de

Views & News

The very early days of LC-elastomers (their “invention”)

Created by Alexey Eremin vor 4 Tagen um 12:05 Uhr:

Rudolf Zentel
Dept. of Chemistry, Johannes Gutenberg University Mainz, Duesbergweg 10-14, 
D-55128 Mainz, Germany
zentel@uni-mainz.de


The first paper about LC-elastomers was written by H. Finkelmann [1]. It dates to 1981, at which time he worked as junior group leader in the lab of Prof. G. Rehage at the TU-Clausthal. This work was soon after extended [2] by him. A bit later (1986), also R. Zentel [3] entered the field. Concerning his status, he was also a junior group leader at the University of Mainz associated with Prof. H. Ringsdorf (for comparison: he was 8 years younger than Finkelmann). While Finkelmann focused more on Physico-chemical aspects (he was working in an Institute for Physical Chemistry), Zentel tried to broader the chemical basis and the molecular structures (for an overview see Fig. 1 and [4]). He was working in Organic Chemistry. Over time, the field “flourished” and in about 1990 a lot of papers on LC-elastomers were available. For recent reviews see especially volume 250 of “Adv. Polymer Sci.” [5] and especially the chapters of Brömmel et al. [6] and Ohm et al. [7]
 
Fig. 1: Schematic representation of LC side-chain and LC main chain elastomers [4]
The polymer chains are marked in red and the crosslinks circled in blue; (original artwork of the author), structure similar to ref. [4]


Now, there was a second route to LC-elastomers. These were the predictions of the properties of LC-elastomers by P.G. de Gennes [8, 9 ](1969 (in French) and 1975), which include also the possibility for a shape change (nowadays most prominent for “actuators”). He was a theoretical physicist and he got the “Nobel price” later on (generally for “theory of soft matter”). However, this work was not cited in the early synthetic papers (how to make LC-elastomers) and -if yes- then not in a prominent  way (see [4] for an exception). This aspect has been discussed recently by Jan Lagerwall [10] for the first time. This raises the question of the relevance of chemistry (to really make the materials) and theoretical predictions (of what “great properties they might show) to advance a field. LC-elastomers are a fine example to show that you need both!


 
Fig. 2: Schematic picture to demonstrate the interaction of anisotropically oriented mesogens and a crosslinked polymer network (red) according to the concept of de Gennes [8, 9]. In this case (taken from [4]) it is assumed that the polymer chains try to expand parallel to the director of the mesogenic groups, which determines their anisotropic chain confirmation.


My redrawing of the ideas of the general ideas of de Gennes [8,9] are presented in Fig.  2. Independent of the type of coupling (or if there is any) mesogens and polymers will “feel each other”. In this way the polymer chains will acquire some anisotropy in the liquid crystalline phase of the mesogens. And in rubbery polymer networks (elastomers) the chain conformation determines the macroscopic size of the elastomer sample. Thus, any change of the anisotropy must lead to a shape change. So far, so good. 
But then it turned out that isotropic networks cannot be swollen with low molar mass liquid crystals in the liquid crystalline phase, see refs. [10 and 11] ( note that [11] is also ref.6 in [4]). So, networks with anisotropic liquid crystalline properties cannot be made so easily (by swelling of classical elastomers). Their preparation requires it either to find (invent) crosslinked elastomers, which are compatible (swellable) with liquid crystalline materials or to invent LC-elastomers directly. And theory cannot tell you, how to solve the challenge. But the chemical preparation [1 -5, 10] of LC-elastomers had solved the problem.


It is interesting that the early ideas of de Gennes had still an outreach, which, however, cannot be tracked today in references. At first ref. [11 cannot be accessed electronically (at list I cannot do so and I have to rely on a paper copy). Secondly, I remember having read an extended abstract from a conference in the 80´ (a paper copy of in an “old” library). It described work of some German polymer scientists. They described having prepared a block of a classical elastomer and swollen it in a nematic material (from Merck) in the isotropic phase. This worked well. But as they lowered the temperature, the system phase separated into the nematic phase of the low molar mass compound and a condensed, deswollen elastomer. And because of this fact, they wrote that they could not go on to look for further promising properties. 
But this means that prior to 1979 polymer scientist had tried to do something following the predictions of de Gennes. But it had not worked. I myself are however sure that G. Rehage (the mentor of Finkelmann) know about these experiments. And in 1982 (one year after the first paper on LC-elastomers [1]) a paper was published at the TU-Clausthal [12], which shows that the new LC-side group polymers were miscible with low molar mass liquid crystals in the nematic phase. So, the experiments predicted by de Gennes could have been done. However, now LC-elastomers could be made directly [1-7] without the need of mixing/swelling.


As most of the LC-elastomers are based on LC-side group polymers, and as also LC-side group polymers demonstrate the problem of coupling two subsystems (mesogens with anisotropic orientation) and polymer chains (statistical chain confirmation) it is appropriate to discuss them briefly (see Fig. 3).


