Table of Contents

Summary chapter 1............................................................................................................1

Chapter 2...........................................................................................................................5
Chapter 3.........................................................................................................................17
Chapter 4.........................................................................................................................27
Chapter 5.........................................................................................................................32
Chapter 6.........................................................................................................................44

Summary chapter 1
What are the 2 Isotropic: have equal properties in all directions, e.g., cheese
types of Anisotropic: have different properties that depend on the orientation,
structures? e.g., meat.

Cheese: bi-dispersed, almost bi-continuous structure where protein and

fat are present as interconnected networks. Meat has a highly fibrous
structure, having alignment already at the level of the size of proteins.
What is the Consist primarily of triacylglycerols (TAGs), which consist of a
composition of glycerol backbone with 3 fatty acids esterified to the three alcohol
fats and oils? groups. They have different chain length, saturation, trans- or cis-bonds,
branching.
What affects the Have large differences in melting point, depending on chain length and
melting point of saturation:
fats? - Longer, fully saturated chains: high boiling point
- Shorter chains and unsaturated groups: lower melting points.
What are fat Apolar. Doesn’t dissolve in water. Mixing with water leads to a
properties? dispersion. Can form crystals: chocolate.
What are 2 categories:
biopolymers? 1. Proteins
2. Carbohydrates
In foods always together with water.
How are water
activity and
moisture content
related?

At low and intermediate mc, a large variation in aw is accompanied by a

 limited change in mc. For very wet products, the opposite is true.
What Temperature and presence of plasticizer (often water, also glucose and
determines the glycerol).
state of a
product?
What is the Eutectic phase behaviour means that the melting temperature of the
eutectic point mixture falls below the melting points of the 2 individual components.
and how is it Above the melting temperature and the solubility line, all molecules are
related to in liquid form. At temperatures below the equilibrium phase boundaries,
crystalline either the solvent or solute may form crystals.
region? The eutectic temperature is the point where the solute and the solvent
equilibrium curves intersect and is the point where a eutectic solid

should form.
Explain the
phase diagram
of water and
sugar

Crystallization of sucrose can only occur at conditions of temp and

concentration that falls between the solubility and glass transitions lines.
Above solubility, there’s no thermodynamic driving force (liquid),
below the glass transition line, the crystallization is constrained by
kinetic effects due to limited mobility.
What is the A non-equilibrium phase often seen in inorganic glasses, synthetic
glassy state? polymers, and biopolymers in foods. Often transparent, solid
appearance, and are brittle. Don’t have an ordered structure and the
volume is larger than that of the crystalline system.
Aka amorphous solids or supercooled liquids (e.g., rubber or sygar
 syrups).
Glass transition temperature in food systems is a property of amorphous
solids that occurs at 100 to 150 C below their equilibrium melting
temperature.
What is the Biopolymers are often hydrophilic in food systems and tend to form
effect of water amorphous, non crystalline structures at low water content. Food
content on processing, like baking, freezing, or extrusion often leads to glass
crystallinity? formation by amorphous or partially crystalline food components.
Glassy food products are extremely water sensitive. E.g., stickiness and
caking of powders and sugar containing products, lack of crispness,
formation of ice crystals, staling of bread.
What is a glass Associated with an increase in molecular mobility in amorphous
transition to systems. It’s a change in heat capacity over a certain temperature range:
rubbery? aka a second order transition.

What are first Such as ice melting or water evaporation. They involve latent heat
order effects and are much clearer seen in e.g., DSC measurements.
transitions?
What is the It influences the glass transition temperature: it interacts with proteins
effect of water and carbs, but hardly with oils and fats.
as plasticizing - Acts as a plasticizer and solvent: increases the free volume in
agent? the material and thereby molecular mobility -> reduces glass
transition temperature.
What is the Tm. The temperature where the last ice crystals melt during heating of a
equilibrium frozen material. it’s dependent on the dissolved food components and
melting their concentration. Below Tm, freezing of water may continue until a
temperature? maximum amount of ice has formed.
What is the Complex Dispersed Systems. To denote different classes of soft
CDS condensed matter physics. The continuous and dispersed phase can be
formulation? either in the gas G, liquid L or solid S state. / = dispersed into.
For gas we use air A. I = ice. Oil fat = F. proteins P. Carbs C. Starch S.
@ means: ingredients absorbed at interfaces. Encapsulated by.
What happens The starch crystals ‘melt’. And water is absorbed (together with
to starch during leaching of amylose). The ‘molten’ starch with the absorbed water
gelatinization? forms a gel (W/S). The crystalline form is indicated purely with S.
How do we Use the symbol |, which means in parallel with. ⊂ means superimposed.
write co- Low molecular weight components that dissolve easily in water, like
continuous salts and sugars, are just part of water phase W. W only refers to free
structures? And and capillary water, not bound water. Solid foams continuous phase:
well (A/P).
distinguishable
macrostructures
? Low
molecular
weight
components?
Emulsions?
Paper by Norton
& Fryer.
Product/Process
integration in
food
manufacture:
Engineering
sustained health.
Why does As a result of changes in lifestyle, diet is increasingly affecting health
Norton propose (incidence of obesity has increased). Food industry can play a major
a different role in reducing the incidence of obesity by this new approach to design
approach to and develop structured food products.
design and
develop
structured food
products?
What is a Typical length scale is 1 to 10 microns. This is the size of emulsion
typical length droplets, gluten domains in dough, etc. Here, molecular details become
scale in less important: the material properties are more dominant (though they
structured food are governed by molecules of course).
products? Can
you give
examples?
What happens These are in-mouth properties. Margarine is mixed with saliva, and the
with margarine fat phase starts to melt. This causes water droplets to coalesce and form
upon a coarse emulsion which leads to phase inversion and therefore the
mastication? release of water soluble components (e.g., salt), which increases flavour
perception.
On what aspects 1. Reduction of saturated fat level (SAFA)
should new 2. Reduction of absolute fat level
innovations in
margarin focus
on, according to
Norton?
How can By encapsulation, components that have an unpleasant taste (e.g.,
encapsulation functional peptides such as in Becel) can be added to food without
help to make decreasing consumer acceptance. They can then be released at the
food healthier? desired place and rate in the GI tract.
Why is it so - Poor taste and texture
difficult to - The sensation of melting is potentially the most difficult to
replace fat and replace
sugar? - Sugar is not only used for sweet taste. It has structural use as
well. E.g., retention of water in cakes, biscuits. To impart
succulence on chewing, or for controlling ice formation and ice
content. And the material properties of composite products,
such as chocolate and sorbets.
They are needed for structuring food products
Describe the Process design should be governed by product requirements. Possibly,
new paradigms new unit operations are needed. Norton indicates the use of
for processing microfluidics.
and
manufacturing.

Chapter 2
What 3 steps are (1)hydration and mixing, (2) heating, and (3)cooling.
important in creation
of structured foods?
What are the states, 1. Gas or vapour: very low viscosity, fast diffusion: flavours
their properties, and emanating from a food, steam, air, CO2 in bread
examples? 2. Fluid:
a. Liquid: low viscosity, free flowing: milk, beer, coffee
b. Rubber: can flow and deform but also has
consistency (elasticity): dough for bread, chewing
gum, bread crumb, cheese
3. Solid:
a. Crystalline: rigid and very hard, diffusion in a crystal
is virtually zero: crystalline sugar, salt, water in ice
cream
b. Glassy: rigid and brittle, diffusion is virtually zero:
potato chips, the crust of bread, dried noodles,
wheat and rice kernels, milk powder
When do you call a When it can be condensed into a liquid under conditions that are
gas a vapour? close to ambient. E.g., if you evaporate water. Air is not called a
vapour.
How are the Molecules are a thousand times closer to each other than in a gas,
molecules in a liquid but still have some freedom. Orientation is more or less random.
ordered? Limited order. It retains its mobility by the thermal motion of
molecules that withstand the attractive forces between molecules. If
the concentration is higher and temperature lower, the viscosity gets
higher and solutions can get some elasticity. It can still flow and
deform, but may partially move back to its original shape: rubber.
What is a rubber? Can still flow and deform, but when stress is released, it will
partially move back towards its original shape. Still a liquid, but
rubber-like behaviour. Aka gelation. A gel.
What is a glass? When the viscosity is so high that it resembles a solid, but is still
What is it on nominally a liquid. It feels brittle and hard solid. Examples: candies,
molecular scale? crispy crust of pizza and bread.
Molecular scale: still a liquid: more or less randomly oriented. Only
they can hardly move, so a glass can’t flow and adjust to stress. Any
material can become a glass. Large biopolymers like proteins or
carbohydrates will form a glass more easily.
What is the It is not in thermodynamic equilibrium, but it is a liquid in a
thermodynamic state vetrified state. It can’t respond anymore to the changes in its
of glass? condition, but would have a driving force to do so.
What is the If you cool down a liquid, allow the molecules to settle, they order
crystalline state? in very regular arrangements. Regular packing, higher density (by
about 20%) than the liquid form. Only exception: water.
Molecules can vibrate slightly in a crystal. High order. Minimal
moving freedom.
Does water Larger molecules move much slower in solution or the liquid state
crystallise quickly? compared to small molecules. So water can crystallize very quickly
Why? And other because the small molecules can quickly reorient themselves to fit
substances? in the lattice. But large molecules need time to orient themselves in
the crystal lattice.
Crystallization of carbs and oil takes a long time.
What is semi- Biopolymers that behave like a random coil often crystallize only
crystalline? Why partly. E.g.,: gelatinized starch: retrograde into a party crystalline
does it happen? state with only small crystals and incorporate a small part of the
Example? starch chain. The rest of the starch chain remains in the liquid state,
with either liquid or rubber-like behaviour (gel). If you cool down
the system, also the non-crystallized parts go into the glassy state.
What is a phase Has usually temperature and solid content, and shows lines with the
diagram? What is areas and equilibrium states.
liquidus? - Liquidus: the line at which ice crystals will start to form.
With no sucrose, this happens near 0 C.

What are ternary e.g., if there’s both carbs and proteins present. At a certain point the
phase diagrams? 2 are not miscible anymore and will form two liquid phases that are
at equilibrium with each other. In this diagram you can change the
concentration of C and P independently. You need 2 axes for the
overall composition. But also consider the water. You can’t get
more than 100%.
What is a state Similar to phase diagram, but doesn’t only show equilibrium states,
diagram? but states that one may encounter in practice. It is similar to phase,
but differs at higher concentrations of the dissolved components.
Also the glass transition. Because crystallization takes take, often a
glass is formed. But in glass there is never an equilibrium reached
because the molecules can’t move.

