5/5/22, 06:50 White without Titanium-Dioxide

MENU

PLUS Nanostructures

White without Titanium-Dioxide

Porous Nanostructures as Replacement for White
Pigments

An innovative process allows to fabricate thin, white polymer surfaces

without white pigments. For that, the polymer is foamed with supercritical
CO2 resulting in a fine structure of nanobubbles. Film thicknesses of a few 10
µm are sufficient to obtain a perfect white surface.

Specialist Article 1

11th Aug 2020

The white beetle Cyphochilus insulanus is almost completely covered with white scales
https://en.kunststoffe.de/a/specialistarticle/white-without-titanium-dioxide-241872 1/14
5/5/22, 06:50 White without Titanium-Dioxide
© Markus Breig, KIT

MENU

For all kinds of consumer goods, a bright white surface is frequently desired to
convey purity and cleanliness. Titanium dioxide (TiO2) is the most commonly
applied white pigment. It is used in many industrial branches and gives plastic
packaging, coatings and paints, as well as food and cosmetics, an opaque and
brilliant whiteness [1, 2]. However, rising raw material costs, the labor-
intensive extraction and large carbon footprint, as well as the cost-intensive
disposal of partly harmful by-products, motivate to replace TiO2 in white
surfaces.

In recent years, there has also been growing concern that TiO2 could be
harmful to human health and the environment. In particular nanometer-sized
TiO2 particles are repeatedly criticized [3]. In France, these concerns have led
to a ban on TiO2 as a food additive [4]. In addition, in the long term, TiO2
could pose a similar problem to that of microplastics, as chemically inert TiO2
particles could be released finally from the embedding medium and
subsequently accumulate in the environment.

Nevertheless, there are many good reasons to use TiO2 as a white pigment
[2]. Some authors and engineers do not see an alternative to this material (see
Kunststoffe international 6–7/2019, [5]). Due to their high optical refractive
index, TiO2 particles scatter light particularly effective, since a strong contrast
of the optical density the matrix (polymer, binder, etc.) is achieved. This
enables a very effective scattering of all wavelengths of visible light at the
interface between medium and TiO2 particles, resulting in a white color
impression and good opacity.

However, a look at nature shows that the classical industrial approach to use
small particles with high optical density as scattering centers is not the only
possible way to effectively scatter light. In nature, there are several examples
of white materials where a different scattering mechanism is utilized. Air-filled
cavities instead of pigment particles act as scattering centers.

https://en.kunststoffe.de/a/specialistarticle/white-without-titanium-dioxide-241872 2/14
5/5/22, 06:50 White without Titanium-Dioxide

The best-known example of this principle in biophotonics is the white beetle

MENU
Cyphochilus insulanus (Title figure), which originates from Southeast Asia [6,
7]. Its white color probably serves as a camouflage, since it lives in a shady
environment on a suitably colored fungus [8]. The upper side of its body is
almost completely covered with white scales, which are about 60 µm wide
and 200 µm long. The scales are porous inside and consist of a network of
fibrous structures (Fig. 1). Despite their small thickness of less than 10 µm,
the scales scatter light of any wavelength almost perfectly. This effect has
been intensively investigated by various groups in recent years and served as
a model for the development of scattering materials [9–12].

Fig. 1. The scanning electron microscopy image shows the inside of a scale of the white
beetle Cyphochilus insulanus. The porous structure consists of chitin and scatters light so
well that a layer thickness of only 10 µm is sufficient to make it appear white
© Julia Syurik, KIT

The example of the beetle Cyphochilus illustrates very well the difference
between natural and man-made structures. While engineers often develop
solutions using materials consisting of many different chemical elements, the
https://en.kunststoffe.de/a/specialistarticle/white-without-titanium-dioxide-241872 3/14
5/5/22, 06:50 White without Titanium-Dioxide

natural ones are usually limited to a single basic material with a rich, complex
MENU
three-dimensional structure. One can be only amazed by mechanical, optical
or physico-chemical properties of such natural solutions. Biomimetics is
concerned with understanding, abstracting and imitating the phenomena of
nature in order to make them technically usable. Therefore, it often leads to
promising approaches which might never have been found in any other way.

The above described effect found in the beetle’s scales can also be
reproduced in man-made materials, for example, by introducing in their
volume very small, air-filled cavities. This effect can be observed in everyday
life by watching soapsuds or sea spray. Light is scattered at the interface
between the pore and the surrounding medium such as water or polymer. The
high optical density contrast results from the low optical density of air
compared to the surrounding medium. The main trick is to make these
bubbles tiny enough to enable a technical use as a coating. When the pore
size is reduced to a few hundred nanometers, all wavelengths of visible light
are scattered effectively, so that even thin layers of the porous material
appear white.

