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Preface Functional materials have been always of interest for human beings, and the everlasting quest for novel, tailored materials has evidently been having a decisive impact on the survival, development, and prosperity of our mankind. Looking back into distant human history, it appears to be nearly impossible for most people to imagine that there had been a period of about five million years in which people have lived almost exclusively from renewable resources. In this period, the human race learned to develop novel functional materials, driven by the demand to be more successful in hunting and gathering, to protect themselves from natural phenomena, to be more effective at fieldwork, to outmatch their enemies, to improve communication, or to realize higher prices for handcraft and special products. Archeological collections or historical museums are places that are suitable to convey an impression of the multitude of functional materials that have been created driven by the genius and aptitude of human beings. Humans succeeded to manufacture knifes, axes, or arrows that had blades or tips from flintstone or obsidian, they found access to metals and invented alloys such as bronze, they manufactured tools, commodity, armor, and weapons from it, they used plant ash as fertilizer and charcoal as soil conditioner, they learned to prepare soap from potash and animal fat, to weave clothes from linen, wool, or silk, to tie ropes from hemp or sisal fibers, to caulk their fishing boats with oakum, and they discovered the hydraulic binding ability of puzzolanic soil that was from that point on used as a high-performance cement in combination with lime, quarrystone, and sheathings from highly porous tuff stone (opus caementicium, 40 B.C.). Early they discovered that a blue dye can be obtained from dyer’s weed or the Indian Indigo plant by fermentation with urine and potash and subsequent air oxidation (ca. 4000 B.C.), that hides and skins are more durable and less susceptible to decomposition when tanned (2500 B.C.), and that charcoal powder in combination with saltpeter and sulfur can be used as gun powder. Felts tough enough to form construction materials were produced by matting, condensing, and pressing woolen fibers, linen sheaths soaked with chemicals or skins made from animal intestines were softened by treatment with sulfur and lye and used as condoms, aqueous suspensions of plant fibers were processed to paper, and celluloid – a mixture of cellulose nitrate and camphor – has been used as ivory substitute, as transparent carrier for photographic films, as liquid plaster, and is still used in high-quality table tennis balls. Even though an incredible long list containing thousands and thousands of other examples could be compiled – some of them keystones in mankind´s advancement, others just minor proofs of men’s unlimited ingenuity – functional xi In Functional Materials from Renewable Sources; Liebner, F., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
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materials have always accompanied the development of the human race. Since the beginning of the industrial age about 200 years ago, evolution and design of novel materials has literally undergone a leap with respect to number, performance, and level of sophistication However, the breathtaking technical and technological development within this short period of human history has also led to a considerable depletion of fossil resources mainly caused by the global energy demand that rose simultaneously at a virtually explosive rate. The enormous annual exploration rates, which added up to 2,940 × 109 m³ of natural gas, 4.22 × 109 tons of crude oil, and 6.38 × 109 tons of coal only for the year 2007, will in not-so-far future inevitably exhaust the remaining reserves and undermine the foundations of the current wealth of large proportion of our civilization. It is commonly acknowledged that the fossil reserves will be exhausted within a comparatively short period of time, which will be most likely not much longer than the time elapsed since the presentation of the first photographic image (Niepce 1826), the discovery of rubber vulcanisation (Goodyear 1839), or the development of the first synthetic dye (Perkin 1856). After the turn of the millennium, we have now approached a time period where the public awareness for the finite nature of fossil resources and the necessity of using renewable sources has reached an encouraging level. Today, renewables are still being mainly used for energy production. However, it is safe to assume that the focus of future resource utilization strategies will increasingly move from energy to materials and platform chemicals; novel, more efficient energy technologies based on wind, water, solar energy or − controversially − nuclear power are at hand, while renewable resources are the only alternative to fossil ones as origin of organic carbon and thus the basis of chemicals and materials. Today, the relatively young term “biorefinery” tries to encompass all approaches aiming on the production of chemicals or materials from aquatic or terrestrial biomass either by extraction, fractionation, modification, or physical, chemical, and biotechnological conversion processes. Furthermore, broad consensus exists that the operating efficiency of biorefinery units largely depends on the profitability of all product lines and the value of individual products. This implies that any sustainable biorefinery approach must use up not only one, but all plant constituents which would be cellulose, hemicelluloses, lignin, and extractives in the case of wood. Following this concept, substantial advances have been recently made with respect to the development of innovative, biopolymer-based functional materials using both up-to-date synthetic and instrumental-analytical tools. Current research in this field − to name but a few examples − targets electronic, photonic, magnetic, and hemocompatible high-performance functional materials, is increasingly based on bionic principles and bioinspiration, and uses sophisticated methods for tailoring the properties for special applications. Nano (NEMS), micro (MEMS), and bio-micro electromechanical systems (bioMEMS) are further hot topics in functional material’s research as billions of such devices are already manufactured annually for sensing, ink jet printing, automotive applications, communications, and medicine. The present book, “Novel Functional Materials from Renewable Resources”, has been prepared with the intention to convey an impression of the current state xii In Functional Materials from Renewable Sources; Liebner, F., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
of research in this field , and to reflect the ample activities in this field that are currently going on worldwide. The compilation of topics is based on presentations given during the 241 Annual Spring Meeting of the American Chemical Society, held in Anaheim in March 2011, at a series of sessions of the ACS Cellulose division. May this book awake and sustain the curiosity of our readers to discover an old and new fascinating field of research that will hopefully contribute to the further wealth of future generations and to reasonable global resource management that will not be stopped by ignorance or lobbying.
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Break-proof Pyrex glass was discovered twice in history with a time span of about 1900 years between the two events. When Tiberius, the second emperor of the Roman Empire, heard about the existence of a glass-maker about whom was said that he would be able to make break-proof glass, he urged the man to appear at his court. When the glass-maker arrived he presented a beautiful transparent vase made of Martiolum to the emperor. To demonstrate the intriguing properties of his functional material he threw the vase to the ground and − it did not shatter into sherds. While the spectators were stunned, frightened or even thought of wizardry, the emperor kept calm and just made inquiries about the material and the names of people that might also know the secrets of its manufacture. After having made sure that the glass-maker was the only secret-keeper of Pyrex glass production, the emperor had the glass-maker put to death and his factory destroyed to be the only owner of break-proof glassware. − Today, Pyrex is one of the most important source of lab glassware for the material’s chemist. (based on John Emsley, Molecules at an Exhibition, Oxford University Press, Inc., New York, 1998)
Falk Liebner and Thomas Rosenau, February 2012
xiii In Functional Materials from Renewable Sources; Liebner, F., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