Explain the free Liquids are not completely dense but contain free volume, aka
volume of liquids, ‘holes’: spaces between molecules larger than average. Occur
holes, and randomly. A molecule not too far from the hole with sufficient
movement of thermal energy can ‘jump’ from its original spot to the available
molecules. hole, creating net movement of the liquid. If you apply shear in a
direction, then the jumps will happen more often in one direction
than the other.
What does the rate 1. The amount of motion of the molecules
of this jumping 2. The number of holes that happen to be present
depend on?
How can you With Eyring’s equation. R = the gas constant. V- is the total volume
determine the that one mole (or one molecule) occupies. V-0 is the volume per
viscosity? mole, that is occupied by the molecules themselves: inaccessible
volume. V-v0 = volume not occupied by molecules, but available to
jump into.
What is the effect of - Molecules have less thermal (Brownian) motion. Less
temperature frequent jumping.
reduction on - Lower amount of thermal motion means that molecules will
viscosity on move closer together. There’s less space needed to
molecular scale? accommodate all the motion. Density will increase. Molar
volume will decrease. Free volume is reduced.
What is the glass It is the temperature where the viscosity becomes very high, but the
temperature? temperature becomes lower to the molecules can no longer
reconfigure and no longer ‘fill the gaps’ in the free volume. The
fractional free volume is then effectively frozen in.
How do you Doolittle’s equation. But if the solution is not too far from the glass
describe this transition, the activation energy can be neglected and the equation
freezing in effect becomes simpler.
with fractional free
volume?
What is the WLF Williams-Landell-Ferry equation. This equation implies a universal
equation? behaviour, for all systems that are relatively close to its glass
transition (50-100 C). ??? hoeveel moet ik dit weten.
What is the If a molecule is longer, it has less freedom to move around and will
dependence on become glassy at a higher temperature than a similar, lower
molecular weight molecular weight component. It becomes glassy at a higher
with glass temperature than a similar, lower molecular weight component.
transition?
Page 13?
How does instant A concentrated solution of a mixture of proteins and carbs is
cappuccino foam exposed to high pressure of nitrogen, which dissolves into the
work? solution. While keeping the high pressure, the solution is atomized
and dried, which causes it to become glassy, while the nitrogen is
trapped inside the glass. The pressure is released and the product is
packaged. Dry, it remains a glass and nitrogen is trapped.
When dissolved in water, the glass becomes liquid, nitrogen is
suddenly released. Product also contains foam stabilisers so the
nitrogen forms fine bubbles.
What is The relatively large reduction of the glass transition by addition of a
plasticization? small amount of a plasticizer, usually a low molecular weight
component with a low glass transition temperature.
Explain semi- In native starch, only 15-39% is crystalline. If we gelatinise starch
crystallinity in and heat above crystallization temp, it loses the crystallinity and
starch mixes with water. If you lower the temp again, it re-crystallizes, but
only in small domains. These domains will act as crosslinks. It
forms a network -> retrogradation.
How does gelatine The dry sheets are glassy: brittle, transparent. When dissolved in
crystallize? warm water. If you cool the water below melting point (35C), small
parts of the gelatine also crystallize partly, up to about 20%. This is
called stiffening or setting.
Why do some foods - Because their melting temperature is very close to the glass
only semi transition. They never reach the crystallization point
crystallize? without being completely vitrified first.
- Globular proteins: they don’t unfold to expose the parts
that could crystallize, but have to crystallize as intact
globules and arrange in a lattice of complete globules. This
takes a lot of time (weeks or years). Doesn’t happen in
food. So we don’t see them as being able to crystallize.
What is - The small crystals in semi-crystalline biopolymers act as
crosslinking? 3 crosslinks: connect different chains to become entrapped in
types? a network.
 - Can also happen with chemically linking SS bridges between
gluten chains.
- Entanglements: in gluten during kneading of dough or
sodium caseinate in imitation mozzarella cheese. Same
effect as the crystallites or the chemical bonds as in gluten,
but they may disentangle given sufficient time. Dough and
mozzarella can exhibit creep: slow relaxation or flow due to
slow disentanglement of the network. If you pull faster, the
material behaves like a rubber: elastic due to the physical
crosslinks created by the entanglements. Pull very fast:
brittle and snap. Behaves like a glass.
Why is it preferable - It allows the candies to be transparent. Since diffusion is
to have hard candies virtually zero, it encapsulates flavour molecules very well.
in the glassy state? Crystals would exclude the flavours, which can leach out
quickly during eating.
- A glass dissolves quickly in the mouth compared to crystals.
Disadvantage:
- It dissolves quickly compared to crystals.
- Glass is very hygroscopic, so you need to pack it well. You
need to keep it below the Tg, otherwise it can crystallize
and become opaque, expel flavour.
- If not packaged adequate, it may pick up moisture from the
air and crystallise out at some point.
How is hard candy - Boil a sugar solution and evaporate the water so the water
made? content is very low (2-5%).
- Add flavours.
- Pour syrup into moulds and allow to cool quickly.
Prevent graining: difficult, but helped by addition of corn syrup
(mostly fructose), which has a much higher Tg (100 C compared to
52C of sucrose), and a lower crystallization temperature (124 C
compared to 192 C).
Describe the baking For cookies with a lot of sugar, you can use the state diagram for
of cookies with the sucrose.
state diagram. - First, batter with moisture (20-30%). When there’s enough
moisture, there’s only dissolved sugar. Otherwise there may
be some sugar in crystalline form.
- In the oven, the temp rises, at the surface becomes 100C
and follows boiling line. Surface evaporates and becomes
more concentrated. Shifts to the right as sucrose %
increases.
- When taken out of the oven, they cool down and enter the
glassy state: become crispy. Important to allow cookies to
cool down.
What happens when Sugar can crystallize out and the texture becomes very different.
cooling down
happens too slowly?
What happens when If you add baking soda, NaHCO3, with water, it slowly decomposes
you add baking above 70 C into Na2CO3, H2O and CO2. The CO2 makes small
soda? bubbles in the batter. When cooling down, it goes to glass state, and
the gas becomes fixated as pores or bubbles. Without the bubbles,
the glassy cookies would be very hard. With bubbles, they are
crispy and crumbly.
Describe the baking Similar to cookies. Main constituent is flour, but we still use the
of crackers? sucrose state diagram. A lot of moisture has to be removed from the
crackers and the surface becomes very concentrated in solids
compared to the inner volume. Surface becomes dense, and most
pores are inside.
- Moisture evaporates at surface -> more concentrated ->
upon cooling goes to glassy region -> crackers with low
moisture content, glassy, low shelf life.
What happens to It absorbs moisture again, leaves glassy region, not crispy, becomes
crackers if there’s rubbery.
moisture?
How is porosity - Yeast: leave it, it ferments and generates CO2, generates
added to crackers? bubbles. But yeast often gives too much porosity in
crackers. Too much gas -> too much isolation -> too thick
cracker -> too long baking time to make a good, crispy
cracker.
- Baking soda: like with cookies
- Not using an oven: using a very hot plate to bake the
crackers. This transfers heat so quickly, while not allowing
much moisture to escape from the surface so the moisture
inside the cracker starts to boil and form steam bubbles.
Why is a cracker so If it’s too thick it would lose moisture from the top but moisture
thin? migration from the inside to the surface would be too slow. You’d
have to bake the cookies for too long.
How is bread made? Has flour (in glassy state). Added water, which develops a gluten
network, which makes protein the initial structural component. CO2
formation in the gluten network. In the oven, moisture migrates
from the surface, maillard reaction takes place: brown crust.
Heat from outside gets into the bread, CO2 in the bubbles expands,
released slowly to outside. This continuous outflow of gas
counteracts the conduction of heat to the inside. So the inside never
gets hotter than 80 C. Doesn’t lose much moisture, remains flexible.
Crust becomes glass again with cooling.
What happens to the The starch gelatinises. During and after baking some of the starch
inside upon baking? retrogrades and forms a strong gel or rubber. Therefore, the
Is the final texture consistency of the final bread is mainly because of the starch and
mainly starch or not the gluten.
gluten?
Gelatinization of starch takes place between 60-80C.
What are the - Mesoscopic (nanometer): 2 permeating networks. Gluten
structures of bread network formed during kneading, formed by forming
on mesoscopic chemical bonds. Starch network is crosslinked by some
scale, microscopic degree of retrogradation: formation of small crystallites
scale, millimeter that incorporate parts of several different starch molecules.
scale, and - Microscopic (micrometer): dough is a continuous gluten
centimeter scale? network, in which starch granules and large CO2 bubbles
are dispersed. During baking, the product becomes
bicontinuous. Starch granules swell and touch each other.
Cooling leads to formation of crosslinks. Gluten network
remains or loses some of its continuity, not as important
anymore.
- Millimeter scale: strongly structured: bubbles give a spongy
structure. High porosity: parts of bread can easily be
separated off: crumbly
- Centimeter: crispy and brown crust. Soft, crumbly inside.
Caused by the inhomogeneous heating and evaporation
conditions during baking.
How would you Using 2 diagrams: one for gluten and one for starch. Or plotting
visualise this in a both in one diagram with different colours.
state diagram?
How is kerupuk Deep-frying. Oil (app. 180 C) quickly transfers heat. They’re thin
made? Frying. so homogeneous heating. Product is in glassy state and can’t
respond quickly. Moisture explodes into vapour bubbles at high
pressures. Quick evaporation -> heat is absorbed -> product cools
down quickly -> retains pores -> enters rubbery zone.
Out of the oil it’s still flexible. After cooling, it glassifies and
becomes crispy.
Porosity: makes it edible. Glass state: makes it crispy.
What would happen Too little moisture: product doesn’t come out of glassy state, no
if it had too little or porosity.
too much water? Too much: enters liquid state. Bubbles collapse before product is
sufficiently solidified.
Draw the diagram
for drying of
kerupuk, and frying
(or microwave).

How is popcorn Kernels are quickly heated. Moisture inside builds up pressure.
made? Hard hull resists pressure, but then releases it. Kernel explosively
releases the moisture as steam. Moisture escapes. After cooling, it
becomes relatively crispy. Kernels are only suitable if they have
enough moisture, otherwise it won’t come out of its glassy state and
not form bubbles. Or too much moisture: collapse of the formed
bubbles because it doesn’t have the rubbery consistency during the
expansion.
 The right one is when it goes wrong and is not popped.
How is spray drying Food is atomized into very small droplets -> sprayed into a large
done? vessel with air heated to 80-250 C, which makes sure that the
relative humidity of the air is extremely low.
Droplets lose moisture due to evaporation -> hot air absorbs
moisture and gives off heat of evaporation to the droplets.
- Constant rate period: temp of the droplets remains
relatively low due to evaporation of moisture that cools.
Droplets remain at the wet bulb temperature.
- Falling rate period: droplets lose so much water that a skin
of solids forms on the outside. Diffusion of water through
the skin determines the evaporation rate and the droplets
heat up. Now they are transferred to a fluidized bed.
- Fluidized bed: fluidized by an upward warm air flow which
is mildly heated so particles don’t overheat. Residence time
is much longer since diffusion of moisture through the skin
is slow.
Explain this through As droplets move closer to the glass transition, moisture diffusion
the state diagram. becomes slower and the droplets will heat up.
How will the final If droplets remain deformable, they will accommodate the reduction
product look? Why? in volume by shrivelling. If the outside is already relatively rigid,
they will keep their spherical shape, but form one or more vacuoles.

