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Optical properties of photochromic pigment

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XXIV International Congress IFATCC 2016

OPTICAL PROPERTIES OF PHOTOCHROMIC PIGMENT

INCORPORATED INTO POLYPROPYLENE FILAMENTS
A. P. Periyasamy, M. Viková and M. Vik

Faculty of Textile Engineering, Technical University of Liberec, Czech Republic

martina.vikova@tul.cz

Abstract: This paper reviews the impact of different concentrations of photochromic pigment as well as
different drawing ratios with respect to the optical properties of multifilament. Temperature variation may
induce very significant and different effects on the behavior of the photochromic system, so there is
a special device such as LCAM FOTOCHROM available in LCAM – TUL which helps us to measure
various optical properties like kinetics of the growth and decay. The results are showing there is
a significant change in the optical properties of polypropylene fibers with respect to drawing ratio.
Key Words: photochromism, colorimetry, functional dyes, smart fabrics, polypropylene

1 INTRODUCTION changing reactions are illustrated in Scheme 1.

Photochromism denotes a reversible color change
upon exposure to light [1-3]. Photochromic
materials have received extensive attention since
they are applicable to photoactive media, such as
optical storage, optical switches, sensors, smart
windows, and so forth [4-14].During the 1950’s,
Hirschberg suggested the term of photochromism
(which comes from Greek words phos, meaning
light, and chroma, meaning color) for the color
changing materials [15, 16]. Photochromism is
defined by IUPAC as a “Light-induced reversible
change of color”, the reversible color changing by
the exposure to electromagnetic radiation (mainly
UV irradiation) [1, 2, 17-20]. Generally,
photoproducts absorb at shorter wavelengths
than their precursor. This is termed negative
photochromism; the photochromic mechanism is
illustrated in Figure 1 [21].
Figure 1 Reaction scheme and UV-VIS
spectra of a photochromic compound [36]
Chromic materials are classified in several types,
of which photochromic and thermochromic
materials are popular due to their wide scope [18].
Typical photochromic compounds and their color
There are huge differences between
photochromism and thermochromism: in
photochromism, the color change is normally
associated with electromagnetic radiation, whereas
heat is responsible for change of color in
thermochromism [22]. Therefore, the presence
of light alone is not sufficient to induce
a photochemical reaction; the light must also have
the correct wavelength to be absorbed by the
reactant species. The reversible change of a single
chemical species between two states having
distinguishably different absorption spectra can be
induced in at least one direction by electromagnetic
radiation [3, 18, 23-25] and furthermore, these two
forms may differ in many other physical properties
such as their redox potential [16, 26], fluorescent
intensity, dipole moment [27, 28], molecular shape
etc.
A more common scenario is that the initial
photochromic species absorbs in the UV range and
upon photolysis produces a colored photoproduct
absorbing in the visible region of the spectrum
(positive photochromism) [29, 30], and the process
involves interconversion of a single molecule
between two chemically distinct forms [31-35].
The activating radiation generally is in the UV
region (300 to 400 nm) but could be in the visible
(400 to 700 nm) [10, 32, 33].
Generally, photochromic compounds are
photochemically stable in terms of absorption
of radiation, but become thermodynamically
metastable in state B from which they revert back to
(reversible color changing) A by the absorption
of electromagnetic radiation or thermal energy
(Eq. 1).
(1)

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Scheme 1 Photochromic (heterolytic cleavage/photocyclization) reaction of spirooxazines [1]

Basic characteristics which are required for the different ratios, the process parameters for the
photochromic materials are given below [15]: drawing process are given in Table 2.
a) Light sensitivity
b) Spontaneous reversibility (and)
c) Color changes.
The B state should be moderately stable;
a. Also B should absorb radiation in different
region of the spectrum than A, and;
b. The change of B A should occur either
thermally or by exposure to electro-magnetic
radiation.
Polypropylene (PP) is a polymer, which is
a member of the ‘polyolefin’ (polymers produced
from alkenes) family. It is a highly versatile material
that has many beneficial physical properties. Figure 2 Samples of photochromic polypropylene
Polypropylene provides superior qualities and is the multifilament
most versatile and cost effective fiber (polymer) in
comparison with other thermo-forming and Table 1 Various parameters which were used in melt
polyolefin materials. It has good impact strength, spinning
surface hardness, excellent abrasion resistance Metallocene Polypropylene
Polypropylene
and resistance to a wide variety of acids, alkali and PP HM 562 R
solvent solutions with a temperature range up to Temperature of melt
220°C
spinning
93°C. For this present research work, we have
5-Chloro-1,3-dihydro-1,3,3-
produced photochromic pigment incorporated in PP Photochromic pigment trimethylspiro[2H-indole-2,3′-
multi-filaments by using four different (3H)naphth[2,1-b](1,4)oxazine]
concentrations of photochromic pigment. Pigment concentration in 0; 0.25; 0.5; 1.5; 2.5 %
The filaments were produced at four drawing ratios. fiber (on weight basis)
Drawing temperature (Td) 120°C
The main goal of this study was to find the Melt flow index 26.6 g/10 min
relationship between concentration of photochromic Number of holes in
13
pigments & drawing ratio with respect to the optical spinneret
properties of polypropylene filaments [37-46].

