Rochester Institute of Technology

RIT Scholar Works

Theses

Thesis/Dissertation Collections

2002

Evaluation of the change on water vapor

transmission rate of different polypropylene films in
contact with d-Limoneme and the effect such
changes have on the shelf life of confectionary
products.
Anna Romero

Follow this and additional works at: http://scholarworks.rit.edu/theses

Recommended Citation
Romero, Anna, "Evaluation of the change on water vapor transmission rate of different polypropylene films in contact with dLimoneme and the effect such changes have on the shelf life of confectionary products." (2002). Thesis. Rochester Institute of
Technology. Accessed from

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EVALUATION OF THE CHANGE ON WATER VAPOR TRANSMISSION RATE

OF DIFFERENT POLYPROPYLENE FILMS IN CONTACT WITH

d-

LIMONEME AND THE EFFECT SUCH CHANGES HAVE ON THE SHELF LIFE
OF CONFECTIONARY PRODUCTS.

By
Anna M. Romero

A thesis

submitted

partial

to the Department

fulfillment

of

Packaging

of the requirements

Science

for the degree

MASTER OF SCIENCE

Rochester Institute

2002

of

and

Technology

of

Technology in

Department of Packaging Science

College of Applied Science and Technology
Rochester Institute of Technology
Rochester, New York

Certificate of Approval

M.S Degree Thesis

The M.S Degree thesis of Anna M. Romero has been examined and approved as
satisfactory for the thesis requirement for the Master of Science Degree

Fritz Yambrach

Deanna Jacobs

James Castellano

EVALUATION OF THE CHANGE ON WATER VAPOR TRANSMISSION RATE

OF DIFFERENT POLYPROPYLENE FILMS IN CONTACT WITH dLIMONEME AND THE EFFECT SUCH CHANGES HAVE ON THE SHELF LIFE
OF CONFECTIONARY PRODUCTS.

I, Anna M. Romero, prefer to be contacted each time a request for reproduction is made. I

can be reached at the following address:

Colinas de la Rosaleda
Villas del Morro: Primera Etapa. No 23
Barquisimeto, Venezuela
Phone Number: 58-251-2547484

Oct 2002

EVALUATION OF THE CHANGE ON WATER VAPOR TRANSMISSION RATE

OF DIFFERENT POLYPROPYLENE FILMS IN CONTACT WITH

d-

LIMONEME AND THE EFFECT SUCH CHANGES HAVE ON THE SHELF LIFE
OF CONFECTIONARY PRODUCTS.

By
Anna M. Romero

2002

ABSTRACT

This

(WVTR)

of

paper

three

discusses the

plastic

films

changes observed

while exposed

The

concentration of

d-limoneme

Gas

Chromatography

and

films

was

determined

Permatran-W 3/31. It

by

on

to different concentrations of d-limoneme.

the films was determined

means of a MOCON-Water

was observed

WVTR increased. These

d-limoneme
discusses

all

which are

the

means of

Headspace

that d-limoneme affected the films in two

results explain

currently

studies.

rate of all

Vapor Permeation Analysis System

the

after certain concentration was

shortened shelf-life of candies

packaged with

the

studied

experimental problems encountered on

improvements for future

by

Mass Spectrometry. The Water Vapor Transmission

lower concentrations, the WVTR decreased but,

the

in Water Vapor Transmission Rate

ways: at

reached,

containing

films. Finally, this

paper

this study as well as possible

TABLE OF CONTENTS
5

ABSTRACT

INTRODUCTION
6

The Shelf-life Concept

Shelf-life Model

Shelf-Life Studies

9
10

Accelerated Shelf-life Studies

The

between

Shelf-life

Relationship
Permeability
Permeability Theory
Permeability Measurements: Determining the WVTR of Films
Methods Available for Determining WVTR
Why Are Some Polymers Better Barriers Than Others?
and

The

Types ofBarrier Films

Selecting an Appropriate Barrier Material for

11
11
15
15
17
18

Packaging

Application

STATEMENT OF THE PROBLEM

19
24

HYPOTHESIS

24

TEST DESIGN AND METHODOLOGY

25

Experiment Design

25

Materials

29

Reagents

29

Polymeric Films

30

RESULTS AND DISCUSSION

A Comparison Between the Results
and

obtained with

the Theoretical Shelf-Life Model

The Observed Shelf-life

Effect

of Absorption of

33

d-Limoneme

on

the

Packaging

Films

32

Revising the Experiment

33

Results of the Experiment

I00LTSC

34

90SPW

35

34

100 LMB

Including

the lost

36
of

barrier

properties on

the Shelf-life Model

36

CONCLUSION

39

BIBLIOGRAPHY

43

INTRODUCTION

Before the packaging

materials such as

packaging

industry

or paper.

glass, metal,

materials and

started

the foods

the

industry

with

and

to

exit or enter

the

package.

encountered a more

their environment

diffuse in

a polymer

certain

film; thus, free

such

of plastic

food items because it

which

shelf-

life is

material

required

did

and metal

not allow

entrance or exit of

different

Such interaction between the

films usually

represents a problem when

In

shelf-life of the product.

plastic

film

used

to package

packaging

other

instances

meat should allow

to use for certain food application is understanding

product

be

compounds will

called permeation.

highly reduces the

from the

any

Polymer films interact

the meat stays red and looks fresh. The first task on

of oxygen so

packaging

materials

and complex material.

permeability is desired. For example, films

permeability

mostly inert

than glass or metal containers. Molecules can dissolve

the vapor phase is

The permeability

relied on

However, when polymeric films began to be used,

observed on packages made with those materials.

and compounds on

plastics, it

In those times, the interaction between the

In any instance those

dynamic

differently

use of

was well understood: glass was

could oxidize so coatings were utilized.

compounds

the widespread

the

deciding

what

kind

of

(Paine 1992).

The Shelf-life Concept

Shelf-life is defined
nutrition, quality,

Usually, it is

Many
food

methods

and

the

life, it is

and

flavor

hard task to
have been

as

which certain

properties when packaged

predict the point at which

used

mode of spoilage.

necessary to

the time in

to determine

In

their

fashion (Hirsh, 1991).

the food can be considered spoiled.

such a point

depending

food

how this food

will

to

products can retain

a certain

package a

order

understand

in

food

on

the nature of the

product and predict

loose its

characteristics, or quality, or even at what point a food can become a

its

shelf-

freshness, flavor

health hazard.

Food

is

spoilage

interactions occurring

oxidation

ingredients

fats,

degeneration is the
and

that

resulting from the

loss

for

It is

that

are

primarily 10

Lipid

Oxidation,

Water

2.

ways

gains or

that

value and

mode of

foods do

moist

not

the food to the outside

the foods

in

which

dehydrate

migration of

environment.

flavor

with aromas or

food

taste, texture

due to the

can also occur

food

molecules

In the

from the

in food degeneration.

In

food deteriorates (Cairns 1974):

flavors

and

which can cause changes

rancidity

in texture,

flavor,

nutritional

the growth of microorganisms.

3.

Non-enzymatic

4.

Vitamin degradation

Absorption

oxygen and some

Another

and enzymes.

critical

which causes off

loss,

most common modes of

between

outside environment can also cause off-flavors and result

general, there

the

due to many

occur

that can cause changes in appearance,

and aroma molecules present on

of

one of

reaction

Flavor degeneration

way, the contamination

that it may

sense

flavoring,

of moisture.

not gain water

and microbiological growth.

opposite

studies agree

oils used

gain or

dry foods do

the flavor

Most

at once.

food degeneration is
such as

issue in the

a complex

of

browning

flavoring

by

agents

the

package or exit of

flavors to the

outside environment

from the

6.

Absorption

7.

Microbiological

8.

Physical degradation:

9.

Pest infestation

10.

Temperature induced texture

Usually,

a package

products.

been

well studied and

by

degradation

Labuza

mechanisms

shelf-life of many

bruising,

is designed to
note

foods

water

crushing,

breaking,

help

minimize

the effect of

and rate of reaction can

have helped in creating

degree

such

of those mechanisms of

ingression/absorption, lipid

with a certain

etc.

changes

that many

their likelihood

on

package or the environment

decay

It is important to

food

studies

of off-odors

models

of accuracy.

be

factors

oxidation,

be

the

degradation have

predicted.

that can

on

used

Specifically,
and

vitamin

to predict the

In
products

fact,

in

many food

final decisions

order to make

for

a specific product.

life

studies

companies use such models to predict the shelf-life of their

It is

on whether to select certain

packaging

systems

also common practice to conduct regular or accelerated

to corroborate any theoretical data

obtained

from the

shelf-

use of such models.

