Monthly Archives: March 2017

On this day in science history: polyethylene was discovered

Polyethylene was first synthesized by the German chemist Hans von Pechmann, who prepared it by accident in 1898 while investigating diazomethane. When his colleagues Eugen Bamberger and Friedrich Tschirner characterized the white, waxy substance that he had created, they recognized that it contained long –CH2– chains and termed it polymethylene.

Polythylene balls, by Lluis tgn (Own work) [CC BY-SA 3.0 (http://ift.tt/HKkdTz) or GFDL (http://ift.tt/KbUOlc)%5D, via Wikimedia Commons
The first industrially practical polyethylene synthesis (diazomethane is a notoriously unstable substance that is generally avoided in industrial application) was discovered in 1933 by Eric Fawcett and Reginald Gibson, again by accident, at the Imperial Chemical Industries (ICI) works in Northwich, England.  Upon applying extremely high pressure (several hundred atmospheres) to a mixture of ethylene and benzaldehyde they again produced a white, waxy material. Because the reaction had been initiated by trace oxygen contamination in their apparatus, the experiment was, at first, difficult to reproduce. It was not until 1935 that another ICI chemist, Michael Perrin, developed this accident into a reproducible high-pressure synthesis for polyethylene that became the basis for industrial LDPE production beginning in 1939. Because polyethylene was found to have very low-loss properties at very high frequency radio waves, commercial distribution in Britain was suspended on the outbreak of World War II, secrecy imposed, and the new process was used to produce insulation for UHF and SHF coaxial cables of radar sets. During World War II, further research was done on the ICI process and in 1944 Bakelite Corporation at Sabine, Texas, and Du Pont at Charleston, West Virginia, began large-scale commercial production under license from ICI.

The breakthrough landmark in the commercial production of polyethylene began with the development of catalyst that promote the polymerization at mild temperatures and pressures. The first of these was a chromium trioxide–based catalyst discovered in 1951 by Robert Banks and J. Paul Hogan at Phillips Petroleum. In 1953 the German chemist Karl Ziegler developed a catalytic system based on titanium halides and organoaluminium compounds that worked at even milder conditions than the Phillips catalyst. The Phillips catalyst is less expensive and easier to work with, however, and both methods are heavily used industrially. By the end of the 1950s both the Phillips- and Ziegler-type catalysts were being used for HDPE production. In the 1970s, the Ziegler system was improved by the incorporation of magnesium chloride. Catalytic systems based on soluble catalysts, the metallocenes, were reported in 1976 by Walter Kaminsky and Hansjörg Sinn. The Ziegler- and metallocene-based catalysts families have proven to be very flexible at copolymerizing ethylene with other olefins and have become the basis for the wide range of polyethylene resins available today, including very low density polyethylene and linear low-density polyethylene. Such resins, in the form of UHMWPE fibers, have (as of 2005) begun to replace aramids in many high-strength applications.

One of the main problems of polyethylene is that without special treatment it’s not readily biodegradable, and thus accumulates. In Japan, getting rid of plastics in an environmentally friendly way was the major problem discussed until the Fukushima disaster in 2011. It was listed as a $90 billion market for solutions. Since 2008, Japan has rapidly increased the recycling of plastics, but still has a large amount of plastic wrapping which goes to waste.

In May 2008, Daniel Burd, a 16-year-old Canadian, won the Canada-Wide Science Fair in Ottawa after discovering that Pseudomonas fluorescens, with the help of Sphingomonas, can degrade over 40% of the weight of plastic bags in less than three months.

The thermophilic bacterium Brevibacillus borstelensis (strain 707) was isolated from a soil sample and found to use low-density polyethylene as a sole carbon source when incubated together at 50°C. Biodegradation increased with time exposed to ultraviolet radiation.

In 2010, a Japanese researcher, Akinori Ito, released the prototype of a machine which creates oil from polyethylene using a small, self-contained vapor distillation process.