How will spray Globular proteins: have a fixed shape, show more rigidity already at
dried globular low concentrations, but water can still diffuse between the proteins.
proteins and So the skin is rigid, before the diffusion rate is too low to block
maltodextrin (carbs) drying.
look? Maltodextrin: very flexible. Only get rigidity very close to the Tg,
at which point the diffusion rate is very low. They will deform
much more.
What is the different Hollow particles: good flowability, low bulk density .
in functionalities Shriveled particles: higher bulk density due to irregular shape. Poor
between shriveled flowability.
and rigid particles?
How can shrivelling By allowing some time for annealing during cooling: allowing the
be prevented? irregular particles so the capillary action can smooth out
irregularity, and then cooling the powder.
How does caking of One cause: deformation of the particles when pushed together,
powders happen? which is related to the viscosity.
- If powders are in the glassy state, change is prevented ->
good flowability and dispersability.
- Caking line/sticky point line: line above which powders
become sticking and start to cake.
What is Involves capturing foods inside a matrix that protects them against
encapsulation and hostile conditions, but also allows release at the moment of
what does it do? function. E.g., probiotics should be protected from extreme pHs in
stomach and duodenum, but also released alive in the intestinal
lumen.
Look at reader for examples in table.
How is The component is dissolved or dispersed in a concentrated solution
encapsulation done of the barrier material (often maltodextrin, corn syrup, modified
by spray drying? starch, gum Arabic, gelatine, cyclodextrin, and whey protein). This
needs to be dried very quickly to ensure the encapsulated
component is not lost during evaporation of water.

The particle size obtained is limited by the size of droplets that can
be made by the nozzle. It depends on the type of matrix material
and type of encapsulated component.
Oil soluble You need to prepare an emulsion of oil droplets into the slurry of
components. What matrix material, which should then have emulsifying properties and
do you need to look allow stable emulsion at high temperatures.
out for? High-molecular weight components (proteins or modified starches)
are suitable, but would give the slurry a too high viscosity. We
often use intermediate molecular weights, such as maltodextrins,
but they don’t have great emulsifying properties.

For emulsifying properties: add specific components. However this

may have an effect on the glass transition: they may act as
plasticizer.

Same for water-soluble components. Be aware of the change in the

glass transition.
How is It’s an extension of other techniques. First spray dried or fluidized.
encapsulation done For liquids, it agglomerates the small particles into larger particles
by fluid bed drying by the formation of liquid bridges. The agglomerates then act as
or drum coating? primary particle.
Fluidized bed encapsulation: you can slowly spray the material that
will accumulate on the outside of the particles. The water then
evaporates and a coating around each particle is generated.
This can lead to very high loadings (outside layer).
 Disadvantage: particles can’t be made very small and particles are
exposed to air for a long time so encapsulation of volatile
components is a problem.

Drum coating: particles can’t be fluidized because they’re too large

(candies, tablets). Placed in a slowly rotating drum. Spraying a
solution of a coating material while blowing (cool) air through the
drum. The droplets that adhere to the outside are slowly dried and
slowly surrounded by a solid coating.
Encapsulation by You can add components in powder form, add water, and have it
extrusion? mixed intensively in an extruder. You can process much more
viscous pastes than with spray drying.
Somewhat comparable to spray drying, but with much more
concentrated material and less moisture to evaporate -> less drying
needed. More suitable for volatile components.
Drawback: encapsulates can’t be very small. Similar loading to
spray drying.
Encapsulation by Congealing: co-freezing. Suitable for hydrophobic components,
congealing or spray since often fats are used as encapsulant.
chilling? Preparing the mixture at a temp above the fat melting temp. Then
atomizing into a spray chiller and cooled to below the fat melting
temperature (allow time for crystallization so active components are
‘frozen’ in matrix).
Problem: crystals don’t grow into a nice shell and doesn’t
encapsulate well. Solution: chill the droplets so fast that the matrix
material becomes glassy. Good as long as it remains glassy.

Gives small particles. Encapsulant is not only at the outside, so

loading is high. Cooling is fast so good for volatile components.
Disadvantage: encapsulation material is a fat, which has to fit the
formulation.
Example of BASF ???. Reader page II 31
Summarize when to - A material just above glass transition (less than 70-100 C):
use which kinetics leathery or rubbery -> Williams-Landell-Ferry (WLF)
system and kinetics
equation. - Dilute solutions and other relaxation-related characteristics
such as diffusion -> Arrhenius kinetics
- Glass transition temperature of a (molecularly) mixed
system -> Couchman-Karasz equation or Gordon-Taylor
equation.
What are semi- When biopolymers make crosslinks and obtain elastic properties.
crystalline Such as starch and gelatine can partially crystallize, which creates
biopolymers? crosslinks.
Chapter 3
What are some facts Crystallization is rearranging of molecules into an ordered
about crystallization? structure, and generally only crystals form with their own kind. So
other components have to diffuse to the growing crystal.
What is a first-order The type of transition that needs re-ordering and typically creates
transition in crystals? a new phase. Crystallization, evaporation, liquid-liquid demixing.
And second-order?
Second-order transition: A transition that only changes the rate at
which changes of properties take place. Glass transition (no new
phase, only rate of diffusivity changes).
At what conditions do It can only happen when the random Brownian motion doesn’t
crystals form? disrupt the ordered structure too much. They can only be formed
at low temperatures, and any crystal can be disrupted by
increasing the temperature.
What interactions are Crystals form because these interactions are then strongest: can be
related? hydrophobic (VdW) or polar (permanent; Debye and induced;
London), or related to hydrogen bonds.
There are different ways for molecules to align in a crystal and
some forms are more stable than others related to their
intermolecular interactions.
What is That molecules can crystallize in different crystals.
polymorphism?
How do small Often cubic, hexagonal, or similar crystals.
molecules usually
form crystals?
How do large They make sheet like crystals: grow by stacking the alkyl chains
molecules like lipids next to each other, such that the polar head groups stick out of this
form crystals? layer and both hydrophobic interactions and hydrophilic
interactions.
How do crystals 1. By excluding other components from their crystal
form? surfaces, which therefore becomes concentrated onto
their surfaces and will diffuse into the rest of the solution.
The surrounding matrix becomes more and more
concentrated in the other component and increases the
viscosity.
2. Crystals interacting: if crystals are far away, they don’t
influence each other. As more crystals form they become
larger and can touch, which forms a network that
becomes continuous -> percolation. E.g., margarine and
chocolate.
What influences the The more oblique the crystals, the faster the network formation:
rate of crystal - Thin needles will interact more at lower volume fractions
formation? than spherical or cubic crystals.
Crystal shape and size is important.
What is the It is used for crystals. Generally valid, except we assume that the
Hildebrand equation? enthalpy of fusion is constant, which it is not, it is temperature
When do we use it? dependent. So it’s not super accurate.
We use it to predict where the crystallization line is in the state
 diagram.
What is the eutectic The point where the crystallization line and freezing line intersect:
point? - At this point we can both make ice crystals and sucrose
crystals.
- Any lower in temp, we just make ice and sugar crystals.
This is the lowest possible temp at which the system can
be in the liquid form.
What lines are below Here there will be an equilibrium of ice and sucrose crystals. So
this point? the crystallization lines actually don’t exist. There’s just 2 areas:
one with pure ice crystals, and one with pure sucrose crystals.
How do we determine The lever rule:
how much of ice or - It gives the weight fraction of ice at the condition.
sucrose crystals is
present?
How can we make a Sucrose has a Tg of 347 K (74 C) and is entirely in the
glass from sucrose crystallization area. If we get close to the Tg, should we not have
while passing through crystals?
the crystallization No: crystal formation takes time. So if you dehydrate quickly
area? enough (heating and boiling away excess water, quick cooling
down), you get a sucrose glass.
This is what happens in candies or sugar cotton.
What is the The relation depends on the type of molecules:
relationship between - Mobile molecules: can rotate easily and is not quickly
glass transition and trapped in a network: low Tg. E.g., water (Tg is only half its
melting point? melting temp Tm). For mobile molecules, the Tm is
typically 1.4 times the Tg.
- Rigid molecules: more difficult to rotate. Higher Tg. It’s
easier to get stuck, so the temp at which it forms into
glass is quite high.
Why does fructose They have the same translational diffusion rates, but:
have a much higher - Fructose is more irregular with bulky groups sticking out.
Tg than glucose? - This gives it very low rotational diffusion, so it’s much
Even though they slower in reorienting itself in a concentrated solution than
have the same Tm? glucose.
- Fructose is often added to products because it makes it
easier to attain a glass transition without obtaining
crystals.
What does When a solution is cooled down below the crystallization
supersaturation mean? temperature, and can in principle crystallize, but can’t due to the
absence of nuclei.
What are nuclei? And A nucleus is a small starter crystal. Formed in 3 ways:
how are they formed 1. Seeding: manually adding it. The crystals then form
in solutions above the around the nuclei which grow in time. When the solution
crystallization loses its supersaturation, the small crystals are separated
(freezing, melting) from the large ones and recycled back to a new volume of
point? supersaturated solution as nuclei.
2. Heterogeneous nucleation: creation of nuclei on surfaces
or particles. E.g., glass. Some particles of this right surface
 can be absorbed onto the solution and form a layer that is
similar to a crystal. When this happens, other molecules
can align themselves to the surface and start a crystal.
Therefore, there’s often not supersaturation in complex or
unpurified solution. For heterogeneous nucleation, some
supersaturation has to occur for the nucleus to be created
on a surface or particle.
3. Homogeneous nucleation: if too pure, heterogeneous
may not occur. We could reach extreme supersaturation.
But at a certain point, crystallization always occurs:
supersaturation becomes larger, dissolved molecules have
poorer and poorer interaction with the surrounding
solvent molecules and associate themselves with each
other. Concentration fluctuations occur: spontaneous
areas with lower and higher concentrations of dissolved
component. At some point the area gets so concentrated
that they act as a nucleus. Then you see very sudden and
fast crystallization.
What is the relation The rate of nucleation shows a maximum when you increase the
between rate of supersaturation, and then decreases again.
nucleation and - When crossing crystallization temperature, the number of
supersaturation? nuclei formed rises non-linearly with increasing
supercooling or supersaturation.
- At larger supersaturation or supercooling, the viscosity of
the solution begins to increase which makes it more
difficult for molecules to come together and form nuclei
(hetero and homogeneous).
So using this how can When the solution is quickly cooled or quickly increased in
you avoid nucleation? concentration, you can avoid nucleation and it will remain
supersaturated. In the end it becomes so viscous that it forms a
glass.
- In sugar solutions: this happens more easily because the
crystallization line and glass transition lines are close to
each other.
Do crystals grow No. They grow faster at specific sides, because the molecules can
equally fast at all easily fit in the regular pattern in which the molecules are
sides? What shapes of arranged in the crystal. On other sides the molecules might have
crystals are there? to be distorted or won’t fit, so it doesn’t grow as fast. Therefore
crystals aren’t spherical but have a specific shape: hexagonal,
cubic, or needle-shaped.
What is the induction Time needed for nucleation and time needed for crystal growth,
time? before significant crystallization takes place. This time is
infinitely long when supersaturation (or supercooling) is zero.
Also infinitely large at the glass transition temp, as the whole
system is immobilized at that point.
What happens when They tend to become very regular: when the growth rate
crystals grow slowly? increases, you can see branching. Because of more growing on the
growing surface, the growing face splits up, and from the face,
 two or even more faces start to grow. E.g., snowflakes.
Explain the effect of
supercooling or
supersaturation on the
induction time.