Shelf-life Model
A
gain or

for predicting the

model

loss

of moisture was

Where:

m
me

mi

Equilibrium
Initial

Water

Thickness

vapor

permeability

of the

at

T]}

time T

W=

Food

mass

Water

vapor pressure of

slope of the moisture sorption

moisture sorption

the food as a function

of the package

film

of transmission

The

food

(Po/ b)

follows:

moisture content with no package

Area

and summarized as

{ (me-mi) / ln A-l [ (P/t) (A/W)

Po/ b

by Labuza

failure is due to

moisture content

me

derived

moisture content of the

shelf-life of a product whose mode of

isotherm

Pure

curve

isotherm

water at storage

between

(MSI)

curve

of the equilibrium relative

temperature, divided

by

the

m and mi

is

a graph of

humidity

the moisture content of

of the environment

surrounding

the food. As can be seen, many of the data needed to calculate shelf-life must be obtained

from

analytical chemical analysis of the

are obtained can

This

be

model

reviewed

has been

crackers, cookies, dried

lifetime

used with a

high degree

fruits, breakfast cereals,

cycle:

ways

in

which

those values

in the literature (Castellano 2001, Gnanasekharan

predictor as no one can estimate

during its

food to be tested. The

the exact

temperature,

etc.

1993)

of success on products such as

However, this

model

is simply

bread,
a good

environmental conditions each package will see

relative

humidity, location in

store,

handling by

consumer,

etc.

In addition, this

package, the product,

There have

degradation

widely

used

the outside environment.

been

also

such as

those models still

and

interactions between the

model cannot predict all possible

attempts to create accurate models

lipid oxidation,

need more work

vitamin

for

other mechanisms of

degradation, flavor permeation,

(Castellano 2001, Gnanasekharan

and so on

1993)

but

and are not

by the food and packaging industry.

Shelf-Life Studies

It is

food

product or

enough

time

common practice

foods

in

in

placed

information for coding

such products can

corroborate

the

food

conduct shelf-life studies

This is done in

a new package system.

expiration

be distributed

any theoretical

industry to

dates

kept in

and

values obtained

determining

and

by

stores.

means of

the

for any

order

new

to have

maximum amount of

This is generally done to

the shelf-life model, or

whenever

there is not an accurate model that can predict all the interactions occurring between the

food

Such

and the environment.

controlled environment

for large

intervals to determine any

usually done in

studies

amounts of

changes.

either one of

the

usually involve placing the

The

quantification of

following

obtain concentration of water or chemical of

microorganisms; and/or

the

product and record

Factors

any

analyzed

Weight: Loss

lost

during

2)

Organoleptic

time. Product is

1) By

ways:

interest,

studies

in

packaged goods

in

analyzed over regular

any quality

or

flavor lost is

means of chemical analysis

to

byproducts

or

presence of chemical

which a panel of people will analyze

comments on appreciable

food

characteristics

differences.

during testing include the following:

or gain of weight can

indicate the

amount of moisture gained or

storage

Seals: Visual inspection

and seal strength

to verify any lost over time

determination

should

be

conducted

Material Integrity: Visual inspection

defects that

occurred over

of opened

package, in

order

to find any

time such as ply separation, discoloration

or pin

holes
Product Inspection: Visual inspection
applicable

Such

be

order

studies are

obtained until

product, this

in

can

usually costly

the successful launch

few

the

product and

sensory testing

when

to record any change.

the product

take

of

reaches

and

time consuming, since the final

the end of its useful shelf-life.

The length

months or several years.

of new products on the

market,

so

results cannot

Depending

the

on

of such studies can affect

instead many

companies

rely

on

accelerated shelf-life studies.

Accelerated Shelf-life Studies

In

accelerated shelf-life

the temperature and/or

its lifetime.

Many

increase in the

studies

rate

temperature. Models
conditions

relative

in the lab

of

in

Labuza

vs.

of

rate

the

or

loss

of moisture.

moisture of

the

product will see

have been done to

to link the

distribution

normal

for

accurate enough

focuses

on

predict

At the

rate of

proportional

of time.

The

replace

the

most

during

the exact

loss,

product

product are measured.

and end of

Critical

10

been done

is

reaction,

and

shelf-life studies.

time.

humidity

placed

by

Usually, data

Humidity

or egress of moisture

packages are weighed over

beginning

all

oxidation

costly

to the change of

In this test,

the accelerated

the world.

of moisture over

ingress

of

This has

around

moisture gain or

to

times

equivalent

environment.

the changes

to increase the

increase is

determined length

extreme environments where

higher than the

and others

created

pressure of the outside environment.

in

the degradative reactions due to the controlled increase in

shelf-life

vapor pressure are used

The

placed

kinetic theories in many labs

flavors is

Accelerated

for

are much

accelerated shelf-life studies

permeability

package.

humidity

have been

means of well-known
obtained

by

is

product

studies,

in

and

from the

and water vapor

environmental rooms

time to measure the gain

the study, the

moisture refers

humidity

and critical

to the amount

of water

needed

to change the physical

properties of the product

to a point at

becomes

unacceptable.

calculate

the equivalence between the time in the environmental

"regular"

The

problem:

The

inside the

affect

are part of the

data is obtained,

spoil

in the

the foodstuff.

the final
shelf-

As

package.

life

shelf-

of

to migrate as determined

moisture.

The

affecting

shelf-life and

migrant

in the

described

by

(L). Before

plastic

parameter

films

At

can

by

earlier,

as

the

on

permeability

are

and

such molecules are responsible

fact,

permeability

for

will

equations

that is

maximum amount of compound

as the shelf-life.

described

by

Apx

package.

The

and the most

widely

Theory

ll

or

The

environmental

initial

factors

the partial pressure of the

package characteristics can

(A), Permeability (P),

this relationship, it

or membranes.

The Permeability

dioxide

measurements such as critical moisture minus

the inside of the

understand

carbon

P A Apx / L

the other factors in the equation: Area

truly

oxygen,

immediate

that the permeability of the film

clear

be interpreted

permeability

atmosphere or

one can

information

an engineer encounters an

(Briston 1974):

In this case, A Mx is interpreted

allowed

the time in the

shelf-life model to predict the

the packaged product. In

A Mx/ At

to

Shelf-life

films,

was stated

predictor model

used

environment.

Therefore, it is

life

room and

product

"regular"

Permeability and

with plastic

is

a mathematical equation

entrance or exit of small molecules such as

spoilage of

greatly

between

packaging foods

water vapor

the

the product would

Relationship
By

all

All the data is then included in the

environment.
rate at which

When

the

which

will

and

be necessary to

recognized

Thickness

review

permeability

be

basic

theory for

Permeability is
of

the film and the difference in

membrane
and

is dictated

the gas, as

well as

Permeation
materials are not a
of molecules

in

the transmission

the degree

completely

the lack

flexible

of

it.

nature

more

less rigid,

networks.

permeation which

free

upon

organized networks

As

consequence, the

only few

vibrate

network of pores

the molecules

less than disorganized

more rigid networks

for

greater

displacement,

permeation process occurs

in four

steps

due to

packed

that arrange in a more

of vibration of

small molecules could permeate.

elastic networks allow more space

tightly

In any case, the

the degree

generally

consist of a network

to the backbones. In those

polymers

spaces.

Such

materials.

polymers can arrange themselves

groups attached

"empty"

depending

matter, but

amorphous regions

limited than in bulkier

are more

Highly

functional

in

Some

membrane

of them.

of polymeric

continuous arrangement of

bulky

allowing for

the properties of both the

between the two

of variable sizes.

"pores"

more or

forming

on

"pores"

disorderly way
be

of interaction

crystalline regions or

for both the thickness

rate at which a gas will permeate through a

in films due to the

occurs

very orderly way in

cases, the

The

pressure.

many factors dependent

containing

orientation or

will

by

rate of a vapor normalized

more

allow some selective

may

On the

other

hand,

larger

so more and

the more

molecules

can permeate.

The
1

Collision

of the

2.

Sorption

Migration through the

of the

Desorption

4.

with

the

permeant and

step, the

its

polymer.

partial

molecules

molecule with

into the

polymer

from the

polymer

penetrant molecules collide with

This step is obviously dependent

pressure, and also depends

polymer absorbs

the polymer

polymer

of the permeant

In the first step, the

blend

penetrating

(Stern 1989):

the

penetrants.

chemical

affinity between the

pressure.