 
Fig. 3: LC-side group polymers [i] and the linking of mesogens and polymer coils via a flexible spacer [13]

 


Polymers (above a critical molecular weight) do not mix with mesogens in the liquid crystalline phase (oligomers, however, might just act like a solvent). This happens because the isotropic polymer coil will reduce the nematic order of the mesogens slightly, whilst -at the same time- the entropy of the isotropic coil is reduced by inducing an anisotropic chain conformation (this corresponds to entropy elasticity on stretching an elastomer). So somehow, both subsystems have to be synthetically coupled to prevent their demixing. On the other side, the coupling should not be too strong, as the orientational tendencies are different. This problem was solved experimentally by introducing the concept of the flexible spacer, which made LC-side group polymers accessible (see [13] for an extended review). The fascinating property of the LC side-chain polymers is, that LC phases get stabilized [13], but if the spacer is removed (Gedankenexperiment) then they would just phase separate.

References:
[1] Liquid crystalline elastomers - A new type of liquid crystalline material H. Finkelmann, H.-J. Kock. G . Rehage. Makromol. Chem. Rapid. Chommun. 2, (1981) 317.
[2] Thermoelastic and photoelastic properties of crosslinked liquid-crystalline side chain polymers  W. Gleim. H. Finkelmann, Makromol. Chem. 188, 1489 (1987).
[3] Liquid crystalline elastomers based on liquid crystalline side group, main chain  and combined polymers
 R. Zentel, G. Reckert, Makromol. Chem. 187, 1915 (1986)
[4] Liquid crystalline elastomers,  R. Zentel, Angew. Chem. Int. Ed. Engl. Adv. Mater. 28, 1407 (1989), Adv. Mater., 321(1989)
[5] Liquid Crystal Elastomers: Materials and Applications, W. de Jeu, (eds) Adv Polym Sci 250 (2012);
[6] Preparation of Liquid Crystalline Elastomers: F. Brömmel, D. Kramer, H. Finkelmann, Adv Polym Sci 250, 1-48 (2012)
[7] Applications of Liquid Crystalline Elastomers; C. Ohm, M. Brehmer, R. Zentel  Adv Polym Sci 250, 49–94 (2012)
[8] Possibilites offertes par la reticulation de polymeres en presence d’un cristal liquide. 
 Pierre-Gilles de Gennes. Phys. Lett. A, 28 (11), 725 (1969)
[9] The Physics of Liquid Crystals, P. G . de Gennes. Clarendon Press. Oxford 1975.
[10] Liquid crystal elastomer actuators and sensors: glimpses of the past, the present and perhaps the future, 
Jan Lagerwall, Programmable Materials,0,1–42 (2023)
[11]  F. Brochard. J. Phys. (Les Ulis, Fr.) 40 (1979) 1049
[12] Phase Studies of Liquid Crystalline Side Chain Polymers Mixed with
Low Molar Mass Liquid Crystals of Similar Structure
H. Finkelmann, H.-J. Kock and G. Rehage
Mol. Cryst. Liq. Cryst.,  89, 23 (1982)
[13] Liquid Crystalline Polymers, R. Zentel  in: Liquid Crystals, H. Stegemeyer (Editor), Steinkopff Verlag Darmstadt 1994,  103 - 140

 

A tribute to Wim de Jeu (WILHELMUS HENDRIKUS DE JEU)

Created by Alexey Eremin vor 42 Tagen um 15:12 Uhr:

The German Liquid Crystal Society mourns the passing of Prof. Wim de Jeu, who died on 3 June 2026.

Wim de Jeu was an inspiring scientist, who worked in the area of soft matter physics whereby he focused on “self-organized” materials, mostly of liquid crystalline nature. He was born 1943 in Leersum (NL) and died recently in Heerlen, NL (June 3rd 2026) at the age of 83. 
Over all, he got famous for his “physical view” on new liquid crystalline materials and the use of refined (X-ray) scattering methods to characterize various smectic phases. In addition, he had a great interest in structure – property relations, which made him an ideal partner for synthetic groups (see the list of his scientific activities, (Link).). In this respect he was essential to the characterization and further development of the new polymeric liquid crystalline compounds. This brought him in close contact with LC-groups in Halle (Fischer), Freiburg (Finkelmann) and Mainz (Zentel). In this context he studied the effect of polymer-networks and their crosslinking points in liquid crystalline elastomers [1, 2] and of phase separation in liquid crystalline block-copolymers [3]. Finally he was awarded the “Alfred Saupe Award” in 2018 at the annual meeting of the “German Liquid Crystal Society” (see Fig. 1). The laudation presented for this purpose is enclosed (Link).

 


Fig. 1: Awarding the Saupe Medal to Wim de Jeu, from left: Frank Giesselmann, Wim de Jeu, Brigitte Saupe (widow of A. Saupe) and Rudolf Zentel


It should be noted that besides his scientific activities Wim de Jeu was also very actively engaged in the education of students and the promotion and training of young up-coming scientists. This showed up by his engagement in the “establishment of the Science Department” at the “Open University of the Netherlands” (1984 -94) for which he acted as dean of the faculty and in the fact that he wrote three books on his topics (Physical Properties of Liquid Crystalline Materials; Liquid Crystal Elastomers, Materials and Applications; Basic X-Ray Scattering for Soft Matter). In addition he used -at the end of his career- much time at the University of Mass. at Amherst and at the TH Aachen for the training of students.