2 EXPERIMENTAL PROCEDURE Table 2 Drawing ratio and concentration of photochromic

pigments
The photochromic pigments incorporated in
Sample Composition Drawing ratio
polypropylene multifilament were produced by
1 PP 562 R 2 2.5 3 3.5
laboratory melt spinning machine and the process 2 PP 562 R + 0.25% Blue 2 2.5 3 3.5
parameters are illustrated in the Table 1. 3 PP 562 R + 0.5% Blue 2 2.5 3 3.5
The produced samples are shown in Figure 2. 4 PP 562 R + 1.5% Blue 2 2.5 3 3.2
The photochromic pigment was mechanically mixed 5 PP 562 R + 2.5% Blue 2 2.5 3 3.2
with polypropylene granulate (chips) and the
mixture added in the hopper of the extruder of the After the drawing process, the multifilament’s
melt spinning machine. After production, the optical properties were analyzed – they were
filaments were carried over for the drawing process determined by using the unique spectrophotometer
due to inferior mechanical behavior of the proto- FOTOCHROM LCAM (often commercial
filaments. The drawing process was carried out at spectrophotometers have limitations in finding out

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optical properties of photochromic materials, due to
color changing properties) which was developed
by LCAM Team at the Technical University
of Liberec. The scheme and picture of the
instrument are shown in Figures 3 and 4,
respectively. The color-measuring instrument
(spectrophotometer) determines the K/S value
of a given filament through Kubelka-Munk equation
(Eq.2) [47, 48].
2
K 1 R
(2)
S 2R
where R - reflectance percentage, K - absorption
and S - scattering of dyes.
This unique spectrophotometer is able to measure
the kinetics of color changes in exposed
Figure 3 Scheme of LCAM FOTOCHROM
Figure 4 Picture of LCAM FOTOCHROM
Vlákna a textil (3) 2016
IFATCC 2016
photochromic samples when the change is visible
by the use of Kubelka-Munk function for the
concentration of photochromic pigment and
the drawing ratio in time. Temperature variation
may induce very significant and different effects on
the behavior of the photochromic system, constant
temperature (20°C ± 2°C) was kept for all the
samples.
3 RESULTS & DISCUSSION
The results are shown in Figures 5 to 9 and they
clearly explain the relationship between Kubelka-
Munk function with respect to the drawing ratio
along with the concentration of photochromic
pigment. It has clearly shown that increasing
of drawing ratio decreases the Kubelka-Munk
value.
173
XXIV International Congress IFATCC 2016

4.0
Concen: 2.5 % 0
2
3.5 2.5
3
3.2
3.0
K/S value

2.5

2.0

1.5

1.0

0.5

0 300 600 900 1200 1500 1800 2100 2400 2700 3000
Time (Sec)
Figure 5 Impact of drawing ratios on optical properties of photochromic filaments

4.0
Concen: 1.5 % 0
2
3.5 2.5
3
3.2
3.0
K/S value

2.5

2.0

1.5

1.0

0.5

0 300 600 900 1200 1500 1800 2100 2400 2700 3000
Time (Sec)
Figure 6 Impact of drawing ratios on optical properties of photochromic filaments

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4.0
Concen: 0.5 % 0
2
3.5 2.5
3
3.5
3.0
K/S value

2.5

2.0

1.5

1.0

0.5

0 300 600 900 1200 1500 1800 2100 2400 2700 3000
Time (Sec)
Figure 7 Impact of drawing ratios on optical properties of photochromic filaments

4.0
Concen: 0.25 % 0
2
3.5 2.5
3
3.5
3.0
K/S value

2.5

2.0

1.5

1.0

0.5

0 300 600 900 1200 1500 1800 2100 2400 2700 3000
Time (Sec)
Figure 8 Impact of drawing ratios on optical properties of photochromic filaments

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4.0
Concen: 2.5 %
0
2
3.5
2.5
3
3.0 3.2
K/S value

2.5

2.0

1.5

1.0

0.5

0 300 600
Time (Sec)
Figure 9 Dependence of K/S function on time – growth and decay phase of photochromic change for different drawing
ratios λ while concentration of pigment is 2.5%

0
Equation y = a + b*x
No Weighting
2
Weight
Residual Sum 0.79768 2.5
of Squares
3
0.99364
4 Pearson's r
Adj. R-Square 0.94714 3.5 (@ 1.5 and 2.5 % are 3.2)
Value Standard Error Linear fit
B Intercept 1.1 --
B Slope 0.90851 0.1737

3
K/S (max)

0.0 0.25 0.5 1.0 1.5 2.0 2.5 3.0

Concen (%)
Figure 10 Dependence of the maximum K/S function of photochromic change for different drawing ratios λ and different
concentrations

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XXIV International Congress
This situation can be described as the effect of the
attenuating of multifilament and the reduction
of fineness and the concentration of photochromic
pigment in the mass of used polypropylene
polymer. The transformations of Kubelka-Munk 9.
function maximum value with respect to the drawing
ratio as well as concentration are shown in Figure
10.
10.
4 CONCLUSION
This research work describes the dependence 11.
of K/S values on concentrations of photochromic
pigment and various drawing ratios. From this work,
we conclude the following points:
Increasing the drawing ratio decreases the K/S
12.
values.
Even though at the same concentration different
K/S values are observed for different drawing
ratios, it seems there is a huge impact on K/S 13.
values with respect to drawing ratio.
ACKNOWLEDGEMENTS: This work was morally supported 14.
under the Student Grant Scheme (SGS-21044) by the
Technical University of Liberec, Czech Republic. The first
author is grateful to the Republic of India for providing the
best life and knowledge, also thanks to Technical
University of Liberec and Ministry of Education, Youth
and Sports of the Czech Republic for the doctoral student 15.
scholarship.
16.
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