In the third step, the

on

the membrane until

on

the concentration of

the film surface area. In the second

This step depends primarily

polymer and

they

on

the polarity and

the penetrant, as well as on temperature and

"jumps"

penetrant

12

through the

"pores"

or

empty

spaces

in the film. The

available

nature and arrangement of the polymer

the penetrant determine this step. The last step consists

This step depends

molecule.

both penetrant

on the

which

difficult to

visualize.

molecules

in

It

the molecules

can

be

more

constant movement

temperatures the molecules

form. Diffusion

migrate

easily

can also

mobility

be

pressure, and

size of

penetrant

chemical nature of

if one

polymer could

most

polymers are

certain

the holes will constantly disappear and re

disappearing

that permeability

be the

increases. Above

occurs when the molecules of the permeant trapped

concluded

that

observes

as temperature

particularly

pore

that new penetrant molecules occupy any

requires

to the

the desorption of the

through the

understood

will vibrate and

through such mechanisms from a

will

to a new one.

"hole"

increase

in the holes

Thus, diffusion only

that becomes

with

jump

vacant.

From this

temperature due to the higher

of the networks.

It has been
initial

partial

addition

and polymer.

The step in

it

temperature,

of

in

period of

proven

reached provided

During

maintained.

process of permeation can reach a

increased permeability from

be

permeation will

that the

that the

of

Diffusion,

A Mx/ At

P
A

film

This

but it does

Transport

steady

vapors

be

in

rate of

sides

is

polymeric structures

written as

(Halek 1988):

P A Apx / L

rate of species x across a

film

permeability

Apx

which can

equilibrium,

state: after an

difference between the two

pressure

the steady state, the permeability of

usually follows Fick's First Law

Where: A Mx/ At

zero until

steady

area

pressure

drop

of species x across

the film

film thickness

equation

not

truly

is widely
explain

used

the

in

the prediction of shelf-life

chemical nature of

13

for many food products,

the permeation occurring in

films.

There is

for the steady

another equation used

diffusion

coefficient

(D)

and the

state

that

coefficient

solubility

consists of

(S). This

can

two

parameters:

the

be described in the

following equation:

The diffusion

coefficient

is

order of the polymer structure and

structure.

The solubility

penetrant molecules

kinetic

that

be

will

films

It
to

keep

temperature

to the degree of cristallinity

or absence of

to diffuse

on

large

reflects

the most

is

several series of

vapor pressure

its relationship to the polarity

and

concentration of

the polymeric material. This

general rules of

or

inside

amorphous areas

indicates the

temperature and

sets of

(Paine 1992).

solubility, such as
of the compounds

as well as their chemical affinities.

makes sense that

the compounds

the solubility

in

coefficient will

a vapor phase.

This may

compounds of

homologous series, solubility

vapor phase.

number of methylene or other groups attached

boiling

conducted

in

points and

heat

in the 1980s. Such

a

be

related

to the energy

The higher the energy, the

stay in the

soluble

value relates

a parameter that

compound will

higher

that measures the rate of transport

the value has been calculated for

which

The solubility coefficient, however,

value with

is

able

different

polymers and permeants at

and

parameter

the presence

coefficient

thermodynamic parameter in

increasing

D*S

through the polymeric film. This

of permeants

the

explain

will

more

why it has been

increase if there is

likely

observed

an

that in

increase in the

Strandburg has

confirmed this

in

results allow us to predict which compounds will

on

the

to the backbone. Such groups usually cause

of vaporization.

determined film base

required

its backbone

and

boiling

points, and

help

studies

be

more

to predict

its permeability.

When trying to
taken

into

account:

compounds

can act

estimate

the permeability of the package, another factor should be

the activity of the permeant in the package wall.

as plasticizers

at

high

concentrations

Luttmann 1991). Plasticizers increase permeability because

14

in

they

some

Many

organic

films (Halek &

allow more

flexibility

between the network,

cause

that is usually ignored when

When there

migrants.

assist or retard

may

general allow more

or a

predict what

the

of

migrating through the

are

the final

The

other.

competing for the

outcome

may be

spaces.

film,

permeation can

On the

effect.

plasticizing

empty

One factor

is the interaction between

packages

are several compounds

decrease because both migrants

is hard to

designing

the migration

increased solubility

in

and

swelling,

hand,

other

one component

increase because

the

of

permeation could

In many

same sorption sites.

and

multiple

it is necessary to

cases

it

obtain empirical

data.

Permeability Measurements: Determining the

Transmission
of stated

dimensions

modeling done

Therefore, the
The

shelf-life.

on

is

rate

the volume or mass of a substance

water vapor

follows the

spoilage

transmission rate

for the

mathematical equation

A
T

mass of water vapor

thickness of barrier

There
of

(100

water vapor

The

Determining

packaging

in

the

transmission

industry to predict

rate

is

as

follows:

(t) / A (T)

(g)

WVTR

materials.

atmosphere

moisture gain

of the

used

of moisture.

in)

sq.

are several methods available

humid

is greatly

of gain/loss

(mils)

One

Standard T448-M49.In this method,

controlled

a structure

(days)

Methods Available for

(WVTR)

transmitted

area of transmission

time

mechanism

value

WVTR

Where: q

passing through

time at a fixed pressure difference. Most shelf-life

within a stated

food

WVTR ofFilms

by

is determined

disadvantages

the

for testing the

method

a water

material

is the

transmission rate

dish

method

material

is

separated

which

is

standard

absorbing

being

water vapor

analyzed,

(TAPPI
from

sealed over a

by weight gained over a determined period of time.

of this method are

the length

15

of time required

to

dish.

Some

get meaningful

data

and

its unsuitability for high barrier

day. Due to

Another way to

instrument,

(4-54

in use, the

less than 1 g/sq

of

is

surrounded

C). The

relative

WVTR is

measure

by

using

special equipment.

dry

by

a water jacket

section can

humidity

in the

dry

be

that

raised or

side

is

maintains

dry

isolated. The
through the

relative

film,

humidity

relative

eliminated

humidity

the relative

air until

humidity

lowered

maintained at

by

The Honeywell

set

to the

increasing

time, the

the

compressed air.

When

not

which

dry

due to the

At

by

weighings required

cell

is

purged

the cell is

passage of water vapor

this point, the

value needed and measurements are started.

the need for the numerous

is the lowest

values and then

rate will stabilize.

this

within

10% RH,

falls below the test

will start

and after a short

is

developed.

the temperature

test level. After insertion of samples and before starting analysis, the
with

meter a

first instrument specifically designed to determine WVTR. In

the

was

a cell

range

WVTR

limitations, more rapid methods to determine WVTR were

these

Model W 825

materials with a

dry

cell

This instrument

the dish method (Paine

1992).

Another commonly

used

instrument

used

for

water

determination is the Mocon Permatran instrument. In this

material

is

reservoir

purging

clamped

(100%

relative

humidity)

with nitrogen or

temperature; the

humidity

in between two halves

air.

The

humidity

instrument,

One half of the

at a constant temperature.

The

whole

movement of water vapor

recorder.

results within a

dry

of a cell.

cell

is then

vapor

The

is isolated

the packaging

cell consists of a water

other

and

half is dried

kept

measured and recorded

recorder employed

is

an

transmission

by

at a constant

by

means of a

infrared detector that

provides

few hours.

Barrier Materials
A barrier

food. Most

material

plastic

films

is

are

one

that impedes the transfer of a substance

finite barriers to gases, moisture,

16

and

food

into

or out of a

constituents

in the

sense

that

they

applications.

barrier

are a number of

They have been used

materials that are

over

time because

properties and good mechanical properties

for

has been done to determine the compatibility

is

a chance

and

that some quality

will

be lost

allow

limited

amount of passage

they have

used

in food packaging

shown appropriate

food

they

those

with

are used

films,

barrier

However, little

well-defined applications.

of

when

commonly

and

therefore there

for packaging

certain

foods

ingredients.

Why Are Some Polymers Better Barriers

Obviously,
low solubility
permeability.

the

that

barrier materials.

are considered

There

However, films

allow some passage.

and

when

coefficients

while

polarity is

polarity is usually determined

alcohol

barrier

is

For example,
polar

due to the hydroxyl

water, but

are

associated with

the solubility coefficient.

associated with

(OH)

group.