 
[1] Induced long-range order in crosslinked "one-dimensional" stacks of fluid monolayers
 G.C.L. Wong, W. de Jeu, H. Shao, K.S. Liang, R. Zentel
NATURE 389, 576 - 579 (1997); https://doi.org/10.1038/39271
[2] Order and Disorder in Liquid-Crystalline Elastomers,
 WH de Jeu, BI Ostrovskii, 
 Adv. Polym. Sci., 250, 187-234 (2012); DOI 10.1007/12_2010_105

[3] Orientational Wetting in Hybrid Liquid Crystalline Block Copolymers
G.C.L. Wong, J. Commandeur, H. Fischer, WH de Jeu, Phys. Rev. Lett. 77, 5221 (1996); DOI 10.1103/PhysRevLett.77.5221

 

written by Rudolf Zentel

Wolfgang Helfrich (1932–2025)

Created by Alexey Eremin am 30.03.2026 um 15:51 Uhr:

The liquid crystal and soft matter community has lost a scientist whose work has had a lasting influence on the field. Wolfgang Helfrich, who passed away in 2025, made fundamental contributions to both liquid crystal research and biophysics.

After studying physics in Göttingen, Munich and Tübingen, and completing his doctorate at the Technical University of Munich in 1961, Helfrich worked in Munich, Ottawa, and at the RCA Laboratories in Princeton. Following his habilitation in 1967, he returned to RCA, where he began developing theoretical ideas on the structure of liquid crystals.

In 1970, at Hoffmann-La Roche in Basel, Helfrich — together with Martin Schadt — developed the first twisted nematic liquid crystal display (LCD). This concept became the basis for a technology that is now used in billions of devices worldwide.

In parallel, Helfrich made important contributions to the physics of membranes. His 1973 paper introduced what is now known as the Helfrich energy, a curvature-based description of membrane elasticity that remains central in biophysics. In the years that followed, he developed key ideas on membrane fluctuations, entropic interactions, and vesicle shapes, which continue to influence research across disciplines.

From 1973 until his retirement in 1997, Helfrich was Professor of Experimental Physics at the Free University of Berlin. He received several distinctions for his work, including the Robert-Wichard-Pohl Prize of the German Physical Society and, in 2012, the Draper Prize of the US National Academy of Engineering.

Wolfgang Helfrich combined theoretical depth with a strong sense for physical problems. He moved between fundamental questions and practical applications and was known for his independent thinking and his critical view of rigid academic and industrial structures.

He will be remembered as a scientist who opened new perspectives in the study of liquid crystals and membranes, and as an inspiration to colleagues and students.


The German Liquid Crystal Society (GLCS / DFKG) honours his memory with respect and gratitude.

From lyotropic liquid crystals to hierarchically structured materials

Created by Alexey Eremin am 19.12.2025 um 21:22 Uhr:

by Johanna Bruckner (University of Stuttgart)

 

Located at the Institute of Physical Chemistry at the University of Stuttgart, Germany, the research group led by Dr. Johanna R. Bruckner deals with the fabrication and analysis of hierarchically structured materials. The group advances from lyotropic liquid crystals (LLCs) to hierarchically structured materials by taking advantage of the self-assembled structures of surfactant-, polymer-, or nanoparticle-based LLCs as precursors for well-defined solid systems. One example for this is the preparation of ordered mesoporous materials, such as silicates and metallosilicates, by direct liquid crystal templating (DLCT). In this approach, the continuous phase of an LLC is polymerized around the regularly arranged micelles, producing a precise replica of the LLC. In contrast to conventional templating methods, DLCT results in exceptionally well-defined materials (Figure 1). Due to their large surface area, uniform pore diameters, and active sites, these materials are used for catalysis, adsorption, and separation applications, as well as confinement studies. Another central research focus of the Bruckner group lies on photonic materials which selectively reflect certain electro-magnetic wavelengths through a periodic modulation of the refractive index. Such a modulation is achieved, for example, by drying chiral nematic LLCs with suitable structural and electronical properties while preserving the helical structure (Figure 2). At the heart of the group’s research is the focus on developing a detailed understanding of the initial systems and the underlying processes governing structure formation. Driven by this scientific curiosity, the group also develops new, eco-friendly LLCs and production methods to enhance sustainability and broaden their application potential.

 

Figure 1. A hexagonal LLC phase, as seen by polarizing optical microscopy (top), which is transferred into an ordered mesoporous material by DLCT. Transmission electron microscopy reveals the uniform cylindrical mesopores (bottom).

 

Figure 2. The helical modulation of the director in the chiral nematic phase gives rise to the characteristic finger print texture visible in polarizing optical microscopy (top). If the structure is retained while drying, the helical arrangement can be visualized by scanning electron microscopy (bottom left) and may lead to the selective reflection of visible light, as in the pictured xanthan film (bottom right).

 

Page 1 of 2 1 2

Last Modification: 03.09.2025 -
Contact Person: