FTIR & UV-VIS

ANALYSIS OF POLYMER Abdullah Al Ashraf

SAMPLES
Spectroscopic Analysis of Polymers (Polystyrene, LDPE)
by Using Fourier Transform Infrared & UV-Vis.
Spectrometer
 1. Introduction:

Fourier Transmittance Infrared (FTIR) is one of the ideal method of infrared

spectroscopy used to identify and analyze the chemical compounds of materials. In this
technique, Infrared radiation is directed at a sample. Some of the IR radiation is absorbed by the
sample, whereas some of it passed through(transmitted). As a result, the molecular adsorption
and transmission are represents by a means of spectrum, that creates a molecular fingerprint of
the sample [1]. FTIR-Spectroscopy is based on electromagnetic-wave absorption due to molecule
vibrations. Characteristic IR-spectra of solid and liquid samples provide qualitative and semi-
quantitative analyses.

The fingerprint of a sample with

absorption peaks which resembles the
frequencies of variations between the
bonds of the atoms making up the
material. Because each different
material is a unique combination of
atoms, no two compounds produce the
exact same infrared spectrum.

Fig.1: Schematic diagram of FTIR technique

In addition, the size of the peaks in the spectrum is a direct indication of the amount of material
present. Therefore the method is widely used to identify unknown materials, determining the
quality or consistency of a sample and the amount of components in a mixture [2].

The combination of alternating electric and magnetic fields that travel through space with
a wave motion considered as the electromagnetic radiation. Because radiation acts as a wave and
electro magnetic is a wave that have energy contingent on the frequency and wavelength which
are related by the following equation: V = C/ λ. Where V is frequency (in second), C is the speed
of the light and λ is wavelength (in meter) [3]. When radiation interacts with matter, different
processes can happen that comprises of reflection, scattering, absorbance etc. Ultraviolet and
visible (UV-Vis) absorption spectroscopy is the measurement of the attenuation of a beam of
light after it passes through a sample or after reflection from a sample surface.
In the case of UV-Vis spectrum, we consider only the absorbance of the light by matter, because
light is a form of energy and absorption of light by matter causes the energy content of the
molecules or atoms to increase. When light passes through or is reflected from a sample, the
amount of light absorbed is the difference between the incident radiation (Io) and the transmitted
radiation (I). The amount of light absorbed is expressed as either transmittance or absorbance
[4]. Transmittance usually is given in terms of a fraction of 1 or as a percentage and is defined as
follows: T= I/I0 or %T = (I/I0)× 100
Whereas, absorbance is defined as A = -log T
When light passes through the compound, energy from the light is used to promote an electron
from a bonding or non-bonding orbital into one of the empty anti-bonding orbitals which is the
cause of the peak to expose.

2. Experimental:

Perkinelmer branded instruments was used to run FTIR model- Spectrum 100 and UV-Vis
model -Lambda 25. test analysis. FTIR Perkinelmer is a spectrometer that determines the
material structure by applying Infrared beam on the sample and measure the ratio between the
incident to transmittance wave. The wave range used between 400-4000 cm-1. the measurement
of FTIR is possible for all kind of materials e.g. solid, powder, liquid and gas. Different types of
method and holders are used to run the gaseous samples. The device contains a crystal area of
diamond where the sample is placed and the pressure gauge is set. Crystal area should be cleaned
to be able for accurate measurement. Solid or powder sample should cover the crystal area and
the sample height should not be more than a few millimeters. Once the solid has been placed on
the crystal area, the pressure arm should be positioned over the crystal/sample area. The pressure
arm locks into a precise position above the diamond crystal until 50 pressure gauge. Force is
applied to the sample, pushing it onto the diamond surface [5]. Polystyrene and Low density
polyethylene was used as the sample during the analysis.