Non-polar

molecules, but

flavors. On the

they

is

for

The

the kind of functional group attached to the main

by

against water and other polar

against

Crystallinity

and polarity.

materials with

parameters are responsible

polyethylene and polypropylene are

molecules such as organic

barrier

is trying to find

one

because those two

Polymers vary in crystallinity

diffusion parameter,

polymer.

for barrier materials,

looking

diffusion

Than Others?

other

better barriers

they

hand,

non-polar, but polyvinyl

materials are

are poor

usually

barriers for

better

non-polar

polar polymers are not a good

against non-polar organic compounds

(Koros 1989).

Another factor affecting

crystalline solid state matter.

to the

rigidity

of

the

such as molecular

The

structure.

weight,

polymer

regularity

properties

more crystalline a

In addition, there

molecular weight

and additives such as plasticizers.

characteristics:

barrier

As

are other

17

factors that

to

affect performance

cross-linking, thermal

rule, barrier

of molecular structure and

1989).

ratio of amorphous

material, the less permeable it is due

distribution,

a general

is the

polymers share

the

history,

following

tight chain to chain packing (Koros

One way
on

of

the mode of

efficiency in

the

for

available

increasing the barrier properties

deformation,

permeation

by means

increased considerably in the food

metallized

in

most

used

films

are excellent

if a

clear package

PVDC, EVOH,

and

is

extent where

of metallization.

orientation.

The

of

Depending

the increased

holes

pores or

The

and

reason

films has

for this is that

reasonably easy to

films is that they

are other options

in

are

barrier

increasing

of

usage of metallized

of metallized

In that case, there

fewer

way

cost-efficient, attractive,

One disadvantage

needed.

popular

industry in the last few years.

barriers,

equipment.

packaging

to an

(Smith 1991). Another

film is

is

increase the barrier because

of the molecules

packing

properties of a certain

one can

of a material

run

cannot

be

the market such as

PVC.

Types ofBarrier Films

Polypropylene: Polypropylene is
When oriented, its barrier

food industry. For food

coated,

is

or metallized

tendency

cannot

be

polyester

for frozen

cookies, crackers,

and

used.

films

confectionery

either

flavors

materials

that

its

molecules are

polymer

presents

is brittle

high

so

it is

its high barrier. PVDC

used

to

is the

main spoilage

This is

this clear,

factor,

there

form. Polypropylene
barrier

not a good

film widely

used

for snacks,

one of the most common

used as a

flexible

coating for

materials used

structure's

density,

high

which

often plasticized

chlorine content.

symmetry:

qualities.

from permeating, but it is

It has been determined

is usually independent

The high barrier

of the

18

over

substrate, but is

However,

decreasing

most

commonly

time that the

totally

this

thus

means of co-polymerization

prevents various gases

is

tight packing is possible and the

imparts the desired

by

in

other more economical

of the advantages of this polymer over other materials

prevent oxygen permeation.

oxygen transmission

and oil.

factor,

main spoilage

clear or metallized

mostly inert due to their high

property is derived from the

molecule

oxygen

in the

a preferred choice

due to its low polarity, it is

Generally, PVDC is

to increase barrier. One

in

is the

water and oxygen.

products.

PVDC: Polyvinylidine Chloride is

the packaging industry.

When

applications and

against organic compounds such as

barrier for both

increase 50-100%, making it

applications where moisture

film is widely

to use

used

properties

an excellent

rate of

controlled

by the

PVDC coating,
PVDC
can

be

so

coatings as a

barrier

placed anywhere on

different layers.

be

substrate can

any

against

and

water, aroma,

flavors

of

different

industry

products.

uses

PVDC

sandwiched

between

provides weak seals that are adequate

for light

the packaging material:

speaking, PVDC

Generally

(Bicerano 1989). Also, the

selected

the surface or

on

products only.

PVC: Polyvinyl Chloride is

against water and oxygen.

by

possible

newer

food

However, its

contamination

higher barrier

thermoplastic film that has

resins of

by

low

use

is

fairly

limited due to

somewhat

weight monomer residues.

the Saran type have

barrier

good

produced new

properties

concerns caused

Later developments in

packaging

opportunities

for the food industry.

EVOH: Ethylene
moisture sensitive

PVDC

can

between

be

due to hydrogen

polyolefin

layers. Data

uses

commonly

limited though due to its high

materials

is

that

EVOH is

so

and

this

price.

it

barrier

must

be

properties

protected

that EVOH is

hydrogen bonds
material as a

One

an

for gases, but it is

from

packaging material, EVOH

suggests

due to its high polarity

industry

excellent

bonding

placed on the surface of the

aroma/flavors

The food

has

vinyl alcohol

moisture.

be

must

sandwiched

excellent

barrier for

high

crystallinity.

with areas of

barrier for flavors. The

advantage of

not made of possible poisonous

this

While

usage

material over other

is

barrier

monomers, so migration is not a

concern.

Selecting an Appropriate Barrier Material for a Packaging Application

When selecting

factors
use

such as the total

that

material

in

properties of both

cost,

current

the food

Usually, film

material

market

for

and

the

information

on structure,
package

application,

one

has to

consider

requirements, availability, barrier needed, ability to

and

the total physical and chemical

package.

and

converters

the different options available

on

a certain

manufacturing equipment,

manufacturers

information

it is up to the

packaging

in

provide

the market.

much needed

Data

sheets

for films

gauge, sealability, barrier properties, yield, and so on.

designer to determine

what

19

film to

use and where

technical

to

contain

However,

locate it in the

package system.

There

few factors that

are a

need careful attention when

choosing

barrier.

Location
to

loss

of

Barrier: Incorrect
so careful

efficiency,

problem arises

environment, locate

Oxygen

also

the barrier in a barrier

be involved in

should

lead

system can

determining not only

the position of each component in the

the

system.

follows:

general considerations are as

If the

position of

thinking

to use in the system, but

materials

few

of

from

the

the components of the

barrier

and water vapor

as close

barriers

outside

to the food as possible.

be located

can

food escaping to the

almost anywhere

in the barrier

system.

Determine

whether migration

the food could be a

contaminant and the

Moisture

sensitive

from any

of

the components

of

the package to

Locate the barrier between the

problem.

source

of

food.

barriers

should

be

protected

from both food

environment, so they should be located

on

If there is interaction between the food

and one of the

and

the outside

intermediate layers.
layer materials,

separate

those two substances with intermediate layers as well (Gerlowski 1989).

Product Package Compatibility:

interaction between

the

packaging

can prove

to be costly, so a

Basically,

there are two ways

packaging:

can

be

1) The food

absorbed

nature of

weight, type

There

life

are

in

material and

which

can react or

and

the

the

understanding

into the packaging

both the food

molecular

key

Usually, little

food

form

can

bond

material.

polymer

of

thought

product

is

given

to the possible

it is intended to

contain.

food-package interaction is

interact
with

This

necessary.

with a polymer material used

the packaging material;

The interaction

including factors

will always

such as

polarity,

2)

for

the food

depend
state of

on

the

matter,

of bonds and so on.

two basic interactions that must be predicted in order to

and/or avoid possible

health hazards. Those two interactions

20

are

1)

increase

shelf-

the migration

from

the packaging material to the product;

compounds

from

interactions

will

Therefore, it

food

the

be strong

can

be

chemical

following are

interactions

1-

in

with

few

the

Sealants

can

product.

Thus in

be

2-

Organic

or

The

to make

examples

sensitive

6-

could

attack

of

or

present on

weaken or

increased ingress

of

the

break,
water,

some other

sealant or

its barrier

properties are

compounds can react with

Flexible film

the adhesive, but affecting the whole

way; for example, plasticizing the flexible material to

key mechanical properties.

which

the adhesive of a lamination causing

the product may be able to migrate through the

some

The

fail because

of the package.

in

quality

understand and

a package can

the solvent, the seals

attack, spillage,

affecting the

color, cristallinity,
5-

that illustrate how

point

Organic

or short run.

light.

package without

4-

cases such

more sensible choices of packaging materials.

constant contact with

compounds

in

long

to solvents or other organic compounds

organic compound of

material

In many

flavor

product.

delaminative failure

absorption of aroma or

it is necessary to have the ability to

which can cause microbial

oxygen,

the possible

to cause package failure in the

enough

order

2)

the packaging material (Arora 1991).

understood that

predict such occurrences

The

by

and

greatly

decreased,

the flexible

materials

as well as

causing

altering

change

in

or other optic properties.

can absorb

flavors

or aroma added

to the food affecting the

of the product.

migration of

the food

potentially toxic

causes a potential

controlled

compounds

health hazard. This

by the FDA

21

found

on plastic materials

one mode of

into

failure is strongly

One important interaction

limoneme

and several

conducted on

commonly

and

confectionery
soluble

and

juices

inn polyolefins)

conducted at

study

saturation

properties: modulus of

impact

due to

Other

limoneme
Such
it

plasticizing

studies

on certain

when

of

that the films

is

solubility

juices,

studies, it can be

barrier

in this

such as

an

this

compound

or

particular

in

the

concluded

following film

elongation,
that

seal

strength,

such changes

determine the solubility

to

applications

orange

absorbing high

for

One

on polyolefins.

for packaging
packaging

non-

chemical models

The study

affected

ultimate

is

quantified the changes

compound.

is

drinks,

of

variety

of study.

researchers reasoned

trying

materials.