You see that the induction time is very high with low
supercooling (Tg), and then becomes lower when the amount of
supercooling becomes less. It become higher again when it
reaches the crystallization temperature. ?????
What is the effect of Branching leads to formation of an ever-widening brush of
branching in needles, that ultimately form a sphere, that contains fat crystals,
crystallization into surrounded by liquid oil. Such a spherulite is therefore porous,
needles? and only partly crystalline.
What happens to In ice cream, ice is constantly scraped off cold walls which
crystals when you introduced tiny flakes of ice in the ice cream, which are highly
store them? Example irregular in shape.
of ice cream. - They’re not very stable and want to recrystallize into more
stable shapes (spherical) to reduce surface area.
- Uncontrolled recrystallization leads to unwanted changes
in the product.
What they do: after making, the product is stored for some time at
-18C which enables the irregular crystals to smooth their surfaces
and become more regular, while other effects are still suppressed.
What crystals are Most stable in one single, large crystal: larger crystals are more
most stable? stable than smaller ones.
- Large ones tend to grow at the cost of smaller ones:
because the solute is slightly better soluble near a smaller
crystal than it is near a larger crystal, which gives a (very
small) concentration difference of solute from small to
large. Slowly the small crystals dissolve and the large ones
grow.
What is Ostwald The total crystallinity remains the same, only you see slow but
ripening? steady growth of the average crystal size, and a widening of the
size distribution.
Aka disproportionation.
When does Happens faster when the temp is not completely constant. During
disproportionation warming, mostly smaller crystals will melt, but during subsequent
happen more often? re-cooling, the ice will mostly form on the larger crystals. After a
What is migratory re- few cycles we have Ostwald ripening, but much faster ->
crystallization? migratory re-crystallization.
Example? When you have ice cream, let it warm up, then freeze again. The
outer sides become much coarser and gritty, because part of the
small crystals melted and re-frozen into large crystals.
What is sintering? (Or In concentrated suspensions the crystals may touch and there may
accretion) be a migration of the molecules to the contact point between 2
 touching crystals, which leads to the formation of a neck between
the 2 crystals. If this happens everywhere, a network of crystals is
created and the product becomes solid.

How can you prevent The small crystals have started to disappear. You can have the ice
formation of larger cream re-crystallize for some time at around -15 C, during which
crystals in re-cooled the crystals become somewhat larger and more regular in shape. If
ice cream? you then freeze the product down to lower temperatures, the
crystals grow, start to touch each other, and fuse through sintering
-> becomes a solid.
How does this happen The needle-shaped crystals fuse together at their contact points
in margarine? and form a network with a yield stress. A random network of
needles is sparse and has relatively few contact points per unit
volume, so it is still a ‘soft solid’. When you scrape it with your
knife, the contact points are broken and the product can deform.
What can happen If the crystallinity is very high, it can lead to a completely dense
eventually through structure and all pores are closed slowly. End: a dense structure
sintering? with only a few percent porosity. The matrix is completely dense
and quite strong. Such a polycrystalline matrix is opaque, but with
similar properties to a monocrystal.
What happens when The ice crystals inside the cells pierce the cell walls, the
you freeze vegetables? intracellular fluid is released, and the turgor/internal pressure is
lost. Cells become deflated. In spinach a la crème this is wanted.
What happens when Product retains firmness. When you start baking, the texture is
you freeze meat? coarser and meat is less juicy:
- Ice crystals have pierced the cell membranes, some serum
is lost.
- But there’s no cell walls and turgor or pressure. Much of
the firmness comes from the proteins inside and around
the cells.
- So the effect on firmness is less than with vegetables.
What is a remedy? Freeze much quicker: ice crystals are smaller, cell walls are less
pierced. Turgor is better retained.
Describe what - Cooling: product hits the liquidus (ice crystallization line).
happens during Crystallization doesn’t immediately happen because it
freezing with the state needs nucleation. Supersaturation gets high enough for
diagram. nucleation. Then the crystals grow fast.
- Crystallization of ice releases heat. Rapid crystallization
results in increase in temp again until it hits the liquidus
line again. The solution now has 2 phases: ice crystals of
pure water and solution surrounding the crystals.
- With time, the crystals will grow and surrounding liquid
becomes more concentrated. Following the liquidus line.
 - If we reduce the freezing temperature, more ice will be
formed and surrounding liquid becomes more
concentrated until it hits the point where it becomes
glassy. Water can’t move towards ice crystals, freezing
can’t continue -> this concentration is cg’, the
temperature is Tg’. This is a single fixed point in the
diagram.
- Below Tg’, it is a brittle solid: dispersion of ice crystals
surrounded by a glass. Not spoonable. Above Tg’, the
dispersion of ice crystals is inside a liquid with rubbery
properties. Then (if not sintered) it’s still deformable.

What is freeze-flo Technique where high-fructose corn syrup is used to ensure a low
technology? T’g, such that the product will retain its fluid properties even at -
20C.
What does Planck’s The time of freezing is linearly dependent on the size of the
equation tell us? product.
Why shouldn’t we use Usually the product is not yet at freezing temperature when it’s
the equation too put in the freezer, which adds extra time to the process. Many
quantitative? assumptions are made which make it inaccurate. But good for
estimations.
How is ice cream The ice crystal size is kept small through mechanical deformation.
made? Solution is cooled in a scraped surface heat exchanger, cooled
with boiling ammonia at the outside (-24 C). Crystals formed are
continuously scraped off. There’s constantly a bit of ice remaining
on the surface creating nucleation. Leads to small crystals that are
irregular. This requires annealing time for the crystals to gain a
smoother, more spherical shape that gain in size due to Ostwald
ripening. This makes it more stable over time.
How is ice cream Ice crystals made on the wall are scraped off by the screw. The
made through large amount of shear forces inside the extruder breaks up large
extrusion? What are crystals and introduces secondary nuclei. Resulting ice cream has
the benefits? a very fine structure. The extruder works with very viscous
materials which makes it possible to go below -10 C. but not too
close (c’g, T’g) or the extruder would stall. High force -> ice
 crystals remain small -> air bubbles become smaller -> creamy
taste and allows you to use less fat.
What is the ‘collapse’ Losing the structural or compositional coherency of a product.
phenomena in ice Happens if product is maintained above T’g.
cream? First collapse: structure itself. The matrix is still a fluid and allows
Ostwald ripening and other coarsening phenomena over time. It’s
not stable in time. Might become solid (sintering) or coarse and
gritty.
Liquid that surrounds the crystals has become very concentrated:
enzymes or components susceptible to degradation will be very
concentrated. Oxidation or browning degradation reactions may
be fast.
What happens to They are very susceptible not just to structural collapse, but also
frozen products above to compositional degradation (oxidation, hydrolysis). So the
T’g? products are not stable anymore.
How can you mitigate With cryoprotectants or cryostabilizers?
this?
What are You need to make sure that the total concentration of non-water
cryoprotectants? components (solids concentration) is higher than c’g. then ice will
never form, cooling the system, and bringing it into the glassy
state. Then there’s no freezing damage. After careful thawing, the
complete structure is recovered.
We replace part of the water by another, glass forming
component, so we make sure that the system doesn’t make ice
crystals: making sure that the system will have a solids content
higher than c’g.
What kind of Low-molecular weight components, because large ones will not
components do you be able to penetrate the matrix and replace water.
need for this? What If you add large components to the outside it might lead to
happens if it goes osmotic dewatering, which will destroy the structure. But this
wrong? depends on the structure.
Also, the component added should not crystallize itself, which
would destroy the structure as the ice crystals do.
What is Using a component that significantly increases the T’g. When you
cryostabilization? freeze, the matrix around the ice crystals becomes more
concentrated. Components with a high Tg will also become more
concentrated and elevate the Tg’ of the whole mixture. The larger
the molecular weight, the stronger the effect of the cryostabilizer
(Tg is inversely related to Mw).
What is the downside A high Mw additive will also significantly change the sensory
of these components? properties of the product.
What are antifreeze Proteins that inhibit growth of ice crystals by absorbing on the
proteins? ice-water interface. They’re folded so they create a surface that
almost exactly matches specific crystal surfaces of ice, in
geometry and polarity. They strongly adhere to any ice surface
and inhibit attachment of new water molecules.
The driving force for crystallization is still present. So if sufficient
nuclei are created, there will not be sufficient antifreeze proteins
present, and crystallization will commence again. Also, other
collapse processes, such as oxidation or enzymatic browning, may
 still take place since the matrix is in the rubbery zone.
How does freeze Consists of the separation of liquid water from a wet solid product
drying work? in the form of a solid phase, ice, and its subsequent removal by
vacuum sublimation, leaving the product in its anhydrous state.

First product is frozen. Then milled into small particles -> spread
over large plate -> put into bacuum. When the water vapour
pressure above the product becomes lower than that of the ice, ice
will sublimate.
How can we calculate With the Clausius-Clapeyron equation.
the heat sublimation
and temperature for
freeze drying?
Explain the state
diagram for freeze
drying.

