12 Polymer Orientation and Crystallinity

Measurements by FT-IR and IR dichroism

Gaetano Lamberti(1) , Giuseppe Titomanlio(1) , Gerrit W.M.Peters(2)
(1) Department of Chemical and Food Engineering, University of Salerno, Italy
(2) Materials Technology, Department of Mechanical Engineering, Eindhoven University of Technology, the Netherlands

Introduction Case histories

Final properties of a polymeric product are determined by its 2 Quenched polypropylene films [2] and film casting
morphology that was developed as a consequence of pro- products [1] were analysed off-line (UNISA).
cessing conditions. Measurement of crystallinity and orien- 2 On-line measurements were performed during film
tation is of importance for process optimization [1]. casting by a dedicated apparatus (UNISA, Fig. 2) [1].
2 Injection moulded samples have been investigated by
a FT-IR microscope (TUE, Fig. 3) [3].
Experimental: FT-IR spectra analysis
Three IR spectra have to be collected (Fig. 1): non-polarized, -500
1.0
-250 0 250 500
1.0
-500
0.7
-250 0 250 500
0.7

Orientation factors,
f841 (crystal)
polarized parallel and perpendicularly to the flow direction.

dimensionless
0.8 f973 (average) 0.8 0.6 0.6

0.5 0.5
0.6 0.6 Xc (from unpolarized spectrum)
Xc (from polarized spectra)
750 850 950 1050 1150 1250 750 850 950 1050 1150 1250 0.4 0.4
Parallel polarized FT-IR signal 0.4 0.4
Orthogonal polarized FT-IR signal 0.3 0.3

dimensionless
Crystallinity,
Absorbance, arbitrary units

Absorbance, arbitrary units

92.63°C
96.00°C
0.2 0.2
99.64°C
0.2 0.2
103.55°C
107.75°C
108.84°C 0.0 0.0 0.1 0.1
109.96°C
111.09°C
112.25°C
113.42°C Thickness, micron S4 Thickness, micron S4
114.62°C -0.2 -0.2 0.0 0.0
115.83°C
117.07°C
-500 -250 0 250 500 -500 -250 0 250 500
118.33°C
119.61°C
120.91°C
122.24°C

129.22°C
123.59°C Figure 3 Left: orientation distribution, Right: crystallinity distribu-
134.97°C

tion, both are obtained from injection moulded sample

141.49°C
148.55°C

750 850 950 1050 1150 1250 750 850 950 1050 1150 1250
-1 -1
Wavenumber, cm Wavenumber, cm

Figure 1 Left: polarized FT-IR spectra from an iPP sample, Right: un- Future work
polarized FT-IR spectra collected during cooling In principle, the techniques can be applied on a rheometer.
Rheological responses (η, G’, G") can directly be related (be-
Crystallinity ing measured during the same experiment) to morphology (f ,
Considering a crystalline peak and a peak insensitive to Xc ). A set-up like the one sketched in Fig. 4, is under devel-
phase content, and starting from Lambert and Beer’s law, opment.
crystallinity Xc can be evaluated as follow: r

Plate-plate IR beam
Xc = (aav /acr ) (Acr /Aav ) rheometer IR mirror

Acr , Aav : absorbancies, acr , aav : absorptivities of crys-

d ZnSe
talline fraction and of a peak insensitive to phase content plates
respectively, (for iPP av = 973 cm−1 , cr = 841 cm−1 and
Sample
a 973 /a 841 = 0.79 [2]). Rheometer to IR detector
shaft
IR mirror
Orientation
The orientation factor can be obtained from Fraser’s theory Figure 4 The system under development at MATE/TUE to gather
(dichroic ratio Dν = (Aπ /Aσ )ν , for iPP K973 = K841 = 1 [2]): transmission spectra during rheology experiments

    
D −1 D0 + 2 D −1
f = = Kν Problems
D +2 D0 − 1 ν D +2 ν
2 Two opposite needs on sample thickness: (i) Rheology:
Personal δ > 300 µm to avoid excessive forces, (ii) FT-IR: δ < 150-
computer
External FT-IR
200 µm to avoid saturated absorbancies
FT-IR detector optical 2 Little room for IR mirror system positioning (ρ ≈ 1-2 cm)
guidelines Extrusion
die 2 No reliable optical fibres available to gather the spec-
tral region between 750-1000 cm−1
FT-IR spectrometer
Chill
FT-IR beam roll References:
Vertically path
travelling
[1] LAMBERTI G, BRUCATO V, TITOMANLIO G, J.Appl.Polym.Sci. 84:1981
table Cast film (2001); LAMBERTI G, LACARRUBBA V, PICCAROLO S, BRUCATO V,
Polym.Bull. submitted (2002)
[2] LAMBERTI G, TITOMANLIO G, Macrom.Symp. 185:167 (2002); LAM-
BERTI G, BRUCATO V, J.Polym.Sci.B:Polym.Phys. submitted (2002).
Figure 2 The system developed at University of Salerno to gather [3] LAMBERTI G, PETERS GWM, SCHRAUWEN BAG in preparation
transmission spectra during polymer film casting (2002).
/department of mechanical engineering PO Box 513, 5600 MB Eindhoven, the Netherlands