LDPE

compound

(Kobayashi 1991).

juice in tetra-pack packages,

quantities of this natural

other people

This solubility

interested in

value

is

pigments,

absorbed

flavor.

knowing the

of great

in the film. Also,

Polypropylene

of d-

importance

those studies

d-limoneme,

other natural

the

flavors found in

in those films increased considerably (Letinski 1992). Thus, from those

concluded

properties of

that d-limoneme plasticized those films

the films considerably. Even

study: metallized

most severe

1988)

of that organic compound

films

"windows"

the

The

of other compounds such as caretonoid

and oxygen

natural

films

(Hirose

d-limoneme

of some relevance

d-limoneme in different

that after

when

used were

predicting the permeability

suggest

noted

because

many; this

flavor to

for this type

d-limoneme has

used

are

importantly,

this organic

conducted

films commonly

review of such studies

solubility

effect

have been

studies were conducted

was observed

The

the

added as a

elasticity, tensile strength,

resistance and oxygen permeability.

occurred

is

University

absorption of

point,

extensively

this flavor

reason

its behavior follows many

and

have been

studies

on several plastic materials

(Brant 1991). The

and most

properties of sealant polymers saturated with

that at the

d-limoneme

perfect example

Michigan State

Several

materials.

so

and

Also,

products.

for permeability, making it the

used

of

in the literature

studied and cited

(highly

polar

packaging

and polypropylene

flavor for many fruits

a natural

desserts

is

used

d-

to this study is the one occurring between

the permeability and solubility

including LDPE, HDPE,

compound

relevant

cases,

indicator that many packaging

or

exposed to

loss

more

dramatic

materials should not

be

and

Such strong interactions

used

the

changes were

d-limoneme developed pinholes,

of metallized areas.

22

and changed

in

are

for foods containing this

flavor,
There

or that

are

the shelf-life

many

predictions should

have the

reviewed

to include those discoveries.

to believe that not only d-limoneme

reasons

films;

mechanical properties of plastic

nature will

be

other

flavoring

affects

the barrier

and

compounds of similar chemical

same effect as well.

STATEMENT OF THE PROBLEM

A company manufacturing hard candy

estimated

for that

the

shelf-life of

their lemon flavored candy to be 50 weeks, the actual shelf-life

only 35

products was

weeks.

the shelf-life of other flavored

the same
model

is

distribution
not

system.

providing

the lemon candies in a

noticed that while their shelf-life model

The

same

model,

candies packaged with

The

objective

however, has

correctly

the same materials and undergoing

is to determine

accurate predictions and

predicted

to find

the reasons

way to

why the

predict

shelf-life

the shelf-life of

quick and economic way.

HYPOTHESIS

The hypothesis is

limoneme)
affecting

interacts

with

that the

flavoring

the packaging

compound used

for confectionery

products (d-

films, decreasing their barrier properties

the shelf-life of the candies.

23

and

thus

TEST DESIGN AND METHODOLOGY:

Experiment Design

Purpose

This
absorption

would

film

be

and

WVTR

by

several plastic

its

increasing

be then

films

studied

point.

would

transmission

water vapor

relationship between
would

films

order

have

direct relationship between the

at

designed in

experiment was

d-limoneme
amount of

any

Three films

given

would

on

their WVTR. It

The

experiment

concentrations

d-limoneme

d-limoneme

be study to

d-limoneme

amount of

rate.

expressed as an equation

at

to determine the

in

order

effect that

was assumed that

intended to

by

given

measure

films

mathematical

WVTR. This relationship

that could be used to predict the WVTR

from

concentration

establish

there

any

absorbed

to establish a

absorbed and

d-limoneme

zero ppm until

of the

the saturation

any trends.

Design

This

Step

experiment was

1: Exposure

of

In this step,
absorption of

limoneme

WVTR
will

reached

samples

by

concentrations

absorb

(at the

this

of

the films

the films

at which

designed in

were unknown.

slowly

in three

performed

steps:

the films to d-Limoneme

d-limoneme

experiment was

designed to be

Two

such a

were

exposed

was unknown.

to

measure

This

to d-limoneme. The rate of

made

the WVTR

way that both the

assumptions were made:

the task of selecting d-

impossible. Instead, the

concentration of

d-limoneme

That film

to

1)

exposed

organic compound until equilibrium with

saturation

point);

2)

The

the

d-limoneme

the environment was

rate of absorption was small enough

24

and

to allow for

weekly

in

performed

environment.

films

variable

before

d-limoneme

and

were exposed

At the

saturation

If needed,

by plotting time vs.

estimated

were placed on a closed

to d-limoneme.

to

d-limoneme,

point,

no

further

changes on

d-limoneme

a rate of absorption of

However, it

concentration.

the higher

exposure and

Finally, it

saturation point.

limoneme
same

decreasing

then a gradually

absorption rates so even though

time, the

during

rate until concentration reached

that the different films

was expected

the WVTR

concentration of d-limoneme on each

would

film

would

the

have different
be done

measurements will

by

was expected

that the rate of absorption would be non-linear, with a fast absorption occurring

initial

be

hourly as needed)

film

until saturation occurred.

be

measurements would

wrong,

measurement was time of exposure

concentration would occur.

could

or

that the longer the time the films

the concentration

the

(daily

a constant amount of

The only

was expected

d-limoneme

second assumption were

shorter periods of time

On this step

It

If the

measurements.

d-

at the

be different.

Sample Preparation
After
prepared.

one roll of each

Testing

film

samples consisted often

two-quart Mason jar. A 22 cc

introduced
to allow

in

as well

films to

"controlled

was supplied

into

each

absorb

the

glass vial

jar. The

by the

(10)

organic compound.
(72

placed

organic compound was

Glass jars

were

tightly

F, 50% RH) Six Samples

room

samples were prepared with

the dates

specified

below. Samples

weeks when saturation was observed

with

time

until

were

for

all

the film

film from

taken for

one

of each

weekly for

rationale was

saturated;

left

open

film

were

the same roll manufactured on

analysis

films. The

was

in

sealed and placed

environment"

All those

increase

packaging film

samples were

one gram of organic compound was

containing the

prepared.

would

grams of

containing

vial

film company, testing

after

a period of

4-5

that the concentration

saturation, concentration

stayed constant.

In addition, two
prior

more sets of samples were

to any conditioning with the

samples.

The

notice that

organic compounds

second set consisted of

this film was

tested. The first set consisted of

film

not printed so

it

used

(zero

ppm).

set was

to package product. It

was a good sample

25

This

to study.

films

the control

is important to

Packages

were

taken from the line

quantify

It

Measurement

The

hard

the

temperature

to

because they

to

candies.

The

the

procedure

films in the

F. This

was

done to

worst possible storage

the amount of organic

d-limoneme

determine the

materials

in the

actual

absorbed

by the

d-limoneme

amount of

film

on

the films was

to separate the d-limoneme from the film followed

determine the

were

120

of

saturation value.

Chromatography

Spectrometry

all cases

of the amount of

method selected

Head Space Gas

selected

that in

was observed

packages corresponded to

Mass

one month at a

the amount of organic compounds on the

conditions.

Step 2:

for

and aged

concentration of

standard

d-limoneme. These

by

methods were

tests followed in the company manufacturing the

described below is the

company's standard procedure

for

determining the amount of solvents on plastic films.

a)

Concentration

Determining the
The

concentration of

chromatography

and mass

all samples were

taken twice.

the

of

Reagent

reagents

spectroscopy

on

Films: GC-MS Method

in the films

was

determined

described below. Note that

as

by headspace

gas

measurements

for

Sample Preparation
Samples

were crumbled

solution of xylene

samples.

in

olive

The final step

was

to fit into

oil, the internal

to crimp-cap

22mL headspace

standard

vials

to

vial.

in this method,

ensure

drop

of

was added

50ppm
to the

that no organic material would

escape.