INFO

Advantages at a Glance

Coloration solely caused by nanostructuring without any pigments.

A tiny layer thickness of about 10 µm is sufficient to achieve a high scattering.
The polymeric material remains pure, which facilitates recycling.

To-Dos till Readiness for Series Production

To up-scale the demonstrated technology according to manufacturer’s needs, for

example, for larger films.
The foamed material cannot directly replace other white pigments in existing production
processes. New approaches are required, to apply it as a coating or to add it as a new
type of pigment particles into a matrix.

Researchers at the Karlsruhe Institute of Technology (KIT), Karlsruhe,

Germany, have developed a process for the production of such coatings. For
this purpose, polymers are foamed with the aid of supercritical CO2 (Fig. 2).
https://en.kunststoffe.de/a/specialistarticle/white-without-titanium-dioxide-241872 4/14
5/5/22, 06:50 White without Titanium-Dioxide

As a non-toxic, inert and non-flammable gas, CO2 has become very important
MENU
not only for foaming, but for various other applications, for example for
polymer blending and simplified polymer modification processes (with CO2 as
the carrier as well as the swelling agent) or for the production of polymeric
particles [14, 17]. This is mainly because it acts as a plasticizer for polymers
with good CO2 solubility. Under the influence of CO2 the glass transition
temperature of these polymers drops significantly [15]. Due to the good
diffusion properties, the gas is often used in the supercritical state at a
pressure of over 73.75 bar and a temperature of over 31 °C. This aggregate
state lies between liquid and gas state.

White Color due to Foaming

In the process developed at KIT (Fig. 2), the polymer is first saturated with
CO2 under constant temperature and pressure conditions, typically until the
gas concentration in the sample reaches the solubility limit. While CO2
diffuses into the polymer, its glass transition temperature decreases. Under
certain conditions, the glass transition temperature is even lower than room
temperature [16]. The polymer swells and also becomes viscous if its
temperature is higher than the current glass transition temperature.

Fig. 2. Foaming with supercritical CO2 enables the creation of nano-sized pores in polymers
such as PMMA. This means that the actually transparent material turns white without
adding pigments due to the structure alone
Source: Luisa Borgmann, KIT, graphic: © Hanser

https://en.kunststoffe.de/a/specialistarticle/white-without-titanium-dioxide-241872 5/14
5/5/22, 06:50 White without Titanium-Dioxide

In the next step, a sudden drop in pressure induces thermodynamic instability.

MENU
This leads to a supersaturation of the polymer, whose solubility for CO2 is
much lower under the new conditions. As a result of the supersaturation,
nucleation occurs, and for further growth the nuclei must reach a critical size.
Now pore growth can take place by diffusion of gas molecules from the
polymer matrix into the newly formed nuclei.

While the gas diffuses from the polymer matrix into the growing pores and
partly out of the material, the glass transition temperature increases again.
The pore structure solidifies when the glass transition temperature has risen
to the actual temperature of the sample [17–19]. Due to the foamed porous
structure the polymer turns white as shown in Figure 2 by the example of a
previously transparent PMMA film. The pore size and density can be
controlled by the process parameters and other process modifications. For
example, a higher temperature ensures longer time for pore growth and thus
larger pores, while a reduction in pressure moderates the pore density.

The optical spectra in Figure 3 show how effectively light is scattered at the
nanopores. For these examples, thin PMMA films with different, precisely
defined layer thicknesses, were applied to a glass substrate and foamed with
supercritical CO2 with optimized parameters. The films were then optically
analyzed. The reflection of these films in the visible range is almost constant
and increases with the thickness of the foamed PMMA. An effective layer
thickness of 9 µm is sufficient to achieve a reflection of approx. 60 %. The
effect increases with layer thickness and at a thickness of 79 µm significantly
more than 90 % of the incident light is reflected. The inset in the figure shows
the inner structure of the film with an effective layer of 9 µm, recorded by
scanning electron microscopy (SEM). The pores have diameters of several 100
nm and are distributed irregularly in the polymer.

https://en.kunststoffe.de/a/specialistarticle/white-without-titanium-dioxide-241872 6/14
5/5/22, 06:50 White without Titanium-Dioxide

MENU

Fig. 3. The graph on the left shows the reflection as a function of wavelength for different
film thicknesses. The SEM image shows the inner structure of an approx. 10 µm thick
foamed PMMA film. The graph on the right compares the foamed PMMA films with other
white materials
Source: Julia Syurik, KIT, graphic: © Hanser

The right graph in Figure 3 compares the scattering of the foamed PMMA
films with white paper, so-called “photonic glass”, and the scales of the
Cyphochilius beetle. The transmission of light is plotted as a function of the
inverse material thickness. This so-called “Ohm’s law for light” gives an
indication of the mean free path length of light and thus allows a simple
comparison between different materials [7, 11]. With this method, the curve
for white paper has the steepest slope, while the curve for “photonic glass” is
much flatter. The scales of the white beetle enable the most effective
scattering in our comparison and the corresponding curve is very flat, since
the mean free path of light scattering is only about 1.47 µm. The foamed
PMMA films perform slightly worse than “photonic glass”, but much better
than white paper. For the human eye, a film of only 10 µm thickness already
appears perfectly white.