- The initial product is frozen and is at the Tg’. There are ice
crystals at the surface and embedded in the glassy
mixture. The matrix itself still contains a lot of water.
- As long as the temp is below Tg’, the water ca’t escape, so
we need to slowly increase the temp until the product is
at T’g again.
- We then again slowly increase the temp and slowly lose
ice and unfrozen water from the matrix through
sublimation. The product follows the glass transition line.
- If you increase the temp too fast, it goes too much above
the glass transition. Moisture diffusion will be faster,
whole product becomes rubbery. Then the whole matrix
collapses. Pores close due to capillary pressure, product
shrinks, loses porosity. Other degradation processes may
take place.
- At the end of freeze drying, the product needs to be
heated to temp above room temp to lose moisture. So
when you cool again, it goes to the glassy area. If you
don’t remove enough moisture, it may become rubbery.
What’s the difference Freeze drying: first freeze, then sublimate ice crystals. Unfrozen
between freeze drying water in matrix also evapores, leaving even smaller pores.
and hot air drying in Dimension of product is similar to original. When rehydrating, it
product morphology? takes up water easily due to capillary action and it is porous. But
the rehydrated product never gets the same sensory properties as
original.
Air drying: becomes much smaller in size. In contact with water,
they rehydrate only slowly as they’re not porous. However, when
rehydrated, the texture is much more similar to that of the
original.
How can you Freeze quickly: small ice crystals, small pores. Ultimate product
influence freeze will be closer to the original one after reconstitution.
drying to get certain Adapt the formulation such, that the Tg will shift. Then we get
properties? different crystal sizes. Can increase Tg by adding a higher-
molecular weight maltodextrin.
How does You can get a crystal of 2 types of fats. It can be 100% one lipid.
crystallization of fats 100% the other lipid crystal. Or a morph crystal of both lipids.
work?

What is the structure It is cocoa butter, with sugar, cocoa grains, and milk powder
of chocolate? suspended in the butter. The cocoa butter is crystalline. The
crystals form a network in which the particles are captured. Due
to sintering, it becomes solid.
Not all crystals are equally stable and they have different melting
temperatures.
To induce certain types of crystals, we have to avoid the
formation of other crystals. Crystal type 1 to 3 form quicker than
higher ones: due to their looser packing, nucleation of these
crystals is easier.
How does tempering Selective crystallization. The cocoa or cocoa butter is first mixed
work? with the other ingredients, grinded until all particles are small.
This ‘conching’ happens at 45 C at which all fat is liquid.
It’s cooled and held at 27 C. At this temp polymorphs (crystals)
type I to III can’t form. Only IV and V. Nucleation of these
crystals takes time, so it needs to be held at this temp, while being
deformed to ensure nuclei are formed.
Then temp is raised to 31 C, at which IV melts and we only have
polymorph V. VI doesn’t form because its nucleation rate is very
slow.
After tempering the still fluid mass is poured or shaped, and
stored for some time at around 20 C. The fat crystals now grow
and form a network by sintering.
What’s another way to By seeding the melt with V crystals (adding shavings of
temper chocolate? chocolate). After seeding, the same procedure of constant
 deformation has to be followed to multiply the number of seeds
and remove the IV form.
What is the effect of If you store at a temp that’s too high, the crystals would
storage? disproportionate and form very large crystals -> gritty. Temp is
too low: the type V polymorph crystal may slowly convert into
the lower polymorphs (also quite stable at low temp).
What happens when Sugar crystals near outside partially dissolve and re-crystallise
chocolate is exposed into larger surface crystals, which occur as whitish stains.
to moisture.
How does fat bloom Results from temperature fluctuations, and sugar bloom from
happen? moisture.
How can you avoid Temper the chocolate such that the smallest crystals have already
this? disappeared, and thus the driving force for recrystallization is
reduced.
What are spherulites? At the corner lines of a crystal (where 2 crystal surfaces intersect),
it’s less stable and there’s a stronger driving force for new
molecules to adhere. This can lead to a defect in the crystal lattice,
which acts as a new nucleus. Then you see needles growing in all
directions giving a spherulite. This is the same polymorph, but is
created of many needle shaped crystals. These crystals exclude
those triglycerides that don’t participate in the crystals. There’s an
accumulation of non-crystallizing triglycerides.
When do spherulites Can form during storage of vegetable oil and accumulate at the
form and how to bottom of the contained. To avoid: oils are often dewaxed, by
avoid? cooling and then filtering the crystals off. Unfiltered oils can be
hazy with crystallization of saturated fats.
How does spreadable Butter fat is melted and held at relatively low temp. the most
butter work? saturated fats will crystallize. The mass is kept under motion to
avoid formation of larger entities like spherulites. After some
time, the mass is filtered and the filtrate is butter fat that has a
lower average melting point: will form less crystals at the
temperature of consumption.
Why does the taste of Your saliva slowly dissolves the sugar at the surface of the candy
candy get less over and it slowly dissolves. The dissolution rate is constant per m2 of
time in your mouth? surface, but the amount of surface is going down, so the taste of
candy in the beginning is the strongest and then slowly goes
down.
Chapter 4
What are some
appropriate types of
films for types of
migration?

How can you avoid 1. Take away the driving force: sometimes by adapting the
the transfer of formulation. Reducing the amount of moisture. Reducing
components? the water activity.
2. Reducing the transfer rate: done in 2 ways:
a. Ensure that the product is (partly) in the glassy
state. Like sugars. Transfer of moisture then
becomes slow.
b. Apply another edible coating designed to reduce
the rate of transfer.
What is the activity 1. Pure component: always has y=1, because the reference
coefficient of some state u = u0. so the activity has to be 1. Then y has to be 1
components? as well. If almost pure water, very dilute solutions, the
coefficient will be close to 1.
2. When a mixture behaves ideally, y=1 for any xi. This
doesn’t happen often.
3. When component I is very dilute in a liquid mixture (xi is
very small). We don’t know the value of y, but we do
know that it’s constant (independent of xi).
What is the equation The chemical potentials of all components are equal in both
when there’s an phases. You can recognize an equilibrium by looking at the water
equilibrium between 2 activity. When the activities are equal in both phases, there is an
phases? equilibrium.
What does it mean Then the pressure in the gas is equal to the saturation pressure
when there’s an (psat).
equilibrium between - Psat is dependent on the temperature.
gas and liquid? - The saturation pressure can be calculated with Antoine’s
equation.
- You can use the psat as the reference pressure.
What type of solutions In general, a very dilute solution will behave ideally. Also,
behave ideally? solutions in which only Van-der-Waals type interactions take
place tend to behave ideal (when all other interactions are absent).
Aqueous solutions with many hydrogen bonds, generally don’t
behave ideally, unless they are dilute.
How do we find the There’s no clear-cut theory for finding it. Just look at models and
activity coefficient for see what gives the best results. For solids often sorption
non-ideal solutions? isotherms.
What is a sorption Relates the composition of one phase to the composition in the
isotherm? When do we other. Henry’s law is used for systems containing only a trace of
use what equation? permeant.
Often, a non-linear increase of the mole fraction of permeant in
food and barrier is seed: sorption levels off at higher mole
fractions. Then we use Langmuir isotherm: for adsorption of a
monolayer of molecules on a surface.
More than only a monolayer of mols can adsorb, polymeric
materials: combination of Henry and Langmuir.

What are some well- Multilayer adsorption theories: BET isotherm and GAB relation.
known isotherms for
food?
What is the driving It’s equal to the negative gradient of the chemical potential. The
force for a component larger the driving force caused by the gradient, the larger the rate
to move? of mass transfer will be.
What forces do One the one hand the driving force, pulling towards the region
molecules experience with lower chemical potential or activity. On the other hand
during transfer? slowed down by friction with the environment. This is dependent
on the difference in velocity.
How do we use the Relation between weight fraction and activity of water is linear:
Henry sorption for the w1 = ma1. We can enter this in the flux equation. If the value for
permeability and the diffusivity and the Henry partition coefficient are both
permeance? constant, the gradient of the activity over the film with thickness
L at steady state will be linear. We have a term which we call the
transfer coefficient or permeability coefficient: unit m2/s or
kg/ms.
What does the symbol The permeability, with unit kg/msPa. This value is only a
P stand for? constant in the case of Henry sorption, and as long as the
 diffusivity is a constant. In all other cases, it’s not a constant.
What is the P/L, which is dependent on the thickness of the film.
permeance?
When are the Henry Not when you see values of the permeability reported that are
adsorption and its dependent on the gradient of water vapour pressure that is applied
requirements valid? over the film.
When do we use When Ka << 1, so small values of a1, this equation becomes
Langmuir sorption? equivalent to the Henry equation. But at higher values of a1, the
relation is different and the activity can be related to its partial
vapour pressure.
- In this case, the permeability P decreases with its
increasing water activity a1.
What is the relation Permeability P can increase with increasing water activity.
between permeability
and water activity for
GAB adsorption?
We have a film with
on one side a water
activity of 0.8 and on
the other side aw = 0.
What is different in
the 3 isotherms? They
all show the same
amount of water
sorption; seem to
behave similarly.

How can you check Check under which circumstances the measurement was done. If
which sorption you apply the film under the same conditions (water activities),
isotherm to use if you you can use the literature data. If it shows that the permeability is
have insufficient data independent of the water activity gradient applied: use literature
to do the full data, indication for Henry sorption, diffusivity is approximately
calculation and would constant.
like to use data from If you only have a rough estimate, you can use the overall
literature? permeability, but you should check how reliable your result is.
What is the Not always thinner film -> higher mass flux through film in a
relationship between linear way.
total flux through the Usually the total flux does not linearly decrease with thickness of
membrane and the film. May vary with a factor dz^n.
thickness of film?
What is the relation
between diffusion
coefficient of water
and a membrane of
hydrophilic materials?

And for non- This diffusivity is usually less dependent on the amount of water
polymeric media? present. However, if a material is glassy, the diffusivity will be
(such as lipids) extremely low and too low to be measured.
What are the 3 models
for in-homogeneous
layers? Heterogeneous
films.

- Series model: the 2 phases are situated as layers normal

to the direction of diffusion. The overall permeability
depends on the volume fraction of the phases and the
permeability P of the individual phases.

- Parallel model: the 2 phases are placed in layers parallel

to the direction of permeant diffusion.

- Maxwell model: assumes that a dispersed phase is

present as a random packing of uniform spheres.