In 2014, a Chinese researcher discovered that Indian mealmoth larvae could metabolize polyethylene from observing that plastic bags at his home had small holes in them. Deducing that the hungry larvae must have digested the plastic somehow, he and his team analyzed their gut bacteria and found a few that could use plastic as their only carbon source. Not only could the bacteria from the guts of the Plodia interpunctella moth larvae metabolize polyethylene, they degraded it significantly, dropping its tensile strength by 50%, its mass by 10% and the molecular weights of its polymeric chains by 13%.

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Why water splashes: New theory reveals secrets

New research from the University of Warwick generates fresh insight into how a raindrop or spilt coffee splashes.

Dr James Sprittles from the Mathematics Institute has created a new theory to explain exactly what happens – in the tiny space between a drop of water and a surface – to cause a splash.

Water splash

When a drop of water falls, it is prevented from spreading smoothly across a surface by a microscopically thin layer of air that it can’t push aside – so instead of wetting the surface, parts of the liquid fly off, and a splash is generated.

A layer of air 1 micron in size – fifty times smaller than the width of a human hair – can obstruct a 1mm drop of water which is one thousand times larger.

This is comparable to a 1cm layer of air stopping a tsunami wave spreading across a beach.

Dr Sprittles has established exactly what happens to this miniscule layer of air during the super-fast action by developing a new theory, capturing its microscopic dynamics – factoring in different physical conditions, such as liquid viscosity and air pressure, to predict whether splashes will occur or not.

The lower the air pressure, the easier the air can escape from the squashed layer – giving less resistance to the water drop – enabling the suppression of splashes. This is why drops are less likely to splash at the top of mountains, where the air pressure is reduced.

Understanding the conditions that cause splashing enables researchers to find out how to prevent it – leading to potential breakthroughs in various fields.

In 3D printing, liquid drops can form the building blocks of tailor-made products such as hearing aids; stopping splashing is key to making products of the desired quality.

Splashes are also a crucial part of forensic science – whether blood drops have splashed or not provides insight into where they came from, which can be vital information in a criminal investigation.

Dr Sprittles comments:

“You would never expect a seemingly simple everyday event to exhibit such complexity. The air layer’s width is so small that it is similar to the distance air molecules travel between collisions, so that traditional models are inaccurate and a microscopic theory is required.

“Most promisingly, the new theory should have applications to a wide range of related phenomena, such as in climate science – to understand how water drops collide during the formation of clouds or to estimate the quantity of gas being dragged into our oceans by rainfall.”

The research, ‘Kinetic Effects in Dynamic Wetting’, is published in Physical Review Letters.

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Looking for signs of the first stars

It may soon be possible to detect the universe’s first stars by looking for the blue colour they emit on explosion.

The universe was dark and filled with hydrogen and helium for 100 million years following the Big Bang. Then, the first stars appeared, and metals were created by thermonuclear fusion reactions within stars.

Stars in the sky, ESA/Hubble [CC BY 4.0 (http://ift.tt/1eRPUFd)%5D, via Wikimedia Commons
These metals were spread around the galaxies by exploding stars or ‘supernovae’. Studying first-generation supernovae, which are more than 13 billion years old, provides a glimpse into what the universe might have looked like when the first stars, galaxies and supermassive black holes formed. But to-date, it has been difficult to distinguish a first-generation supernova from a later one.

New research, led by Alexey Tolstov from the Kavli Institute for the Physics and Mathematics of the Universe, has identified characteristic differences between these supernovae types after experimenting with supernovae models based on observations of extremely metal-poor stars.

Similar to all supernovae, the luminosity of metal-poor supernovae shows a characteristic rise to a peak brightness followed by a decline. The phenomenon starts when a star explodes with a bright flash, caused by a shock wave emerging from its surface after its core collapses. This is followed by a long ‘plateau’ phase of almost constant luminosity lasting several months, followed by a slow exponential decay.

The team calculated the light curves of metal-poor blue versus metal-rich red supergiant stars. The shock wave and plateau phases are shorter, bluer and fainter in metal-poor supernovae. The team concluded that the colour blue could be used as an indicator of a first-generation supernova. In the near future, new, large telescopes, such as the James Webb Space Telescope scheduled to be launched in 2018, will be able to detect the first explosions of stars and may be able to identify them using this method.

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