Suitable for PMMA, TPU and PLA

The presented process successfully avoids the need for potentially harmful
pigments by creating porous polymeric structures. Just like the bubbles of
shaving or bath foam, the structure of these also scatters light, making the

https://en.kunststoffe.de/a/specialistarticle/white-without-titanium-dioxide-241872 7/14
5/5/22, 06:50 White without Titanium-Dioxide

material appear white. The technique is inexpensive and suits not only for
MENU
PMMA but also for various thermoplastics such as thermoplastic
polyurethanes (TPU) and biodegradable polylactides (PLA).

The thin polymer films are very flexible and light. Although nanostructuring
changes the elastic properties of the material, the films are mechanically
stable enough [20] to be thermoformed and applied as a coating to various
surfaces [11].

Foaming with supercritical CO2 does not leave any residues of solvents, as the
process of generating a pore structure is purely physical. Accordingly, there is
great potential in applications where solvent residues are to be avoided and
where TiO2 alternatives are particularly in demand, for example in food and
cosmetics packaging. The increasing demand for efficient recycling of
products is another advantage, as the inserted pores are much easier to
reverse than embedded particles. If the polymer is heated accordingly, the
nanobubbles disappear without residue. Furthermore, the localized heating
above the material’s glass transition temperature allows the white films to
become locally transparent again and can be beneficial for ink-free stamping
or counterfeit protection.

https://en.kunststoffe.de/a/specialistarticle/white-without-titanium-dioxide-241872 8/14
5/5/22, 06:50 White without Titanium-Dioxide

MENU

Fig. 4. The process is also suitable for foaming PMMA particles. In the future, these
particles will be further tested for their suitability as pigments
Source: Luisa Borgmann, KIT, graphic: © Hanser

Since many white consumer goods from packaging to furniture surfaces are
made of polymers or polymeric coatings with added TiO2, there is a wide
range of applications for the foamed films. In addition, there is a growing
willingness to replace TiO2 particles. On the one hand this is desired by end
users and on the other hand by manufacturers expecting further legal
restrictions for TiO2 usage in the future.

However, the foamed material is not a 1:1 replacement for TiO2 or other
white pigments. It requires new approaches to apply the foamed polymer as a
film. Instead of using complete polymer coatings or foils, foamed particles
could also be introduced into a plastic matrix. Figure 4 shows that particles
can also be foamed: an originally transparent particle of PMMA appears white
after foaming. This technique can also be used to whiten materials that
cannot be foamed directly.

https://en.kunststoffe.de/a/specialistarticle/white-without-titanium-dioxide-241872 9/14
5/5/22, 06:50 White without Titanium-Dioxide

THE AUTHORS
MENU

Luisa Borgmann, M.Sc., has been working on the further development of the method in her
PhD at KIT since 2019.

Dr. Julia Syurik developed the presented method during her time at KIT from 2012 to 2017.

Prof. Dr. Hendrik Hölscher has been head of the Department of Bionic Surfaces at KIT
since 2008; hendrik.hoelscher@kit.edu

Acknowledgments

It is a pleasure to thank Gabriele Wiegand and Siegbert Johnsen from KIT for their
continuous support of this project.

Advert

Downloads

White without Titanium-Diox …

https://en.kunststoffe.de/a/specialistarticle/white-without-titanium-dioxide-241872 10/14
5/5/22, 06:50 White without Titanium-Dioxide

Issue MENU

Issue 2020/06
Page: 13 to 16

Keywords

Dyes and Pigments | Dyes | Foaming / Reactive Processing | Additives

Company Information

Karlsruher Institut für Technologie (KIT)

D 76131 Karlsruhe
info@kit.edu
www.kit.edu

References

1. Weir, A., et al.: Titanium Dioxide Nanoparticles in Food and Personal Care Products.
Environmental Science & Technology 46 (2012) 4: p. 2242–2250

2. Winkler, J.: Titan Dioxide – Production, Properties and Effective Usuage. 2nd Revised Edition.
Vincentz Network, Hannover 2013

3. Nau, K. and H.F. Krug, Sichere Nanomaterialien?! Physik Journal 15 (2017): P. 29–34
https://en.kunststoffe.de/a/specialistarticle/white-without-titanium-dioxide-241872 11/14
5/5/22, 06:50 White without Titanium-Dioxide