What are some - Applying thick coatings:

solutions to avoid o Typically applied 4-10 times. can be expensive.
defects in coatings? - Using emulsions:
o Mechanical properties from the matrix. The
Permeation properties are improved through the
dispersed phase. Reduced light transmittance.
 - Applying multiple layers of the same material
- Application of a combination of a low and high permeable
film
- Curing:
o Using capillary pressure to result in closure of
pores. Most effective with very small pores. There
may be possible side effects on the film and
product due to heat.
Properties of Proteins and carbohydrates:
biopolymers? - Hydrophilic in nature: poor moisture barrier, but good for
oxygen, CO2, or lipids.
- Glassy in pure form: elastic when plasticized.
What are properties of e.g., butter, chocolate, beeswax, carnauba wax, paraffins.
lipids? - Poor mechanical properties: crystallinity, not polymeric.
- Hydrophobic in nature: good moisture barrier. Also for
CO2. Less for oxygen, flavours, and colourants.
- Crystalline when solid: plate-like crystals, very low
moisture permeability. But brittle, low strength, and
difficult to improve without adding an extra phase.
Properties of - Continuous biopolymeric phase, filled with droplets of
emulsions and lipids
composites? - Used for restoration/ avoidance of inhomogeneous films /
defects. Surface spreading
What are some other - Plasticizers: 5-15% make a glassy biopolymer flexible and
additives that can be strong (rubbery). Increases the moisture permeability.
used as coating? Water, glycerol, polyethylene glycols. It may migrate from
the film.
- Antioxidants, antimicrobials, etc.
What are surfactants? - Small and stable droplet size
- Provide stability against sedimentation or creaming
through adhesion to the substrate.
- They can wet the surface and coat it. It shouldn’t wet too
little, and not too much.
How are edible films - Mechanical spreading:
applied? o Using a curtain or a brush. For highly viscous
solutions. With brush you get a thin layer, which
may need several passes.
o For enrobing, we pass it through a falling film,
which gives a thick layer. We might need more
passes for full enrobing.
- Dip coating:
o Dipped once or several times with subsequent
drying/curing. Like magnum ice cream.
- Spray coating:
o Solvent evaporation: apply a solution of
biopolymers through spraying and subsequent
evaporation to remove water and get a thin
 coating. May require additives for pH adjustment,
surfactants, or crosslinking.
o Drum coating: solution is sprayed on
granules/tablets while rotating. Heat is applied for
evaporation. The solvent evaporates, and the
dissolved components coat the particles.
-

Chapter 5
What are Dispersions of immiscible fluids in the form of droplets of one fluid
emulsions? dispersed in the other. They tend to rapidly destabilize. But can be
made metastable for some time with emulsifiers.
What processes are - Application of intense flow fields: machines rotor-stator
used to make systems (stirred tanks, etc), high pressure homogenizers and
emulsions? ultrasonicators.
- Membrane or micro-channel emulsification: each droplets is
individually shaped at the mouth of a membrane pore or
channel. Can yield monodisperse emulsions with low
energy.
What are foams? Like emulsions, but the dispersed phase is a gas instead of a liquid.
What are double Emulsions of emulsions. W/O/W.
emulsions?
What is interfacial Aka interfacial energy. Caused by the difference in cohesion
tension? between molecules of the two phases. Molecules are more attracted
to other alike molecules. At the interface, a molecule will have a net
attraction back into the bulk. Creating an interface costs energy =
interfacial tension = the amount of Gibbs energy needed to create 1
m2 of interfacial area (N/m or J/m2). The system will always try to
minimize the interface: go to larger bubbles. There’s a driving force
for destruction of an emulsion. Gibbs energy is always positive, and
a system strives to reduce this energy.
What is the Laplace The pressure proportional to the curvature of an interface of a
pressure? spherical droplet. The pressure inside a droplet is always higher
than in the continuous phase. The smaller the domain, the higher the
pressure difference.
What is Results from the density difference between the continuous and
gravitational dispersed phases. Described by Stokes law.
separation? - V = positive: the droplets move upwards, which is called
creaming.
- V = negative: the droplets more downward: sedimentation.
Gravitational separation can be slowed down by decreasing the
droplet size and/or by increasing the viscosity of the continuous
phase (thickeners).
What is Aggregation of two or more emulsion droplets to form a floc. The
flocculation? dispersed phase material of the droplets involved in the floc doesn’t
merge. Occurs if the attractive forces between dispersed phase
droplets overcomes repulsive force: interaction potential V(s):
 -
- Vvdw, Ve, and Vsr are van der waals, electrostatic, and
short-range interaction potentials.
- VDW is always attractive. Is counterbalanced by repulsive
long-range and repulsive short-range interactions.
- Electrostatic interactions are strongly dependent on
conditions.
May be reversible.
What is bridging In biopolymer-stabilized emulsions with a limiting biopolymer
flocculation? concentration.
What is depletion Occurs in the presence of high concentrations of excess emulsifier.
flocculation?
What are the results - Leads to an increase in the effective dispersed phase
of flocculation? particle size: may enhance rate of gravitation separation.
- Effective dispersed phase fraction increases because the
flocs entrap a fraction of the continuous phase. Viscosity
increases. Can even form a gel.
What is The interfacial film ruptures and the dispersed phase material of the
coalescence? droplets merge. This is irreversible.
- Droplet coalescence leads to decrease in total interfacial
area. Increase polydispersity of emulsions and accelerate
rate of droplet coarsening. If extensive coalescence occurs,
a separate oil layer can form and grow on the emulsion
sample.
Why can partial Can be desired to achieve certain properties. Like ice cream:
coalescence be required for fat droplets to form an interconnected network that
good? entraps air bubbles.
What is Ostwald In an emulsion with a degree of polydispersity, a diffusive transfer
ripening? of the dispersed phase from smaller to larger droplets may occur.
Driven by Laplace pressure between droplets of different size.
What are the 2 main Amphiphilic molecules adsorb at the oil-water interface. Has 2
roles of emulsifiers? consequences:
1. Interfacial tension is decreased, which facilitates droplet
break-up during emulsification and decreases the free
energy of the system.
2. After emulsion formation, the interfacial film can be
responsible for repulsive droplet-droplet interactions which
contributes to the physical stability. Repulsion is because of
electrostatic interactions (charger emulsifiers) and steric
interactions (overlapping of interfacial molecules).
What are low Aka surfactants: they have a side with more affinity for one liquid
molecular weight and one with more affinity for the other liquid. It sits at the interface
emulsifiers and how of the 2 phases. Usually a non-ionic yet polar chain. They decrease
do they work? the interfacial tension between liquids and reduce the free energy of
the system. Also they form a barrier which prevents 2 droplets from
coming close, by:
- Steric hindrance: because it sits at the interface, the droplet
 has a coat of hydrophilic chains sticking out of the interface.
When 2 droplets approach each other, the 2 coats first
make contact, which repel each other.
- Electrostatic repulsion: when surfactant is an anionic or
cationic surfactant, the oil droplets are coated by chains
with charged groups. The droplet has a net negative or
positive charge. Droplets can’t get close enough to coalesce.
Usually reversible.
What happens when When it reaches the critical micelle concentration (CMC), it won’t
there’s too much dissolve molecularly in the liquid anymore, but cluster together and
surfactant? form micelles, with hydrophilic parts towards the surrounding
water.
What is the Bancroft The phase in which the surfactant is dissolved usually becomes the
rule? continuous phase.
Gibbs-Marangoni effect: when 2 droplets approach each other, the
continuous phase gets expelled from the slit formed between the
droplets. This slit drags surfactant molecules along the interface
leading to a concentration gradient of surfactant molecules at the
interface.
When surfactants are soluble in the continuous phase, the
concentration gradient is quickly compensated by a flow of liquid
coming in the slot and then the droplets separate.
If this were opposite and surfactant was dissolved in the dispersed
phase, this concentration gradient wouldn’t be counteracted and
coalescence would take place more easily.
Therefore, we have to select an emulsifier based on its solubility in
the continuous phase.
What is the HLB: tells us about the ratio of hydrophilic to lipophilic groups in
hydrophilic- the surfactant molecules. The higher the HLB, the higher the
lipophilic balance? affinity for aqueous media. Lower HLB: more affinity for oil
phases.
What are Biopolymers that contain both hydrophobic and hydrophilic groups.
amphiphilic Have affinity for oil-water interfaces. Mostly proteins.
biopolymers?
How are proteins When adsorbed, the conformation may change so the other
adsorbed at hydrophobic parts of the molecules become exposed to the oil-water
interfaces? interface and it adsorbs to the interface even stronger. Adsorption is
usually irreversible. It forms a solid “skin” on the surface.
- Proteins are large and diffuse slowly through the aqueous
phase towards the interface.
- When at the interface, re-folding takes time.
- Stabilization takes some time.
How are When they contain non-polar groups such as methylated groups, or
polysaccharides exogenous moieties such as lipids or proteins bound to the
emulsifiers? polysaccharide. Mostly used: gum Arabic, modified starch, pectins,
galactomannans.
What are pickering Emulsions stabilized with particles that form a very strong
emulsions? membrane around emulsion droplets. The particles partially stick
out, which gives steric hindrance.
What happens when Different emulsifiers may compete for adsorption at the oil-water.
there’s more The composition of the interface depends on the relative surface
surface-active activities of the molecules, their adsorption rate, and availability.
components - Competitive adsorption occurs between dairy proteins and
present? surfactants. Above a certain surfactant-to-protein ratio,
water-soluble surfactants fully dominate the interface and
prevent protein adsorption.
How is the droplet In a cumulative distribution curve: counting the number of particles
size of emulsions that are smaller than a specific size, for many different sizes. Then
displayed? plotted as a curve.

Count all particles that have a size within an interval of sizes, and
do this for all intervals. Results in a frequency distribution.

