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Episodes from the History of Liquid Crystals

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Episodes from the History of Liquid Crystals School of Mathematics UNIVERSITY OF SOUTHAMPTON EpisodEs From ThE hisTory Of Liquid CrysTaLs Tim Sluckin University of Southampton 26/06/2013 I-CAMP, Cambridge 2013 1 School of Mathematics CoNTENTs UNIVERSITY OF SOUTHAMPTON • Liquid crystal physics • Early German and French History • Optical devices and all that • Non-optical applications • Some brief comments about current work in the field • Commercial 26/06/2013 I-CAMP, Cambridge 2013 2 School of Mathematics UNIVERSITY OF SOUTHAMPTON This is the Isaac Newton Institute for Mathematical Sciences, so I thought I would show you some equations 26/06/2013 I-CAMP, Cambridge 2013 3 School of Mathematics UNIVERSITY OF SOUTHAMPTON OK… That’s all for equations today 26/06/2013 I-CAMP, Cambridge 2013 4 School of Mathematics UNIVERSITY OF SOUTHAMPTON • This is a story of some accidental and some deliberate discoveries • A large part of the early story is a German story • I shall try to talk about some of the personalities, some of the physics and some of the social history • As with all history, I have to select, and others would select differently! • At the end is a commercial for the books I have written on this subject 26/06/2013 I-CAMP, Cambridge 2013 5 School of Mathematics UNIVERSITY OF SOUTHAMPTON A brief summary of liquid crystal physics Much more in the next 10 days 1. Liquid crystals are structurally intermediate between liquid and crystalline phases (except when they are not…) 2. They are not crystals! 3. Rich panoply of “mesomorphic phases” 4. Non-Newtonian hydrodynamics 5. Broken symmetry statistical mechanics phases 6. ∃ topological defects whose nature depends on the phase symmetry 7. Optically birefringent 26/06/2013 I-CAMP, Cambridge 2013 6 School of Mathematics UNIVERSITY OF SOUTHAMPTON SOME FACTS ABOUT LIQUID CRYSTALS • Liquid crystals are not crystals, but liquids with some remnant of crystalline order • Liquid crystals are usually made from rod-like molecules, but are sometimes made from disc-like molecules • Liquid crystal phases are optically anisotropic • Between crossed polarisers, liquid crystals produce brightly coloured patterns known as textures • Liquid crystal phase diagrams are complex, with often many phases between liquid and crystalline solid • Two flavours: thermotropic (change temperature) and lyotropic (change concentration in a water solution) • Inhomogeneous liquid crystal phases sustain topological defects where the order is not defined 26/06/2013 I-CAMP, Cambridge 2013 7 School of Mathematics UNIVERSITY OF SOUTHAMPTON Molecular organisation (after Friedel 1922) Nematic phase Smectic A (layered) phase 26/06/2013 I-CAMP, Cambridge 2013 8 School of Mathematics UNIVERSITY OF SOUTHAMPTON Chiral and tilted phases • The cholesteric (or chiral nematic) phase is chiral. • The director configuration is helical • Repeat length is known as the pitch. The smectic C phase is tilted. 26/06/2013 I-CAMP, Cambridge 2013 9 School of Mathematics UNIVERSITY OF SOUTHAMPTON TNI 26/06/2013 I-CAMP, Cambridge 2013 10 School of Mathematics UNIVERSITY OF SOUTHAMPTON FriEdriCh ReiNiTzEr (1857-1927) About 1½ years ago, I reported the results of some studies of a cholesterol occurring in the root of the carrot. Husemann [1] named this compound hydrocarotene. ……. 26/06/2013 I-CAMP, Cambridge 2013 11 School of Mathematics UNIVERSITY OF SOUTHAMPTON The first experiment - 1888 • Friedrich Reinitzer(1857-1927) Imperial Institute for Plant Physiology German University of Prague COO • Studies of cholesteryl benzoate Interested in cholesterol compounds from • Double melting – carrots. (i) crystal to cloudy fluid Cholesteryl benzoate the first liquid crystal (ii) cloudy fluid to clear liquid C27H45 . C7H5O2 (iii) colours close to clearing point (iv) Lehmann has observed Crystal melts to liquid crystal 145.5°C crystallites Liquid crystal clears to liquid 178.5 °C 26/06/2013 I-CAMP, Cambridge 2013 12 School of Mathematics UNIVERSITY OF SOUTHAMPTON A liquid crystal sample 26/06/2013 I-CAMP, Cambridge 2013 13 School of Mathematics QUESTION No.1 UNIVERSITY OF SOUTHAMPTON THE BOTTLE ON THE DESK CONTAINS: A. A sample of bull’s semen from a farm in Granchester B. Milk from the fridge upstairs containing coloured chocolate nanodroplets C. A cholesteric liquid crystal with a formula to long to fit into the margin of this slide D. White paint scooped up from my floor because I am a hopeless experimentalist 26/06/2013question I-CAMP, Cambridge 2013 14 School of Mathematics UNIVERSITY OF SOUTHAMPTON rEiNiTzEr’s PUZZLEs What is causing the peculiar double melting? What is causing the peculiar colours? Must be some pigment somewhere… Thank you Dr Lehmann for some microscopy! 