UV-Vis. Perkinelmer is a double-beam and double-monochromator spectrophotometer

(UV/VIS/NIR) with holographic gratings and tungsten-halogen (NIR) and deuterium lamps (UV-
Vis) used as sources. It is capable of measuring transmission, reflectance and absorption in solid
or liquid state materials [6]. It has an enough energy to excite electrons for anti-bonding. The
technique is quantitative. Before using the device, It should be cleaned by using acetone. First, 2
reference samples are used to calibrate the system. After calibration, one reference sample is
removed and replaced by the original sample. The sample was polystyrene and was dissolved in
xylene as a solvent.

3. Results & Discussion:

Fig.1: FTIR spectrometer result for Sample 1

FTIR results for sample 1 is shown in Fig.1. The absorbance peaks are located in a wide
range of spectra scale. The first peak at 3025.63cm-1 is for aromatic C-H stretching vibration,
the second peak is for C-H stretching at 2921.61cm-1 occurred due to the presents of some
impurities on the sample. The next three peaks that are located at 1600, 1492 and 1451 cm-1
respectively indicates aromatic C-H bond stretching vibration. The peaks at 1260, 1017, 796,
749, 695 cm-1 corresponds to aromatic C-H deformation vibration [7]. The result of sample-1
is a qualitative and confirmed that the vibrations positions belongs to Polystyrene which
further confirmed by the reviewed literature [8].
 Fig.2: FTIR spectroscopy result for sample 2

The FTIR result of sample 2 is shown in Fig.2. The peak at 3392 is for O-H stretching
probably because of the presence of moisture on the sample. Peaks at 2916 and 2848 cm-1
are corresponds to C-H asymmetric and symmetric stretching band respectively. The peaks at
1462, 1377, 1262, 729 and 719 cm-1 are corresponds to C-H bending deformation, CH3
symmetric deformation, twisting deformation and rocking deformation respectively. The
result of sample-2 is a qualitative and confirmed that the vibrations positions belongs to
LDPE which further confirmed by the reviewed literature [9].

maximum absorption at
this wavelength UV-Vis. diagram of Polystyrene
3
λmax= 238nm
2.5
2
Absorbance

1.5
1 Polystyrene

0.5
0
0 100 200 300 400 500 600 700 800 900
-0.5
Wave length (nm)

Diagram 1: UV-Vis result for Polystyrene sample.

Diagram 1 shows the UV-visible absorption spectrum for polystyrene. Absorbance on the
vertical axis is the measure of the amount of light absorbed. The higher the value, the more of a
particular wavelength is being absorbed. The absorption peaks at a value of 238 nm. This is in
the ultra-violet and so there would be no visible sign of any light being absorbed so the
polystyrene is colourless. You read the symbol on the graph as "lambda-max". in polystyrene-
(C8H8)n, there are no non-bonding electrons. That means that the only electron jumps taking
place (within the range that the spectrometer can measure) are from pi bonding to pi anti-
bonding orbitals [10-12].