Headspace

Sampling

A Perkin-Elmer HS-40 Static Headspace Sampler

the

to

parameters used

give

the

for

all sets of samples.

was used.

Experimentally,

most reliable results:

26

The

following

were

these parameters were proven

Thermostat Time

=10 minutes

Thermostat Temp

=100

Pressurization Time
Injection Time

Withdrawal Time
Needle

Temp

Transfer Line

=1.0 minute

2.0

minutes

0.2

120

minutes

deg C

from the

liquid

vial and

Temp =120 deg

The HS-40 thermostated the

sample

deg C

sample vial

for the

injected it into the GC column,

time, then

specified

which was

held

at

withdrew a

-40

deg

with

nitrogen.

Gas Chromatography:
The

following were the

Column
Initial

J&W 60

Temp

Initial Hold

Final Hold

samples

the

trapped

all

ramped

to 200

the

column as

column

to

they

stationary

partition

into

4.0

-40

5.0

meter

deg

in

phase

deg

C/minute to 200

the mass

Mass

Each

of

the

deg

um

film thickness

their

(a 0.25

were cryofocused on

band

boiling point.
um

layer

the

the head of the

at

above, which

of

column at

column.

caused compounds

The interactions

The

-40

deg C,

which

column was

then

to begin to move down

of the compounds with

5%-phenyl-methyl polysiloxane)

caused

the

them

the stationary phase according to their affinity for the phase.

The differences in affinity for the

separate.

ID, 0.25

minutes

a narrow

and out of

mm

minutes

as specified

neared

DB-5 MS, 0.25

from the HS-40

volatiles

deg

Temp Ramp

The

equipment and parameters used:

compounds

phase

among different

thus exited the

spectrometer.

Spectrometry

27

compounds caused

column at a

different time,

them to

and entered

The

equipment used was the

Finnigan Magnum

Ion-Trap

GC-MS. The

parameters

used were:

MS Transfer Line Temperature

Mass Range Scanned

Ionization Mode

As

into the

the peaks

mass

220

deg C

29 to 650 AMU

Electron Ionization

corresponding to

spectrometer,

them to ionize and

where

fragment. The

(EI)

each compound exited

the GC column,

they

passed

the compounds were bombarded with electrons, causing

pattern of

fragmentation (ion

mass and

abundance)

was

the fingerprint for the compound and was therefore used for identification purposes. The

intensity

the total ions produced (the

of

area

under

to the concentration of the compound,

proportional

the chromatographic peak) is

and was

thus used for quantitation

purposes.

Quantitation
The

amount

ppm=

(ppm)

(Area

of each compound was

Measurement

It

was

d-limoneme

from the

sample

sample was

analyze

of

weight(g)

the WVTR

of

+ standard

the films

important to determine the WVTR

was

being
to

by the following formula:

of contaminant peak/Area of standard peak)(standard solution

added(g)/(sample

Step 3:

determined

measured.

measure

divided into three

Immediately

Weight(g)))*(50)

exposed

at

the same time that the concentration of

after a small amount of

d-limoneme concentration,
pieces and placed

WVTR.

WVTR Determination

28

to d-limoneme

larger

film

was

portion of

in three different MOCON

taken

the same

3/3 1 to

The Water Vapor Transmission

MOCON

rate of all

films

was

determined

Water Vapor Permeation Analysis System Permatran

taken three times. The

measurements were

by

means of a

W 3/31. All

following parameters were used:

Parametersfor All Films

Temp: 37.8 C

Cell RH: 100%

Nitrogen Flow: 100.0

Conditioning Time:
Number

of

3.0 Hours

Cycles: 15

Cycle Time: 45

Those

seem

minutes

parameters were used

because that

that company. In this particular instrument

humidity
give

be

could

be

changed.

the film time to

more accurate.

This issue

the

neither

The conditioning time

stabilize at that

will

of

temperature and

be discussed

the

was

on more

standard

temperature,

testing
nor

procedure of

the cell relative

three hours was done in order to

relative

detail

humidity

on

the

so

the values

discussion

will

section.

Materials

Reagents
The

reagent used

was supplied

by Aldrich

for this

experiment was:

d-limoneme. This

Chemical Company.

d-Limonene, 97%

Molecular Formula: CI OH 16
Molecular Weight: 136.24
Assay: 97%
Density: 0.840
Comments:

Boiling Point (C):

175.5 to 176 / 760

Limoneme's Chemical Structure:

29

organic compound

Uses: Orange

and

Lime flavors

Polymeric Films
Three

(3) films

Bicor 90 SPW High

of the

films

lemon hard

if they

were selected

Energy Surface Wound,

could

The

study:

and

for this study because it

was selected

candy.

for this

other two materials were

increase the

shelf-life of the product.

taken from technical data sheets

provided

by the

Bicor 100 LTSC Acrylic Wound Out,

100 LMB LTSC Sealant Wound In. One

was

the packaging

being

considered

material used

for future

for the

applications

All information regarding the films

was

films'

suppliers:

Bicor 100 LTSC Acrylic Wound Out:

Supplier: Mobil Chemical

Structure:

Coating/Adhesion

Acrylic
Core/

Company

adhesion

mil

WVTR: 5.0

2001

Gauge

g/m2/24

H/ 38 C/ 90 % RH

Usage: Inner wrapping for

Width: 3

Tablets

Cherry

1/16"

CutOfflength:2

Bicor 90 SPW High

1/8"

Energy

Surface Wound.

Supplier: Mobil Chemical

Company

Structure: Treated Surface (High

Manufacturing
Gauge: 0.90
WVTR: 5.4

mil

Date:

Energy Layer)/ Core

January 17,

2001

Gauge

g/m2/

Usage: Inner
Width: 3

Layer/ Polypropylene

layer/ LTSC

Manufacturing date: January 11,

Gauge: 1.0

Promoting

24 h/ 38 C/ 90 % RH

Wrapping for Mint Tablets

1/16"

Cut-Off Length: 2

1/8"

30

Polypropylene/ Sealant

100 LMB LTSC Sealant Wound In

Supplier: Mobil Chemical

Structure: PVdC
Adhesion
Gauge: 1

.0

Company

Coating/Adhesion

Layers/Polypropylene/

Promoting Layer/ Low temperature

Seal

Coating

mil

WVTR: 3.9

g/m2/24H/38

C/ 90 % RH

Manufacturing Date: January

Usage: Proposed
Width: 3

Promoting

09 2001

Packaging Material

1/16"

Cut-Off Length: 2

It is important to

1/8"

note

same rolls manufactured on

that all the film samples that

the dates

specified above.

printed.

31

were

Also,

tested

none of

came

from the

the films

were

RESULTS AND DISCUSSION

A Comparison Between the Results

and

The theoretical

for

moisture gain and

mode of spoilage

shelf

lives

lost. This

for the

was not observed prior

calculations were made

Company

and

relative

humidity were

and the

Shelf -Life

be 50

weeks.

agree with

for the

It had been

product.

to the candy's

the

1-

35

was

Revising the

Before

flavoring

water absorption.

model.

the WVTR information

The

shelf-life

provided

by

the

internal Report. The

storage

by

copy

Using this

the company, the shelf-life

of

the

seemed

report

products and

it

information

was estimated

obtained) That

from the field. The

obvious

temperature and

value

does

not

observed shelf-life

that the theoretical model

could not account

to

was

for the differences

on

the

Packaging Films

experiment:

discussing

the

effect

that d-limoneme had

on

the

films, it is important

to more details. After the study was conducted, several

Many

the

Unfortunately, due

and ways

It

by

of all

observed

information previously determined experimentally

d-Limoneme

the

will

included in the

was not

account

on an

both

observed on

discussion

repeatedly that the loss

model

for both flavors.

of

experiment

results.

noted

to be 22C and 75% respectively.

weeks.

shelf-life of

Absorption

discuss the

Published

using the Labuza

to be effective, as this is the

observed shelf-life values obtained

candies

of

into

computer model used

shelf lives observed

Effect

by taking

estimated

were calculated

physical changes as caused

flavor

of

(See Appendix A for

overestimating the

in

the candies

as well as critical moisture

suppliers,
the

of

method proved

Due to that observation, the loss

by

the Theoretical Shelf-Life Model

obtained with

The Observed Shelf-life

experiment.

be based

on

to improve it for

the

of those

to the

reason

flaws

author

why this

other studies.