The derivative of the cumulative curve to the particle size will give
a curve similar to the discrete frequency distribution.
How can we count - Counting the number of particles smaller than a specific
the particles to get size. But a very small droplet counts for 1, just as a very
this distribution? large droplet, even though the amount of oil present in the
This is not really larger droplet is much larger. So this method really stresses
used, so not really the smaller droplets.
important - Use the total interfacial area present on the particles,
instead of number of particles. Here smaller droplets are
counted less extremely. The distribution is more realistic.
- Use the volume of the particles smaller than a specific size.
This gives the total amount of oil present in the droplets.
What is the modal Looking at the frequency distribution of the average droplet size
size? and taking the size at which the distribution is maximal.
What is the Sauter D32. Found by summing up the volume of the particles, and
diameter? dividing it by the surface area of the particles.
What is the span of The width of the distribution. The average droplet size can be the
the distribution and same, but a monodisperse emulsion (droplets with the same
why is it important? diameter) may be much more stable than a polydisperse emulsion.
What are some - Microscopy: larger than 1 um
methods for - Light scattering: different refractive index.
determining the - Follow the dynamics of droplets. Dynamic light scattering:
droplet size the Doppler shift relative to the frequency of the incident
distribution? light, in the scattered light is measured. Doppler shift comes
from Brownian motion of droplets.
- Count droplets individually: Coulter counter method: first
dilute emulsion. Then push it through a small hole, measure
electrical conductivity. Every time a droplet moves through
the hole, it obscures part of the hole. which reduces the
conductivity through the hole. Larger droplet: stronger
effect.
What is the specific Surface of interface between 2 liquids: interfacial area per mass unit
surface area? of dispersed phase.
What is the surface The mass of emulsifier per unit of oil-water interface.
load?
What is the zeta- The effective surface potential of a droplet suspended in a medium,
potential? which takes into account that charged species in the surrounding
medium may adsorb to the surface of the droplet and alter its
charge. Can be assessed by measuring the movement of droplets
placed in a static field, e.g., with dynamic light scattering.
It's sensitive to compositional parameters of the emulsion, such as
ionic strength or pH.
What are rotor- They have an element that rotates quickly very close to a corrugated
stator machines? element that stands still (the stator). The flow between these 2 can
be very intense when they’re very close together (can be less than a
mm). Most used: stirred tank, colloid mill, toothed mill.
How does a stirred Flow field is not very intense as the stirrer is not very close to the
tank work? wall. Droplets remain relatively large (> 10 um). Droplet size
distribution is usually relatively wide. Becomes smaller with longer
treatment times.
How does a colloid Used a lot. It’s a conical rotator that turns in a stator of the same
mill work? shape, leaving a very narrow gap between rotor and stator. Liquid
comes from the top and flows through the narrow gap. Due to high
rotation and small gap, shear forces are very intense and small
droplet sizes are realized. Depends on the viscosity of the mixture at
what regime the mill operates. When highly viscous, the flow will
be laminar. When turbulent, the Reynolds number is used to
characterize flow.
- Re < 370: laminar.
- Re > 370: turbulent.
How does a toothed Hollow rotor with openings through the rotor wall rotates in a stator
mill work? also having openings. Gap is very small: large shear forces. Mixture
is pumped into the centre of the rotor, flows through openings, and
subjected to intense mixing and shearing. Flows out through the
openings in stator. Flow pattern is turbulent.
What is a high- Mixture is pumped through a very small hole or gap. Extensional
pressure flow, turbulence and other phenomena give break-up of large
homogenizer? droplets into smaller ones. Break-up is caused by turbulence and by
cavitation: causes a strong and very local turbulence that breaks
droplets up further.
- Small, lab-scale homogenizer operate in laminar flow
regime. Industrial-scale systems operate in turbulent
regime.
Can use valve systems or nozzle systems.
What are valve Mostly used in dairy industry. Narrow gap is created with a valve
systems? which is pressed shut with a disk and a strong spring. Pressing
liquid through the valve lifts the disk somewhat and the force of the
spring ensures that the gap width remains small.
What are nozzle No valve, just a small opening through which the liquid is squeezed.
systems?
What is cavitation? When the velocity of the liquid inside the nozzle is much higher
than that outside it, the pressure inside must be lower than the
external pressure. When the velocity is high enough, the pressure
 can become lower than the vapour pressure of water, and bubbles of
water vapour will be formed, which collapse violently when the
liquid comes out of the small nozzle. This creates a lot of local
turbulence. It should be limited because it may form radicals, which
may compromise product quality.
What are ultrasound Inducing turbulence and cavitation with sound: propagating
systems? pressure fluctuations. These pressure fluctuations can become so
large that the pressure becomes lower than the vapour pressure of
water, which induces formation of small bubbles which implode
almost immediately -> intense local turbulence.
- Generated with an actuator which vibrates with the
specified frequency.
It’s not suited for large scale production, because the treatment
chamber has to be relatively small.
Not suitable for systems with unsaturated fatty acids, or other
chemically labile molecules, because cavitation is a danger.
What is the Weber The ratio of the externally applied stress and the internal, coherent
number? tension. When the droplet is subjected for a short time to disruptive
stress, the viscosity of the internal phase will cause the droplet to
react slowly to the external stress, and we also take into account the
coherent viscous forces.
- If Weber is sufficiently high, a droplet will break up into 2 or
more smaller droplets.
What is simple The flow of a liquid of viscosity nc over itself along a plane.
shear flow? Through a tube or flow over a planar surface.
What is extensional Takes place when the liquid is squeezed into a small opening. When
flow? enters a channel or is pushed through a small hole. In most practical
cases, the flow pattern is a mixture of simple shear flow and
extensional flow. In extensional flow, it will also experience a drag
force exerted by the flow. The value of We cr is different.
Extensional flow is more effective than simple shear flow in
disrupting a droplet. Therefore Wecr is much smaller.
Explain comparison
between shear and
extensional flow.

What is turbulent The liquid starts to flow in a chaotic way, forming large and small
flow? swirls and eddies. Transition from laminar to turbulent is
characterized by the Reynolds number.
The swirls and eddies impinge on the emulsion droplet, deform
them, and when deformation is sufficiently strong and long enough,
the droplet breaks up.
What is the measure The power density: the amount of energy used per unit of volume of
for the intensity of liquid, per unit of time. The larger the power input, the more intense
the eddies? and the smaller the eddies are.
- Turbulence is not too large: main force on the droplets is
 caused by the shear imposed by the surrounding eddies.
Size of eddies is the same order of magnitude as the size of
the droplets, and viscous forces dominate.
- Higher turbulence: eddies become very small, and the
viscous forces exerted are not the dominant force anymore:
inertia of the liquid impinging on the droplets becomes the
disruptive force: intertial forces.
How does break-up
by turbulent flow
look like? With the
eddies impinging on
the droplet.

When does, in the

turbulent regime,
the transition from When the droplets are larger than:
viscous-dominated
break-up to intertia-
dominated break-up
take place?
How is mayonnaise It’s an O/W emulsion with very high dispersed phase fraction. Made
made? using either continuous or batch processes.
- Batch: usually a premixing tank. Aqueous ingredients are
mixed together for adequate dissolution. Then oil is fed to
the tank under continuous agitation which creates a pre-
emulsion. This is then discharged to a colloid mill, where
the droplet size and polydispersity is reduced. Droplet size:
1 to a few um.
How are infant Contain a blend of vegetable oils or mixtures of vegetable oils with
formulas made? bovine milk fat, lactose, vitamins, minerals, and other ingredients.
Emulsifiers are used to prevent separation of the oil phase from
water.
- Hydrating/mixing powdered ingredients in the aqueous
phase.
- Homogenization with oil phase using high pressure
homogenization. The oil volume fraction is about 5-10%.
- Emulsion is spray-dried and packaged, leads to small oil
droplet sizes.
How are non-dairy Such as fruit or cola drinks (non-carbonated O/W emulsions):
beverage emulsions - Usually prepared in concentrated form (oil volume fraction
made? is larger than in the final application).
- Oil-phase may be non-flavoured oils or flavour oils, or
mixtures.
- Flavour oils are more polar, so more prone to Ostwald
ripening and have a lower density: can be unstable to
creaming.
- Weighting agents can be added to the oil prior to
 homogenization: increases its density.
How made:
1. Initially: water-soluble components and oil soluble
components are separately mixed with water and oil
respectively. Both phases are homogenized (first with high-
speed mixer to form a coarse emulsion). Then passed
through a high pressure homogenizer to achieve a small
droplet size.
2. Finished product made by diluting emulsion with an
aqueous phase containing acidulents, colours, etc.
3. Final oil content: less than 0.1%.
4. After dilution: another homogenization step to ensure all
hydrophobic components added are incorporated into the
oil.

What processes - Cross-flow membrane emulsification

make emulsions - Dead-end (premix) membrane emulsification
using membranes - Micro-channel emulsification.
and microchannels?
What is cross-flow Each droplet is formed individually on the mouth of a pore. The
membrane emulsions produced can be very highly monodisperse, but the
emulsification? permeation rate of oil through the membrane is often relatively low.
Only suitable for small-volume, high-value products with a low
volume fraction of dispersed phase.
What is an essential The membrane is preferentially wetted by the continuous phase: to
for this process? make an O/W emulsion, the membrane should have hydrophilic
surface properties. To make W/O emulsion, the membrane should
have hydrophobic properties.
How do the droplets Oil emerges out of a pore and forms a small droplet on top of the
form? pore mouth. It’s retained in this position by the interfacial tension.
The cross-flowing continuous phase then exerts a drag force on the
droplet. In this size range, other forces such as gravity and intertial
lift forces are negligible.
What is the capillary It represents the ratio between forces by the drag force and forces
number? by interfacial tension. Similar to Weber number.
What happens when SPG: a porous membrane made of volcanic ashes. Instead of the
we use SPG droplet size being dependent on the cross-flow velocity of the
membranes? continuous phase: the droplet size is independent of the cross-flow
velocity. Small droplets can emerge even when there is no cross-
flow at all.
Why does this Once the oil emerges from a pore in the membrane, there’s a change
happen? DIT SNAP in Laplace pressure. When oil is forced into the membrane, it has to
IK NOG NIET overcome the Laplace pressure difference.
There’s a moment that the droplet has a Laplace pressure difference
with the continuous phase that is smaller than that of the pore. Then
there’s a pressure gradient from the oil in the pore, towards the
droplet, and oil can flow spontaneously from the pore into the
droplet. This happens when the the pore structure is strongly
interconnected.
 At a certain moment, the cylinder of oil in the pore snaps off and the
droplet is released. This snap-off is spontaneous, driven by the
interfacial tension and not by the cross-flow.
Therefore, cross-flow doesn’t have much influence on the process
and droplet size.
This only happens when the cylinder of oil in the pore doesn’t
remain intact.

When do we see the When there’s low flow rates. Because at higher flow rates, when the
spontaneous snap- continuous phase should replace the oil in the pore, it doesn’t have
off? enough time. The droplets will still be formed, but they will be
larger and will be detached by the cross-flow of the continuous
phase over the membrane.
When does As soon as the droplet radius (Rd) is twice as large as the pore
spontaneous snap- radius (Rp), there’s a possibility for spontaneous snap-off. But it
off take place? depends on the shaep of the pore structure and flow rate of the oil.
What is dead-end Starting with a coarse pre-emulsion with large droplets. Then
(premix) pushing this through a porous membrane. On the other side you get
membrane a fine emulsion with narrow droplet size distribution. The
emulsification? throughput is higher than other systems. It depends on the pre-
emulsion how narrow the droplet size distribution is. Repeating this
procedure a few times helps, continuing until only small droplets
remain. There may be several mechanisms happening:
- Snap-off due to localized shear.
- Break-up due to interfacial tensions effects.
- Break-up due to steric hindrance.
What properties It should have a relatively narrow pore size distribution and should
should the be wetted by the phase in the continuous phase. The typical droplet
membrane have? size is a bit larger than the average pore size of the membrane.
What is a Its sensitivity to internal fouling, especially when proteins are used
disadvantage of this as emulsion stabilizers. All components need to flow through the
process? membrane. Some particles, like proteins, have a tendency to adsorb
on interfaces inside the pores. Fouling inside a membrane is almost
impossible to remove. So membrane has to be replaced.
What happens when It would result in a W/O emulsion. It is inverted. The opposite is
you prepare an O/W true as well.
emulsion and press
it through a
hydrophobic
membrane?
What are Either shear-based devices or devices based on spontaneous droplet
microfluidic formation can be used to generate droplets. Some advantages: high
techniques? energy efficiency, high droplet monodispersity, and potential use
for the production of high added-value and fragile products. How
does it work: 2 stages: one formation phase and a snap-off phase
during which the droplet can still grow before actually being
detached.
They are limited used at industrial level due to low throughputs and
challenges for upscaling.
How can phase During phase inversion, the continuous phase becomes the
inversion be used dispersed phase and vice versa. It’s difficult to prepare an emulsion
for preparation of in which the viscosity of one of the 2 phases is much higher than the
products? other. In these situations, phase inversion can help. Firstly, droplets
are made of the low-viscous phase in the higher-viscous, and then
the emulsion is inverted.
- By catastrophic (sudden) inversion: by adding more and
more of the dispersed phase.
- Transitional inversion: the properties of the emulsion are
changed from favouring droplets of the low-viscous phase
to droplets of the high-viscous phase.
How does You start with the phase that should become the dispersed phase
catastrophic phase (phase A). you slowly add phase B to phase A, while agitating.
inversion take Initially, droplets of phase B are formed which are broken up into
place? smaller droplets by agitation. More droplets are formed. It becomes
so concentrated and the viscosity becomes so high, that droplets of
B are sheared apart and start to coalesce. Once this starts, all
droplets start to coalesce. B combines to form a continuous phase,
taking up droplets of phase A.
It can take a long time before inversion takes place, because you can
go to high volume fractions of phase B. the system shows strong
hysteresis.
What happens when It can take a long time before inversion takes place, because you can
you add phase B go to high volume fractions of phase B. the system shows strong
slower or use less hysteresis.
agitation? If you add phase B quicker or agitate the system less, the droplets of
B will even have inclusions of phase A. this is much less stable
against inversion, which will take place at lower volume fractions of
phase B. then it shows less hysteresis.
When do we use With products that naturally occur as O/W emulsions, but are to be
catastrophic phase used as W/O emulsions (margarine). Also when the dispersed phase
inversion? has a high viscosity. However, the final droplet size is not very
 small and the emulsion can be rather polydisperse.
What is transitional Firstly, prepare an emulsion of the phase that should become the
phase inversion? continuous phase (phase B) in a continuous phase (A). now the
surfactant is chosen so that it favours the formation of a B-in-A
emulsion. Once emulsion is prepared, the conditions are changed so
the surfactant will favour the A-in-B emulsion. This is done by
changing the temperature, or pH, or else: changing the affinity of
the surfactants to the two phases.
This happens when the affinity of the surfactant system towards
both phases is approximately equal. So you can easily change the
system. There’s no clear B-in-A or A-in-B emulsion, but intimately
mixed. Aka micro-emulsion.
These emulsions can have droplet sizes far below 1 um, even from
systems in which phases have very different viscosity.
This is not used in the food industry, because it’s difficult to find a
good surfactant for the properties of oils commonly used. Mostly
used in cosmetic and coating industries.

