A NOVEL FTIR ANALYSER for

ACETALDEHYDE in PET
CONTAINERS

Mauro PROFAIZER
R&D Sanpellegrino Nestl Waters Italy
INTRODUCTION

Today, the containers for mineral waters and other

beverages are manufactured mostly in plastic (PET).

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INTRODUCTION
PET Resin
Bottles
Preforms

Injection moulding Blow moulding

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WHAT IS ACETALDEHYDE (AA)?

Injection stage PET pellets

High temperature Molten PET

AA generation

9 Acetaldehyde (AA) is naturally occurring in many foods

and it is not toxic when ingested.
9 But, AA is able to alter the neutral taste of water,
imparting a sweety flavour even at very low levels.
9 Thus, the industry needs to control AA in the preforms.

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ACETALDEHYDE MEASUREMENT

The reference method

is headspace gas
cromatography Labour
(HS-GC) after intensive
sample grinding. method
It requires manual
preparation of the
sample, which
introduces potential
error sources and
increases the
analysis time. AA is
measured in ppm
(g/g).

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THE FTIR ANALYSER ALTERNATIVE

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THE FTIR ANALYSER: HEATING BLOCK

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THE FTIR ANALYSER: GAS CELL

Variable Pathlength cell Model 20-V

from Infrared Analysis, Inc.

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EXAMPLES OF PREFORMS SPECTRA

Aldehydes bands

CO bands
H2O bands

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PREFORMS SAMPLING

9 Both techniques (GC-HS and FTIR) are destructive.

9 Preforms from consecutive shots and from the same
mould cavity were taken each time.
9 FTIR analyses were always performed first, on the same
day of sampling.
9 Reference analyses (GC-HS) were performed the next
day, after preform storage at 18C.
9 A total of 286 preforms were analysed, having 5 different
sizes, 2 colours and made with 2 different PET types.

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PRETREATMENT OF THE SPECTRA
1. Conversion to absorbance
2. Baseline correction
3. Wavelength truncation below 800 cm-1
4. Wavelength exclusion of some of the H2O and CO bands, namely
1500-1680,1880-2590, 3200-4000 cm-1
5. Division of the absorbance values by a RELEASE FACTOR, linked to
the geometry of the preforms (signal correction)
6. Mean centering

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THE RELEASE FACTORS
Why do we need release factors? Amount of AA diffused per 1 ppm of initial AA in
the preform
Large 9
preform 8.2

Mass of AA diffused [ g]
8
7
6
5
Same initial 4
AA content 3
2
1
0
0 10 20 30 40
Heating time [min]

Amount of AA diffused per 1 ppm of initial AA in

Small the preform
9
preform

Mass of AA diffused [ g]
8
7
6
5
4
3 3.3
2
1
0
0 10 20 30 40
Heating time [min]

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THE RELEASE FACTORS

The diffusion of AA during heating is not a steady-state

process.

Different preforms sizes mean:

9 Different surfaces
9 Different temperature distributions

To get the release factors, we used a numerical modeling

of the physical system (FEM), for each preform type.

The problems to solve for simultaneously were:

9 conductive-radiative heat transfer
9 AA vapour diffusion

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 C

The different colours indicate

the temperature distribution
AA streamline

Heating bands
THE RELEASE FACTORS

Different preform sizes

No signal
correction Initial AA =
4.5 ppm for
all preforms

Signal Initial AA =
correction 4.5 ppm for
Different preform sizes
all preforms

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PLS1 ALGORITHM and MAHALANOBIS DISTANCE
The standard PLS1 of The
Unscrambler was used to
calibrate and validate the At least 70 samples are required.
system (only mean centering
was used).
0.5

Cross-valid. SEP in calibration [ppm]

The calibration set was selected 0.45

applying the Neighbourhood 0.4

Mahalanobis Distance criterion 0.35

in the normalised PC space.
The spectrum with the most
0.3

neighbours at a distance 0.25

smaller than a defined 0.2

threshold is detected and all 0 20 40 60 80 100 120 140 160 180

the neighbours are eliminated. N. of samples in the calibration set chosen as per MD

This procedure is repeated

among the the remaining
spectra.

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PRINCIPAL COMPONENTS EXTRACTED

Loading weights of first PC obtained by PLS1 applied to

AA, plotted in comparison with a standard of AA

Loading weights for 1st component

AA standard injection

40 00 .0 36 00 32 00 28 00 24 00 20 00 18 00 16 00 14 00 12 00 10 00 80 0.0
cm-1

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TRAINING DATA SET

Cross-validation of a calibration data set of 74 spectra

r = 0.98
RMSECV = 0.35 ppm
SECV = 0.35 ppm
SDD(GC-HS) = 0.30 ppm*

*Standard deviation of difference calculated on triplicates of 44 samples

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TEST SET

AA validation on a data set of 128 spectra

r = 0.96
RMSEP = 0.34 ppm
SEP = 0.34 ppm
SDD(GC-HS) = 0.30 ppm*

*Standard deviation of difference calculated on triplicates of 44 samples

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INDIPENDENT VALIDATION

AA validation on a totally indipendent data set of 32 spectra

r = 0.95
RMSEP = 0.38 ppm
SEP = 0.38 ppm
SDD(GC-HS) = 0.30 ppm*

*Standard deviation of difference calculated on triplicates of 44 samples

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CONCLUSIONS

9 A new rapid FTIR analyser for AA in PET preforms has

been developed and tested extensively.
9 A very good correlation with the reference GC technique
has been shown to exist.
9 Repeatability (SD=0.20 ppm) is just slightly higher than
the GC method (SD=0.17 ppm).
9 SEP is approximately equal to SDD and largely < 2SDD
9 The factory has now implemented the new, quicker
system since 5 months with really satisfactory results.

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 THANK
YOU!

A.M.D.G.

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