32

can

seriously

inability

to

compromise

re-run

experiment was not

flaws

to

were

the validity

of

the experiment, this

completely

successful

a)

The

samples on

from the

this

same roll.

particular

roll

b)

The
the

c)

This

means

different days to

number of samples on

samples on this

study

came

should

account

this study

was

have been taken from different

for manufacturing
too

small

rolls

variability.

compromising the

significance of

results

Although the WVTR

done

measurements were

films coming from

on pieces of

accurate value

for the WVTR

taken from other areas of the

d)

All

that we can only infer the effects of d-limonme on that

film. Samples

of

manufactured on

experiment were not randomized:

WVTR

of

done

three times

from different

period one can assume that some of

correspond with

sample,

we can

they

have

were

a more

that sample, we really can't tell if pieces of films

roll or

values

each

While

the same roll.

rolls will

measurements were performed after a three-hour

Therefore the WVTR

for

from these

the measured concentrations but

with

same.

conditioning time. After this

the d-limoneme has

obtained

behave exactly the

from the film.

evaporated

measurements

lower

don't trully

unknown concentrations

of d-limoneme

e)

WVTR

was always

standard.

However,

done

on

the outside face

the WVTR could

of

the film

as stated on

the company's

have been different if the inside face

was

measured.

2-

The

results

of the

experiment

100 LTSC

As

shown

limoneme

in Table 1, the

are non-linear.

changes

From this data it

this film decreased its

water vapor

certain concentration of

d-limoneme

saturation point.

At the

impossible to clearly
Another

reason

saturation

state

why it

in WVTR for 100 LTSC film due to

was

seems

like

transmission rate
was

point,

when

absorbing

becoming

achieved, the WVTR

smaller

increasing until the

a maximum value.

the transition points because there are very few

impossible to derive

33

an equation

amounts,

better barrier. After

started

the WVTR achieved

absorption of d-

data

It is

points.

that could describe this film

behavior

while

absorbing d-limoneme is that

difference. Example
point, the WVTR

of

was

this is the WVTR obtained

6.83

data

some

on week

C/ 100 RH. This

g/m2/24/38

points showed no significant

value

and

2. At the

saturation

is 1.45 times higher than

the WVTR obtained at zero concentration (4.74 g/m2/24/38 C/ 100 RH). This means that
the shelf-life of the product could be only 70% of the expected shelf-life
product

if no interaction between the flavor

Previous
absorption of

d-limoneme have

limoneme
limoneme
the

be

absorbed

amount of water

perhaps

at

the

saturation point

that at the saturation point, d-

the polymer network.

on

has

not yet

in higher

quantities

been

is that

However,
explained

at

the initial decrease in

in the literature to the

low concentrations, both the

same sorption sites.

due to its

non-polar

In this

nature, thus

case d-

decreasing

that the film can absorb and permeate. Evidence for this theory could

over a

Amount

shown

only

the OTR. It is agreed that this is due to the

plasticizing

of

Scanning Electron Microscopy.

Table 1 : Water Vapor Transmission Rate

Week#

conducted

competing for the

being obtained by means

100% RH

been

possible explanation

and water vapor are

will

same

the package were to occur.

it has been

concentrations

knowledge. One

author's

or

has

effect this organic compound

low limoneme

always

all studies

limoneme increased the WVTR

at

the

studies conducted on the change of properties of polypropylene after

(Hirose, Paick, Halek). In

WVTR

and

of

of

(WVTR)

of

100 LTSC film tested

at

38 C

and

period1

week

Limoneme

WVTR (g/m2/24 H/ 38 C/ 100%

RH)2

(ppm)2

4.74

6730

52

9522

11

14000

120

4.99

14790

6.83

1-

All

2.28

measurements were made on

measurements showed

.56

3.0.14ns

Saturday

different d-limoneme

at

pm.

WVTR

concentrations

.9

.10

and concentrations were measured at

(in

ppm).

Concentration

at week

the same time.

four was determined

Weekly
as

the saturation

point.

2-

Mean Value
p>0.05; n

standard

error;

mean values

in

columns and rows

sharing the

3)

34

same superscript

letters

are not

significantly different

90 SPW

Table 2
LTSC

Again,

shows

that d-limoneme had the same effect

samples

showed not significant

could

be that

from week 1

difference

some of the

on

and

can't

2 exhibiting lower

90 SPW film

it did

as

on

concentrations of d-limoneme

their WVTR. A possible explanation for this trend

d-limoneme

WVTR measurements. Samples from

respectively) didn't

on

evaporated
week

also showed a significant

and

during the sample conditioning before

4

10129

ppm and

1 1360

difference in WVTR. Once

ppm

again

this data

help to understand the exact relationship between d-limoneme ppm and WVTR.

However, this data

film before

shows that

absorption of

WVTR was 7.27

there is

d-limoneme

g/m2/24/38

a significant

and after saturation.

C/ 100 RH. This

obtained at zero concentration

(5.1

Week#

over a

Amount

of

value

g/m2/24/38

Table 2: Water Vapor Transmission Rate

1 00% RH

difference between the WVTR

At the

saturation

of the

point, the

is 1.43 times higher than

the

WVTR

C/ 100 RH).

(WVTR) of the

90 SPW film tested

at

38 C

and

period1

week

WVTR (g/m2/24 H/ 38 C/ 100%

Limoneme

RH)2

(ppm)2

5.1

8350

22

3.02

8700

2.72

10129

100

6.94

11360

37

7.27

1-

All

measurements were made on

measurements showed

.10

Saturday at 2 pm. WVTR and concentrations were measured at the same time. Weekly

different d-limoneme

concentrations

(in

ppm).

Concentration

at week

four was determined

as the saturation

point.

2-

Mean Value

p>0.05; n

standard

error; mean values in columns and rows sharing the same superscript letters are not significantly

3)

100 LMB:

35

different

At first

decrease

impression,
WVTR

on

is

difference

WVTR

on

low

at

concentration

Table 3

Zero

ppm and

trend exists for all polypropylene

support such observation at a

At the
value

saturation

9,460

of this

is

affected

to

Week#

film

set

While the
on

increase

is showing
author

films:

after certain

no significant

truly believes

this particular film

was

6.75

g/m2/24/38

obtained at zero concentration

a greater

Table 3: Water Vapor Transmission Rate

over a

this data

ppm.

high barrier properties derived from the PVDC

RH

a rapid

previous

such

can't

95% Confidence Level.

point, the WVTR

material

by

films studied, the data

is 2.1 times higher than the WVTR

C/ 100 RH). This

trends observed in the

followed

concentrations

However, statistically

reached.

at

shows the same

of the

degree

by

C/ 100 RH. This

(3.24

g/m2/24/38

d-limoneme due to its initial

coating.

100 LMB film tested

at

38 C

and

100%

period1

week

Amount

of

Limoneme

(ppm)2

WVTR (g/m2/24 H/ 38 C/ 100%

RH)2

9460

116300

6.27

13040

6.75

1-

AH

3.24

Mean Value

p>0.05;

2.356

29

measurements were made on

Saturday at 2 pm.

standard

.10
.36

and concentrations were measured at

ppm).

Concentration

at week

was

the same time.

determined

Weekly

as the saturation point.

error; mean values in columns and rows sharing the same superscript letters are not significantly different

3)

Including the

lost

of

barrier

Experimentally, it
the

WVTR

different d-limoneme concentrations (in

measurements showed
2-

162

concentration

of

properties on

was observed

the Shelf-life Model

that the WVTR of the different films varied

d-limoneme in the film. However, this

experiment

with

could not

accomplish some of the original objectives:

1 ) Describe

by

means of a mathematical equation

concentration and

2)

Estimate the

3)

Predict the

the relationship between d-limoneme

WVTR.

rate of absorption of

exact shelf

life

of the

d-limoneme

by the films studied

lemon flavored

36

candied on

any

of the

films

studied.

