al. Food Structure 18 (2018) 1–13

activity determines the vapour pressure driving the bubble expansion.


Hence, continued bubble expansion is expected. Furthermore, due to
the low amount of fillers bubble wall opening will also happen at a late
stage, enhancing the chance for bubble coalescence. Bubble coalesence
and extended bubble expansion will lead to large bubble diameters and
thick bubble walls (van der Sman, 2016).
In the compact CCM the expansion ratio Qx has only a moderate
negative correlation with PF, which also follows from the PCA plot.
From the larger CCM follows that Qx correlates better with Peakexp,
which also holds for poroexp and Peakexp/D43exp. Peakexp is related to
the number of potato-based fillers remaining in the expanded snack
(recall that PFx also includes protein aggregates). Hence, we conclude
that the expansion ratio and porosity correlates negatively with the
amount of potato fillers remaining after expansion.
The AETA parameters for hardness are positively correlated with
remaining native starches in the pellet RNS, and negatively correlated
with soluble starches in the pellet SOL. The opposite trend is observed
for the correlation of the AETA parameters for crispiness
{SnPulsesKramer, FnPulsesKramer} and the formulation parameters:
they are positively correlated with the amount of soluble starch in the
pellet SOL, and negatively correlated with the amount of remaining
native starch RNS. This makes that the crispiness parameters and the
hardness parameters are not independent parameters. This dependency
is probably strengthened by the negative correlation between the re-
maining starches in the expanded snack RCS and the crispiness para-
meters {SnPulsesKramer, FnPulsesKramer}. The negative correlation
between RCS and the number of pulses (fracture events) can be ex-
plained by the structural inhomogeneity in the bubble wall induced by
Fig. 18. Concept matrix showing the clustering and correlations between mi-
the remaining starch granule, which makes the bubble wall fracture in crostructure, AETA and formulation parameters. The matrix is further explained
one single event, reducing the crispiness. As there is a strong correlation in the text.
between RCS and RNS, probably creates the dependency between the
crispiness and hardness parameters.
plots. P2 and P4 are characterized by a coarse texture, with a large
From the larger CCM we find that the RVA parameters have strong
bubble size. In the PCA plot they show indeed strong correlation with
correlations with both formulation and with AETA parameters. The
awx and diax. However, they differ in PC3 – which is shown to be
RVA parameters of the pellet correlate strongly with RNS, while the
dominated by RCS. Both P3 and P4 have a high value of RCS. P2, P3, and
RVA parameters of the expanded snack correlate strongly with RCS.
P4 are also characterized by a low amount of PF in the pellets. P5 and P6
Furthermore, the RVA parameters of the expanded strongly correlate
are characterized by their high content of soft fillers (PF) in their for-
with the released sound energy {StotalpulseEnergyKramer,
mulation. Furthermore, they show low expansion ratio, and a low va-
SmaxIntensityKramer} and mechanical work {FworkInTimeSpan,
lues for mechanical work (FworkInTimeSpan). P1 and P7 do not differ
FmaxForceStartDropKramer}, which are a measure for hardness.
much in their values of PC1 and PC2, but there is a difference in the
Furthermore, the RVA parameters of the expanded snack correlate ne-
PC3, which correlates with RCS and Wwall. P1 and P7 have a similar
gatively with the number of acoustic and mechanical fracture events
amount of PF in the pellet, but P7 has more gelatinized starch DG, and
{SnPulsesKramer, FnPulsesKramer}. Hence, the RVA measurement has
very little fillers (hard or soft) in the expanded snack.
strong predictive value.
The number of fracture events, indicative for crispiness, and the
total amount of (mechanical or acoustic) work, indicative for hardness, 4.4. Hypotheses: formulation and structure, texture/crispiness
are not fully independent variables, as shown by the PCA plot. While
the works correlates negatively with PC1, the number of fractures is Based on the results of the multivariate statistical analysis we pose
explained partly by PC1 and PC2. A similar result is shown by the PCA the hypothesis that the textural properties of expanded snacks is largely
analysis of (Chanvrier et al., 2014). All-in-all our PCA plot is quite in determined by filler particles present in the pellet, where one should
line with that study, only in our case the porosity (or equivalently Qx) is distinguish hard and soft filler particles. Hard filler particles are star-
more along the PC2 axis, while in (Chanvrier et al., 2014) it is explained ches that are still ungelatinized after expansion (RCS). In the in-
by both PC1 and PC2. vestigated formulations these hard fillers mainly originate from cereal
We have summarized the correlations and clustering as follow from flour: rice and wheat. It is probable that the protein matrix of the flour
the multivariate analysis in a concept matrix, as depicted in Fig. 18. The restricts the starch in absorbing water, and gelatinize. As soft fillers we
matrix elements indicate whether a positive or negative correlation is understand potato dehydrates (PPG and PFL) and starches that have
observed between particular clusters of parameters, as indicated by the gelatinized after expansion (RNS-RCS).
blue (+) and red (−) fields. If no red or blue field is present, there is no We assume that the presence of hard fillers lead thick bubble walls,
correlation found between the two clusters of parameters. In the for- bubble coalescence or premature bubble rupture, and thus a coarse and
mulation a distinction is made between hard and soft fillers. The hard hard texture. Pellet P4 is representative of a pellet with many hard
fillers are the still ungelatinized starches (RNS or RCS), and the soft fillers. Soft fillers are assumed to promote nucleation and cell opening.
fillers are the still intact potato dehydrates, which are indicated by large If bubbles are nucleated in these soft fillers it is likely that the filler
peak in the PSD. Protein aggregates are also regarded as hard fillers. particle is disrupted/gelatinized in the course of the bubble expansion.
Given the decomposition of the pellet and snack formulation, and Due to the enhancement of cell opening the expansion ratio of the snack
their correlation with microstructure, crispiness and hardness para- will be limited by the presence of soft fillers promoting nucleation, and
meters, we now focus on the position of the various samples in the PCA the bubble diameter will be small. However, if neither soft or hard