MENU
4. Frankreich verbietet umstrittenen Weißmacher Titandioxid. 2019; Quelle:
https://www.spiegel.de/gesundheit/ernaehrung/titandioxid-frankreich-verbietet-weissmacher-
in-lebensmitteln-a-1263406.html;
https://www.legifrance.gouv.fr/eli/arrete/2019/4/17/ECOC1911549A/jo/texte

5. Schlotter, U. and I. Sartorius: An Irreplaceable Additive – Use and Recovery of TiO2 in Plastics
Products. Kunststoffe international 6–7 (2019): p. 6–8

6. Vukusic, P., B. Hallam, and J. Noyes: Brilliant Whiteness in Ultrathin Beetle Scales. Science 315
(2007): p. 348

7. Burresi, M., et al.: Bright-White Beetle Scales Optimise Multiple Scattering of Light. Scientific
Reports 4 (2014): P. 6075

8. Wilts, B.D., et al.: Evolutionary-Optimized Photonic Network Structure in White Beetle Wing
Scales. Advanced Materials. 30 (2018) 19: p. e1702057

9. Hallam, B.T., A.G. Hiorns, and P. Vukusic: Developing optical efficiency through optimized
coating structure: biomimetic inspiration from white beetles. Applied Optics 17 (2009): p. 3243–
3249

10. Akerlind, C., et al.: Scattering and polarization properties of the scarab beetle Cyphochilus
insulanus cuticle. Applied Optics 54 (2015) 19: p. 6037–6045

11. Syurik, J., et al.: Bio-inspired, large scale, highly-scattering films for nanoparticle-alternative
white surfaces. Scientific Reports 7 (2017): p. 46637

12. Syurik, J., et al.: Bio-inspired Highly Scattering Networks via Polymer Phase Separation.
Advanced Functional Materials 28 (2018) 24: p. 1706901

13. US Patent 4,473,665: Microcellular closed cell foams and their method of manufacture
(1984) Martini-Vvedensky, J.E., N.P. Suh, and F.A. Waldman

14. Hentze, H. and M. Antonietti: Porous polymers and resins for biotechnological and
biomedical applications. Journal of Biotechnology 90 (2002) 1: P.p. 27–53

15. Chiou, J.S., J.W. Barlow, and D.R. Paul: Plasticization of Glassy-Polymers by CO2. Journal of
Applied Polymer Science 30 (1985) 6: p. 2633–2642

16. Goel, S.K. and E.J. Beckman: Generation of Microcellular Polymeric Foams Using
Supercritical Carbon-Dioxide. 1. Effect of Pressure and Temperature on Nucleation. Polymer
Engineering and Science 34 (1994) 14: p. 1137–1147

17. Tomasko, D.L., et al.: A review of CO2 applications in the processing of polymers. Industrial &
Engineering Chemistry Research 42(2003) 25: p. 6431–6456

18 Costeux S : CO2-Blown Nanocellular Foams Journal of Applied Polymer Science 131(2014)

https://en.kunststoffe.de/a/specialistarticle/white-without-titanium-dioxide-241872 12/14
5/5/22, 06:50 White without Titanium-Dioxide
18. Costeux, S.: CO2-Blown Nanocellular Foams. Journal of Applied Polymer Science 131(2014)
23: p. MENU
2633–2642

19. Okolieocha, C., et al.: Microcellular to nanocellular polymer foams: Progress (2004–2015)
and future directions – A review. European Polymer Journal 73 (2015): p. 500–519

20. Syurik, J., et al.: Bio-inspired micro-to-nanoporous polymers with tunable stiffness. Beilstein
Journal of Nanotechnology 8 (2017): p. 906–914.

Related Content

PLUS Thermoforming
PLUS Trends
PET: From A to C
What Will Be the Co-
PLUS Titanium Oxide lor of 2021?
An Irreplaceable
Additive

1/5

Follow us

About the Journal My Login

Contact Subscription

Jobs

Media Data

Newsletter
Get the latest business information for free!

Subscribe
https://en.kunststoffe.de/a/specialistarticle/white-without-titanium-dioxide-241872 13/14
5/5/22, 06:50 White without Titanium-Dioxide
Subscribe

MENU

More Technical Portals

Kunststoffe

FORM+Werkzeug

HANSER automotive

QZ Qualität und Zuverlässigkeit

WB Werkstatt + Betrieb

Hanser Divisions

HANSER Fachbuch

HANSER Literaturverlage

IMPRINT TERMS AND CONDITIONS PRIVACY POLICY

https://en.kunststoffe.de/a/specialistarticle/white-without-titanium-dioxide-241872 14/14