The First

objective could not

1-

The WVTR does

2-

The relationship

3-

Some data

Samples

did

points

because

to the

was non-linear so a

of several reasons:

measured concentrations

larger

amount of

data points

differences due to the

not show significant

were needed

small number of

(n=3)

were not

selected

randomly

from

big

All

population.

samples came

same roll of film

from the

Although, it is impossible
concentration and

At the

a)

achieved

not correspond

samples measured

4-

be

WVTR, it is
saturation

to describe the

clear

point,

that

exact

relationship between d-limoneme

all samples showed an

increase

on

WVTR making

clear

that d-limoneme has a plasticizing effect on all the films

At low

b)

concentrations of

showed a small

studied as

The

limoneme
shelf-life

film

(taking

second and

was

be

up to 4

WVTR. Also,

would

can

be

for

the film

of

order

WVTR. This

to

predict shelf

will not

flavor

be

saturated

complicated.

saturated at all points.

that the increase in WVTR

90

SPW

to be further

a rate of absorption of d-

In

accurately.

like

seems

vapors escape

estimating the WVTR

be extremely

life

Obtaining

films) During that period

the

and

observation needs

model, it is necessary to know

From this study it

some

once most of

The task

both the 100 LTSC

been discussed in the literature.

of a theoretical

weeks

on

third objectives are connected.

at all times.

can assume that

flavors

not yet

necessary in

by means

would

it has

decrease

d-limoneme

Based

but it

of

what

of

time,

the

from the inside

will

to estimate the

the WVTR of the

saturation occurs

slowly

film
of

release all

very slowly

will

be varying

the package, one

d-limoneme.

the films due to the interaction with the

good assumption could

on

order

be to believe that the film

this assumption, it would make sense to believe

observed at saturation will

37

be followed

by

direct

proportional

decrease in
twice as

shelf-life.

high, the

Such

an

shelf-life would

assumption,

direct relationship
model and

weeks

For example, if at the

of

exhibited a

WVTR

by half.

too simplistic. In

fact,

predicted shelf-life

for

complex

be impossible to

decrease in barrier

the food ingredients can

material

The

point, the film

experimentally, such a

for the candy using Labuza

the saturated point WVTR was 25 weeks while in reality, the shelf-life was 35

(See Appendix B). Due to the

level

reduced

however, is

was not observed.

an accurate prediction could

the

be

saturation

help

properties

interactions between the films

calculate.

However,

that a film can

undergo

and

flavors,

basic understanding

due to interactions

of

with

the packaging engineer to select a more appropriate package

a specific application.

38

CONCLUSION

The

purpose of

this study

different flexible packaging

1988)
but

d-limoneme has

that

noted

study failed to

such

WVTR. In this study,

exposed

to

different

experiment
could not

design,

be

materials

permeability to

on

Previous study (Hirose

Water Vapor Transmission Rates,

concentration and

were studied showed changes

d-limoneme. However, due to

concentrations of

relationship between d-limoneme

a clear

d-limoneme has

relationship between limoneme

films that

the

effect that

water vapor.

a significant effect on

establish a

all of

determine the

to

was

in WVTR

some

flaws

concentration and

when

on

the

WVTR

established.

Suggestions for Further Studies:

During the
order

For future

design, film

locations in

Increase the
order

3-

Increase the

mathematical

already

made

in

to have random samples.

(for both

concentration and

WVTR measurements) in

statistical significance.

data

For example,

points.

be taken

daily instead

function to

predict

d-limoneme to the

measurements

of weekly.

WVTR

during

Decrease conditioning time

escape of

suggestions were

be taken from different manufacturing dates

samples should

order

number of

can

design, few

data:

of the

number of samples

to increase

WVTR

4-

of the experiment

to improve the significance

and/or

2-

discussion

at

This

will

any d-limoneme

WVTR

measurements

environment and

for

concentration and

help

to establish a

concentration.

to a minimum to avoid the

thus samples

with

lower

concentration

than measured.
5-

Measure the d-limoneme

(to exactly know in

what

the time that the WVTR

6-

To

measure

significant

concentration of the samples after

degree the

was

WVTR in both

concentration of

WVTR has been

d-limoneme

measured

was reduced

during

being measured)

sides of

the film (inside and outside

difference.

39

face) to

establish

any

7-

To

use

Scanning

Electron

to observe film behavior at the

Microscopy

microscopic

level.

In

addition

to the

previous

the

following

After the film is saturated,

recommendations, this study

scenarios:

film? Would the WVTR

follow the

same

what

of

function

happens

from it? Such

when

the d-limoneme is

the films undergoing opposite

water

questions are

process

even after

permeability

important because

at

macroscopic

2-

The

level)

after

The

films? Can

The Importance

of

This study

this is

on

the

not

tell if

presence of d-

microscopic and

WVTR forever.

processes:

bigger

the

the films (at a

or perhaps the same

packaging

metallization prevent

on

compounds

films permeability based

or

films

used

for this

coating, metallization,

smaller

changes on

impact

barrier

on

and

printed

or

properties caused

these films. Can one predict which

on chemical structure?

this Study:

proves

that a previous understanding of the

different films

packaging

interactions that may

their packaging materials is necessary

for food items. Studies

whether

done,

lowering the

different films

some common

products and

package system

determine

on

made on

the d-limoneme is

compound?

compounds will affect

between food

irreparable thus

of other organic

effect

d-limoneme

Does d-limoneme have

by this organic

are

undergoing

printing.

metallized

changes

d-limoneme

effect of

study

/or

if the

or

from the

(de-absorption)

this point one can

the changes d-limoneme caused on the films are temporal (based

limoneme)

released

time observed in this experiment?

of concentration vs.

Would the films have increased

released

further investigate

could

will

can

be

interact

engineer will not

with

be

40

conducted prior

by

designing

to selecting materials to

the food to lower

surprised

before

occur

barrier

packages

properties.

providing

If

shorter

shelf

lives

after production

money in the

If
shelf-life

better

There is

started.

no

doubt

that such research can save

long run.

after

in

has been

preliminary testing,

a cost-effective

way, at least the packaging

estimate of the shelf-life so

Increasing

that he

storage and

Distributing

and

provide adequate

engineer on charge will

have

or she can make changes such as:

the ratio of food to packaging material to increase

packages as opposed to single

Shortening

the available materials can

none of

shelf-life

(i.e, larger

serving packages)

distribution times.

storing

products

in

less humid

or warm environment

Planning production based on a shorter shelf-life.

Obviously,
obtained

such

decisions may

from interaction

packaging

alternatives or

not

studies would

to look for other

be feasible in many cases, but the information

greatly

help

solutions.

41

food company to think

about

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46

60-

APPENDICES

APPENDIX

A-

Calculations for the Shelf-life

Candies using Labuza Model

of the
and

Cherry

WVTR

and

Wintergreen Mint

of films at zero organic

compound concentration

APPENDIX

B-

Calculations for the Shelf-life

of the

Candies using Labuza Model

and

point

47

Cherry and Wintergreen Mint

WVTR

of films at

the saturation

APPENDIX

A-

Calculations for
WVTR

of

films

the

Shelf-life

of the

Candies using Labuza Model

at zero organic compound concentration

48

and

Output

Shelf Life Report

Date:

Type

of

Product Name: nfectionary

14/10/02

Package 100 LMB

Product

Product Weight

Initial Relative

of

0.01

Humidity (%)

30

(%)

0.1

Humidity (%)

38

The Product

Critical Relative

450

(%)

Product Initial Moisture

Critical Moisture

Package Parameter:

parameters:

Film Area

3.24

meters)

0.002

Environmental Parameters:

Storage HR

Temperature

Length

Estimated Shelf

(sq

WVTR:

Life=

Page 1

345 dias

of

of

Storage

(%)

75

(22)

22

Study (days)

400

o
o

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LD

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o

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LO
CO

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o
CO
^^^

^4?

_>

CB

O)

cn

C
0)

LO
CNI

!_____

g
CD

o
0)

_.

3
CO

o
o
CM

(A

O
CO
ra
_

O
(0

__

>
ra
73

*"""

OS

LO

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o

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a

cs

o
LO

of

CM

oo

(o/0)

CO
o

It

juejuoo ejnS!0|/\|

CM
O

O
O

APPENDIX

B-

Calculations for the Shelf-life

WVTR

of

films

at

of the

Candies using Labuza Model

the saturation point

49

and

Output

Shelf Life Report

Date:

Type

of

14/10/02

Product Name: nfectionary

Package 100 LMB

Product

Product Weight

Product Initial Moisture

Initial Relative

Critical Moisture

of

450

(%)

0.01

Humidity (%)

30

The Product

Critical Relative

Package Parameter:

parameters:

(%)

0.1

Humidity (%)

38

Film Area

6.75

meters)

0.002

Environmental Parameters:

Storage HR

Temperature

Length

Estimated Shelf

(sq

WVTR:

Life=

Page 1

166 dias

of

of

Storage

(%)

75

(22)

22

Study (days)

400

o
LO

o
o

o
LO
co

o
o
CO

so
LO

(A
>
re

CM
O

i-

a)

3 5
</>
^

O
O
CM

a>
o>
ra
_.

o
CO

_s

o
(0

LO

o
o

0)
co

d>

10

o
LO

of

O
CM

LO

CM

LO

LO

(%)

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