What is partial Happens when 2 or more partly crystalline oil droplets come into
coalescence? contact such that the interfacial film surrounding each droplet
breaks and the droplets partially merge. Because of the fraction of
solid fat in the droplets, it doesn’t result in relaxation of the merged
droplets into a larger, spherical droplet, but the formation of
irregularly shaped aggregates.
Important in dairy products, because of broad melting range of milk
fat.
What is partial It starts with dairy cream (O/W emulsion), which is cooled to a
coalescence in temp where the droplets are partly crystalline, then mechanically
butter formation? agitated. When the partly crystalline fat droplets collide with each
other, they undergo partial coalescence, which leads to the
formation of clumps of aggregated fat droplets. Upon agitation, the
clumps grow in size until phase inversion occurs. Fat phase
becomes continuous phase. Butter finally is a W/O emulsion.
What methods does Mostly intense flow fields. Membranes and micro-channels have a
food industry mostly large potential for making more complex products (monodisperse or
use? double emulsions). The third class (phase inversion) is used in the
production of foods, but also other industries where emulsions need
to be made in which the dispersed phase has a high viscosity
compared to the continuous phase.
Chapter 6
What distinctions of - Homopolymers: chain consists of one type of
synthetic polymers are monomers. E.g., starch.
made? - Copolymer: chain consists of two types of
monomers, which can be alternating, blockwise, or
randomly oriented. E.g., galactomannan, gums.
- Terpolymer: chain consists of three types of
monomers.
How are polymers - Thermoplastic polymers: contain linear chains and
distinguished as a function melt upon heating.
of their structure-related - Thermoset polymers: chains are heavily cross-linked
behaviour? and can’t melt.
- Elastomers: chains are slightly cross-linked and
show elastic properties.
How is the length of the The molar mass (Mi) is related to the degree of
chain and the length polymerization (i) and the molar mass of the monomer
distribution established? (M0).
Then you can calculate the average molecular weight by
dividing the total polymer chain length by the number of
the polymer chains:

What is the polydispersity PDI. A measure of the molar mass distribution:

index? What does it mean? Mw/Mn. (average molar weight/ average molar mass).
- PDI = 1: monodisperse polymer sample (all polymer
chains have the same length).
- PDI>1: polydispersity. The polymer properties, such
as melting and glass transition, become less well-
defined and more difficult to measure. Aka no sharp
thermodynamic transitions.
What does the water activity It describes how tightly water is bound to the biopolymer.
with high molecular weight This is done with the Flory Huggins theory.
polymers describe? And
what calculation can we P1 is the volume fraction.
use?
What does the interaction X is the polymer-solvent interaction parameter. If the
potential describe? interaction between biopolymer and water is the same then
X = 0.
If X is negative: dissolved biopolymer has high affinity for
moisture. X is positive: biopolymer does not really like
water.
Water in starch: X = 0.8.
Many proteins in water: X = 0.7-0.85.

X1: interaction parameter of the dry system.

X0: interaction parameter of a highly diluted system
containing biopolymers.
What forces are involved in It’s a result of solvent-network interaction and the
swelling and water binding? counteracting of swelling by strained crosslinks.
What equation? The biopolymer forms a network, which leads to
crosslinking. The crosslinks between the polymer chains
prevent the biopolymer molecules from simply dissolving
in excess water, and also affects (limits) the ability to swell.
Crosslinking: Flory-Huggins equation extended. Flory-
Rehner equation.
The total water activity: originates from the interaction
between the biopolymer and the water, and the elastic
contribution of the biopolymer network.

What does the p1 value in It’s the polymer volume fraction. X is the polymer-solvent
this equation stand for? And interaction parameter. E is the elastic modulus. Vw is the
the other values? molar volume of water, and p0 is the volume fraction of the
gel in the relaxed state.
What do the things in this Ps is the density of the polymers. Mc is the molar weight of
equation stand for? the polymeric units between the crosslinks (inverse of
crosslink density).

How can swelling capacity Changing either X1 and/or Mc.

be influenced (with these - Low aw: swelling is predominantly governed by
equations)? What interaction between the networked biopolymer and
determines swelling capacity the solvent (water)
at low and high aw. - High aw: swelling is mostly governed by the
crosslink density.
What is a prerequisite for
complete mixing with Gibbs
free energy? dG should be negative.
When is the interaction Positive: endothermic mixing.
parameter positive or Negative: exothermic mixing.
negative?
A negative enthalpy value means a negative free energy, so
molecules will be miscible.
Explain in which regions
phase separation occurs and
the phases.

Curve A: full miscibility. Negative value for interaction

parameter (exothermic mixing).
Curve B: 3 regions. Positive interaction parameter.
- 0 to ‘b and “b to 1: very low solute volume
fractions: mixing occurs because the entropic term is
dominant at low volume fractions.
- Between ‘s and “s: spontaneous phase separation
occurs in the spinodal region. There’s no energy
barrier that prevents phase separation. It always
occurs.
- Between ‘b – ‘s, and “b – “s: phase separation
doesn’t occur spontaneously because of an energy
barrier. Metastable system.
Know how to read phase
diagrams for protein-
polysaccharide systems with
binodals and tielines and
know what it means.

What are isotropic The properties of a material do not vary with directions
materials? (e.g., cheese, milk).
Anisotropic: fibrous product like meat.
What is an ideal liquid? And Ideal liquid: Newtonian fluid. Flows when force is applied.
an ideal solid? Ideal solid: behaves as a Hookean spring: doesn’t flow but
deforms elastically.
What is a visco-elastic liquid Doesn’t flow but deforms elastically. Aka soft solid:
or soft solid? Has a response to a force applied that is partly viscous and
partly elastic.
Exact properties depend on the microstructure of the
product

What is the equation for Linear relationship between stress and shear rate. The slope
Newtonian liquids? What
are the units? equals the viscosity.
Unit of stress: Pascal = N/m^2. Shear rate: s^-1. Viscosity:
Pa s.
What does the term That the viscosity changes for different shear rates. And
‘apparent viscosity’ imply? sometimes, a material needs a certain critical stress or yield
 stress before it will move.
For non-newtonian K is the consistency factor. N (small n) is the flow
behaviour, what does the behaviour index.
parameter n and K tell us? N<1: shear thinning
N>1: shear thickening
What factor does the - Volume fraction (φ): fraction of the volume
rheology of a multiphase occupied by the dispersed phase.
product depend on? What Forces:
forces are relevant? - Interactions between the particles
- Forces related to Brownian motion for particles
smaller than 1 um
- Viscous forces originating from local velocity
differences between the dispersed phase and the
surrounding fluid
What equations do we use Einstein’s equation for small particles compared to the
when for particle-filled sample size:
liquids? Higher particle concentrations:

When viscosity becomes infinite (i.e., material becomes

glass, particles touch each other): for rigid particles that
don’t deform when the product deforms: maximum packing
condition: φmax:

When the inner phase is still mobile, like emulsions, and

flows and creates circulations:

(ηdr: ns: viscosity of continuous phase. Nd:

viscosity of dispersed phase (droplets).
In case of rigid droplets, the viscosity ratio is very large and
the equation simplifies to Einstein’s equation.
What do we do when the It’s preferred to measure the complex modulus G* instead
continuous phase is non- of viscosity.
Newtonian?
What are E, G, and G’? E: Young’s modulus
G: shear modulus
G’: storage modulus
What are the values in the M can be either E, G, or G’. n can be:
equation? - N=1: isostrain
o For a blend in which the moduli of both
phases are similar or the dispersed phase is
weaker.
- N=-1: isostress, where one component is dispersed
in the other.
o For a blend with a dispersed phase with a
 high viscosity
- N=0.2: bi-continuous
o Both phases form a continuous phase and
therefore contribute more equally to the
final product properties
What changes does Most important: starch gelatinization, protein denaturation,
extrusion lead to for and structuring of ingredients, including emulsification and
biopolymers? blending.
What is the effect of shear Thermal treatment leads to gelatinization, which can lead to
and thermal treatment in starch degradation and dextrinization. Application of shear
starch? enhances the rate of this. Leads to increased solubility.
What is the effect of high Can lead to denaturation and formation of internal
temperature extrusion in crosslinks. Through disulphide bonds, this leads to a
proteins? reduced solubility and increased firmness of the material.
electrostatic interactions cause setting of the texturized
product inside the extruder, finalized by formation of
disulphide bonds, hydrogen bonds, and hydrophobic
interactions during cooling at the end of the process.
Wheat flour: unfolding and exposing of hydrophobic and
reactive sites, followed by aggregating and crosslinking ->
reduced solubility.
Very high temperature (>180 C): might lead to disruption
of protein molecules and slight increase in solubility.