10
R.G.M. van der Sman et al. Food Structure 18 (2018) 1–13

Fig. 19. Expansion ratio Q versus the effective amount of fillers


Fig. 21. Mean acoustic energy, as measured with Kramer cell, versus the ex-
EF = RNS − RCS + PFL + PPG, for all pellets excluding P2 and P4. Solid line is
pansion ratio (Q). If P3 is excluded, a correlation is found between expansion
via linear regression showing r2 = 0.68.
ratio and acoustic energy, as shown by the solid line (with r2 = 0.71).

fillers are present, only a few bubbles will be nucleated. These bubbles
also higher – as the bubbles are less stabilized by the soft fillers. A
can grow large, but they are also prone to coalescence - rendering thick
higher amount of fillers, increases the strength of the cell walls, and
bubble walls in the final expanded snack. Absence of fillers also leads to
leads to a firmer texture, and more work required for fracturing. At
a coarse texture, but its hardness will be low. Pellet P2 is an example of
increasing amounts of fillers the cells walls become thick. The latter
a snack with little fillers. Furthermore, P2 and P4 show that low
indicates that the soft fillers are not finely dispersed, either due to ag-
amounts of fillers, lead to enhanced water binding in the pellets, and
gregation or their large size (in case of PPG).
higher water activity – which reduces crispiness.
If hard fillers are added to pellets with a moderate amount of soft
We try to verify the hypotheses on the soft fillers by analyzing re-
fillers, such as P1, P3, and P5, we expect that the number of fracture
sults by excluding P2 and P4. The amount of soft fillers is indicated by
events decrease, and the hardness to increase. The moderate amount of
EF = RNS − RCS + PFL + PPG (EF = effective filler). We find indeed
soft filler is a precondition of the prevention of the development of a
that the expansion ratio Qx has a negative correlation with EF, as shown
coarse texture, as in case of P2 and P4. Subsequently, one can modulate
in Fig. 19. There is also a slight correlation between acoustic energy and
the hardness (crunchiness) by the amount of hard fillers. In the re-
EF, see Fig. 20, which is also confirmed by the negative correlation
ference snack product, P1, there is probably an optimal mix of hard and
between expansion ration and acoustic energy, see Fig. 21.
soft fillers, leading to a snack with a sufficient crispiness, but still with a
At constant amount of hard fillers, but increasing the amount of soft
sufficient firm bite.
fillers, EF, we expect that:
We will compare our conclusions and hypotheses with earlier stu-

• the expansion ratio to decrease,


dies investigating crispiness and structure of expanded, solid foams, via

• the bubble diameter to decrease,


combining AETA with X-ray tomography (Chanvrier et al., 2014, 2015;

• the acoustic energy, mechanical work, firmness, and cell


Gondek et al., 2013; Karkle, Alavi, & Dogan, 2012). We note that these
wall
findings are mainly based on directly expanded snacks (via extrusion).
thickness to increase, and
• the crispiness, and amount of fracture events to decrease.
Furthermore, their snacks do not have a mixture of both soft and hard
fillers. In several of their discussions the amount of energy released per
fracture event is an important parameter. For the discussion below, we
The above results can be understood from the functionality of the
have computed these energies, which are depicted in Fig. 6 for the
soft fillers. They act as nucleation agent and cell openers, rendering a
samples investigated.
larger number of bubbles – but with smaller diameter. Due to cell
Expanded snacks with apple pomace fibers are investigated by
opening, the expansion is not as large as a lower amount of fillers. A
Karkle et al. (2012). It is found that addition of fibers up to 28% lead to
lower amount of fillers leads to higher expansion, but the coalescence is
thinning of bubble walls, decrease of bubble diameter, decrease in ex-
pansion ratio, and increase of hardness. If fibers can be viewed as soft
fillers, the above cited results are inline with our findings. Furthermore,
important remarks are made about homogeneity of bubble size dis-
tribution. For a more homogeneous distribution of bubble size, it is
expected that multiple fractures will happen simultaneously, and will
be recorded as a single event. Also, the apparent amount of energy
released per fracture event will increase. Samples with low amounts of
fibers show a high degree of heterogeneity. This heterogeneity is for
directly expanded snacks much starker than for indirectly expanded
snacks. The expansion is larger and number of bubbles is much less in
direct expanded snacks, due to high expansion temperatures and large
degree of coalescence. From Fig. 5 it follows that P3 have a narrow pore
size distribution, while P2 and P4 have a broad distribution. Viewing the
energy released per fracture, as displayed in Fig. 6, we observe that P3
indeed has a high energy release, and P2 a low energy release. This is
consistent with the homogeneity hypothesis of Karkle et al. (2012).
Fig. 20. Mean acoustic energy, as measured with Kramer cell, versus the Extruded crisp breads are investigated by Gondek et al. (2013).
amount of effective fillers (EF = RNS − RCS + PFL + PPG). Solid line shows They have concluded that increase of wall thickness lead to lower
the linear regression result (with r2 = 0.54).

11
R.G.M. van der Sman et al. Food Structure 18 (2018) 1–13

low number of investigated snack products in this study, we re-


commend validation of our hypotheses in further research.

Acknowledgements

The authors would like to acknowledge the funding made available


from PepsiCo which enabled this work. The views expressed in this
report are those of the authors and do not necessarily represent position
or policy of PepsiCo, Inc.

Appendix A. Supplementary data

Supplementary data associated with this article can be found, in the


online version, at https://doi.org/10.1016/j.foostr.2018.10.001.

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