26/06/2013 I-CAMP, Cambridge 2013 15 School of Mathematics Letter from Reinitzer to Herr UNIVERSITY OF SOUTHAMPTON Otto Lehmann (Aachen) Dr Knoll in Karlsruhe interpreted these letters 26/06/2013 I-CAMP, Cambridge 2013 16 School of Mathematics UNIVERSITY OF SOUTHAMPTON Otto LEhmann (1855-1922) Professor at Technische Hochschule, Karlsruhe, 1890-1922 • Fliessende Krystalle (1890) Schleimig flüssige kristalle • Krystalline Flüssigkeit (1890) • Flüssige Kristalle (1900) Tropfbar flüssige kristalle 26/06/2013 I-CAMP, Cambridge 2013 17 School of Mathematics UNIVERSITY OF SOUTHAMPTON Lehmann’s studies 1889 - • Otto Lehmann (1855 – 1922) Institute of Physics University of Karlsruhe • Developed the use of the polarising microscope with heating stage – applied it to Reinitzer’s cholesteryl benzoate • Identified birefringence (a property of crystals) and flow (a property of liquids) • Coined the phrase Flowing Crystals 26/06/2013 I-CAMP, Cambridge 2013 18 School of Mathematics UNIVERSITY OF SOUTHAMPTON The Lehmann microscope 26/06/2013 I-CAMP, Cambridge 2013 19 School of Mathematics UNIVERSITY OF SOUTHAMPTON The title page of Lehmann’s 1904 book on liquid crystals There is not time to do justice to Lehmann’s catholic interests 26/06/2013 I-CAMP, Cambridge 2013 20 School of Mathematics UNIVERSITY OF SOUTHAMPTON Lehmann’s microscopic observations (from 1904 book) artificial colour, photos in b/w 26/06/2013 I-CAMP, Cambridge 2013 21 School of Mathematics UNIVERSITY OF SOUTHAMPTON Ludwig gaTTErmann (1860-1920) Gattermann and Ritschke On azoxyphenyl ethers Berichte der Deutschen chemischen Gesellschaft 23, 1738-40 (1890) Gattermann was the first to synthesise a liquid crystal Para-azoxyanisole K-116ºC-cloudy -134 ºC-clear liquid PAA became the experimental liquid crystal of choice Gattermann later became a famous organic chemist, and authored the premier textbook of the day (“Gattermanns Kochbuch”) The Dye Company thought that the bright colours in the liquid crystal displays under the microscope could be used in dyes and colourings. So they funded Gattermann’s work… 26/06/2013 I-CAMP, Cambridge 2013 22 School of Mathematics UNIVERSITY OF SOUTHAMPTON Son of a Baker (!) Gattermann reaction (1890) Gattermann-Koch reaction (1897) Gattermann aldehyde synthesis (1898) Gattermann-Stika pyridine synthesis (1916) Pure explosive nitrogen trichloride Liquid Crystal work sponsored by Bayer’s Dyeworks in Elderfeld I26/06/2013-CAMP, Cambridge 23 2013 School of Mathematics UNIVERSITY OF SOUTHAMPTON Lehmann’s drops can merge……….. The patterns deform………..very quickly…………. No-one understood Lehmann’s patterns. They saw ‘lines of force’ and ‘Schliere’ Gattermann had a vivid imagination… 26/06/2013 I-CAMP, Cambridge 2013 24 School of Mathematics UNIVERSITY OF SOUTHAMPTON After the drops amalgamate the molecules reorient according to the mutual lines of force. I call this process copulation. If the merging drops are very small then the copulation proceeds so quickly that it cannot be separated from the amalgamation I26/06/2013-CAMP, Cambridge 25 2013 School of Mathematics Textures UNIVERSITY OF SOUTHAMPTON The term “texture”, for the brilliant coloured patterns observed between crossed nicols, entered the field very early. • Texture below was a liquide à fils or liquide à noyaux, Schlieren texture., also flüssige Kristalle • Textures on the right were batonnets, liquides à coniques, also fliessende Kristalle Each texture was associated with a phase. Flow properties and patterns seemed to be related 26/06/2013 I-CAMP, Cambridge 2013 26 School of Mathematics gusTav Tammann UNIVERSITY OF SOUTHAMPTON (1861-1938) •Two articles in Annalen der Physik 1900-1 •“On the so-called liquid crystals” •Intense controversy with Lehmann •Liquid crystals are cloudy for the same reason that milk is. •Professor of Physical Chemistry at Göttingen •Founder of modern metallurgy 26/06/2013 I-CAMP, Cambridge 2013 27 School of Mathematics WHAT IS GOING UNIVERSITY OF SOUTHAMPTON ON (1890-1900)? • Two (or even three) melting points • Cloudy and birefringent phase • Structural and flow properties between solid and liquid Eureka! A liquid crystal! • Maybe the system is impure? (Quincke, Tammann) • Maybe a suspension of crystals inside a liquid? (Quincke, Wulff ) • Maybe an emulsion of two liquids? (Tammann, Nernst) • No, a liquid crystal ! (Schenck,Lehmann) But what is a liquid crystal? 26/06/2013 I-CAMP, Cambridge 2013 28 School of Mathematics UNIVERSITY OF SOUTHAMPTON Tammann’s controversy with Lehmann continued for several years (1901-1906) with great bitterness. Lehmann referred to Tammann as “my opponent” Tammann did not believe that crystals could be liquid, because he believed in the lattice theory of solids, which at that time had not been experimentally proved. He thought liquid crystals were mixtures, which could be separated Lehmann was convinced that he had actually seen
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