4. Conclusion:
The properties of the sample were successfully determined by using FTIR and UV-Vis.
spectroscopy techniques. We could illustrates that the use of spectroscopy methods is decent to
use in measuring the functional properties and bonding vibration of compounds that provides
precise & accurate result.
References:
[1] Griffiths, P. and De Haseth, J. (2007). Fourier transform infrared spectrometry. Hoboken,
N.J.: Wiley-Interscience.
[2] Labcompare.com, (2014). Infrared Spectroscopy (IR / FTIR) - Labcompare. [online]
Available at: http://www.labcompare.com/Spectroscopy/165-Infrared-Spectroscopy-IR-FTIR
[Accessed 26 Oct. 2014].
[3] Owen, T. (2000). Fundamentals of UV-visible spectroscopy. [Waldbronn]: Agilent
Technologies.
[4] Human, M. (1985). Basic UV/visible spectrophotometry. Cambridge: Pharmacia LKB
Biochrom.
[5] Anon, (2014). [online] Available at: http://www.research.usf.edu/rf/docs/perkin-elmer-
spectrum-100-ftir-users-guide.pdf [Accessed 28 Oct. 2014].
[6] Anon, (2014). [online] Available at:
http://people.bath.ac.uk/gp304/uv/PerkinElmer_Lambda35_manual_EN.pdf [Accessed 28 Oct.
2014].
[7] Sites.google.com, (2014). Polystyrene (PS) - ISU MatE453/MSE 553 - Lab 3 - FTIR.
[online] Available at: https://sites.google.com/site/isumate453lab3group8/data/polystyrene-ps
[Accessed 29 Oct. 2014].
[8] Wu, H., Wu, S., Wu, I. and Chang, F. (2001). Novel determination of the crystallinity of
syndiotactic polystyrene using FTIR spectrum. Polymer, 42(10), pp.4719--4725.
[9] Gulmine, J., Janissek, P., Heise, H. and Akcelrud, L. (2002). Polyethylene characterization by
FTIR. Polymer Testing, 21(5), pp.557--563.
[10] Pinto, L., Goi, B., Schmitt, C. and Neumann, M. (2013). Photodegradation of polystyrene
films containing UV-visible sensitizers. Journal of Research Updates in Polymer Science, 2(1),
pp.39--47.
[11] Li, T., Zhou, C. and Jiang, M. (1991). UV absorption spectra of polystyrene. Polymer
bulletin, 25(2), pp.211--216.
[12] Chemguide.co.uk, (2014). UV-visible absorption spectra. [online] Available at:
http://www.chemguide.co.uk/analysis/uvvisible/theory.html [Accessed 29 Oct. 2014].
Appendix:

frequency, cm–1 bond functional group

3640–3610 (s, sh) O–H stretch, free hydroxyl alcohols, phenols
3500–3200 (s,b) O–H stretch, H–bonded alcohols, phenols
primary, secondary amines,
3400–3250 (m) N–H stretch
amides
3300–2500 (m) O–H stretch carboxylic acids
–C(triple bond)C–H: C–H
3330–3270 (n, s) alkynes (terminal)
stretch
3100–3000 (s) C–H stretch aromatics
3100–3000 (m) =C–H stretch alkenes
3000–2850 (m) C–H stretch alkanes
2830–2695 (m) H–C=O: C–H stretch aldehydes
2260–2210 (v) C(triple bond)N stretch nitriles
2260–2100 (w) –C(triple bond)C– stretch alkynes
1760–1665 (s C=O stretch carbonyls (general)
1760–1690 (s) C=O stretch carboxylic acids
1750–1735 (s) C=O stretch esters, saturated aliphatic
aldehydes, saturated
1740–1720 (s) C=O stretch
aliphatic
alpha,beta–unsaturated
1730–1715 (s) C=O stretch
esters
1715 (s) C=O stretch ketones, saturated aliphatic
alpha,beta–unsaturated
1710–1665 (s) C=O stretch
aldehydes, ketones
1680–1640 (m) –C=C– stretch alkenes
1650–1580 (m) N–H bend primary amines
1600–1585 (m) C–C stretch (in–ring) aromatics
 1550–1475 (s) N–O asymmetric stretch nitro compounds
1500–1400 (m) C–C stretch (in–ring) aromatics
1470–1450 (m) C–H bend alkanes
1370–1350 (m) C–H rock alkanes
1360–1290 (m) N–O symmetric stretch nitro compounds
1335–1250 (s) C–N stretch aromatic amines
alcohols, carboxylic acids,
1320–1000 (s) C–O stretch
esters, ethers
1300–1150 (m) C–H wag (–CH2X) alkyl halides
1300–1150 (m) C–H wag (–CH2X) alkyl halides
1250–1020 (m) C–N stretch aliphatic amines
1000–650 (s) =C–H bend alkenes
950–910 (m) O–H bend carboxylic acids
910–665 (s, b) N–H wag primary, secondary amines
900–675 (s) C–H "oop" aromatics
850–550 (m) C–Cl stretch alkyl halides
725–720 (m) C–H rock alkanes
–C(triple bond)C–H: C–H
700–610 (b, s) alkynes
bend
690–515 (m) C–Br stretch alkyl halides

Abbreviations: v - variable, m - medium, s - strong, br - broad, w - weak