A History of Plastics

from Charles the First

to Charles the Third

Geoff PritchardWorcester U3A

Raw materials for plastics

make starting materials for carbon-neutral “nylons” for vehicle parts. (CO2 is absorbed during bean growth)

21st Century: castor beans, palm oil, sugar, cotton, corn, tapioca, algae, biomass

Before 1900: plants

1880-1945: coal; milk; plants

In modern times: salt; oil and natural gas

Castor oil beans

Note: the rise in the price of sugar raised the UN FAO Food Price Index to 234 in June 2011, near to its record level of 239

Sir Robert Hooke, 1635--1703

Not popular. No portraits survive. Disfigured by smallpox as a child; orphan; father committed suicide when he was 13; difficult temperament, enemies (such as Isaac Newton) prevented recognition as an English Leonardo da Vinci.

Inventor of:

the iris diaphragm in cameras, the universal joint in vehicles, the balance wheel in watches, etc.

First to use the word 'cell' in the context of biology

Author of the first book on microscopy

Surveyor of the City of London after the Great Fire.

Architect, astronomer; deputy to Sir Christopher Wren.

Known today for “Hooke’s Law” and the concept of extrusion.

PART ONE: Natural Plastics (resins)

Flowers, foliage and fruit of the Isonandra Gutta Percha Tree

A resin is obtained by evaporating and coagulating the milk from the gutta percha tree trunk. Itcan be shaped in boiling water.

http://www.bouncing-balls.com/serendipity/gutta.htm

Gutta percha---a natural plastic or “resin”

John Tradescant (1608-62) the younger (head gardener to Queen Henrietta Maria at Greenwich, 1638-42) obtained Mazer wood, via a merchant, from Singapore (1656). Used for knife handles (1843)*, medical devices, jewellery; to insulate undersea cables (1847 till 1940s).

First gutta golf ball in 1840’s by Rev. Dr. Paterson. (Previously, wood or leather stuffed with feathers). Much cheaper, making golf more popular.

1845 Lagrénée returned to France with some gutta percha which he named “gum plastic”.

(Tradescantia wasnamed after his dad)

Synthetic gutta percha developed at Dunlop for golf ball covers, 1960-2.

One litrePyrexreactionvessel

Stirrer shaft

Gutta percha is trans 1, 4 polyisoprene whereas natural rubber is cis 1, 4 polyisoprene

SEE RIGHT HAND COLUMN

MARCH 29,1851

From:

Notes and Queries

In 1839 a German apothecary, Eduard Simon, distilled an oil from the resin of the Sweetgum tree, and named it "styrol". Over a few days it formed a jelly, which he called “styrol oxide”. It was actually poor quality polystyrene and not an oxide.

It’s not recognised as the first fully man-made plastic; usable polystyrene only came in 1933!

Trunk of rubber tree, Hevea brasiliensis, with cup for collecting “milk”

The rubber is coagulated, dried and “over-cooked”with sulphur to form ebonite for gramophone records, bowls, castors, (smoking) pipes.

PLASTICS FROM COWS! Casein plastics

(1899) (“The most beautiful of all plastics”)

A protein is separated from milk by the enzyme rennin. It is

moulded to shape under heat and pressure, and hardened by soaking in formalin (health hazard!). Casein products are machined from sheet, rod, or tube. Now confined mostly to buttons in New Zealand

Inventors:Krisch & Spitteler(Germany)

“Artificial horn”

Alexander Parkes

1846 Parkes patented a mixture of natural rubber with gutta

percha. The world’s first blended and toughened plastic?

1813 - 1890

Manager of the metal casting department at Elkington, Mason & Co. in Birmingham.

1856: The world’s first semi-synthetic plastic

Invented in Birmingham

Parkes took out over 80 patents and made the world’s first artificial plastic, cellulose nitrate. He called it “Parkesine,” [shown at the International Exhibition in London in 1862].

Awarded a medal, made no profit.

The American printer / inventor John Wesley Hyatt was asked by Phelan & Collander (manufacturers of billiard balls) to find a substitute for ivory (elephants were scarce).

.

Hyatt made cellulose nitrate, called it “Celluloid”. His “stuffing machine” (1872) was a forerunner of modern injection moulding machines

Cotton + Nitric Acid, Sulphuric Acid Nitrocellulose

Ethanol, dye

Heat, pressure,reaction vessel

Clean-up,ethanolremoval

Pure Celluloid withadded camphorto adjust softness

Powdering

Mouldedarticle

“Stuffing machine” (1872)

1

2

34

Four stages of celluloid production and moulding(Celluloid Manufacturing Co., Albany, NY, USA)

19th Century Celluloid UsesDental plates (1871); knife handles; toys; washable collarsand cuffs; billiard balls, buttons, brooches,dolls, folding toothpicks, combs, paperweights, thimbles, shoe-horns, table tennis balls, etc.

Celluloid Figurines

Celluloid strips were coated with a photosensitive gelatin emulsion

and used in early motion pictures (1880s) ---big fire problem!

Later replaced by cellulose acetate or polyester .

Pen

PART TWO: MAN-MADE PLASTICS

Dr Leo Baekeland (Belgian) made P-F resins; Founded General Bakelite Co. in 1910 in USA

Bayer (Germany) and Luft (Austria) had alreadymade similar resins, but failed to commercialise them .

Phenol + Formaldehyde P-F resin + water

Bakelite Companies.

James Swinburne formed Fireproof CelluloidSyndicate Ltd in 1904 to investigate the P-Finsulating resins shown him by Luft of Austria. Hefailed to make insulator mouldings, but made ahard lacquer, more durable than shellac, and usedit for coating brass to prevent tarnishing - (brassbedsteads were fashionable and made inBirmingham).

In 1910 he formed the Damard Lacquer Co. in alean-to shed in Birmingham. Successful. Demandrose. Patent struggles with Baekeland.

BAKELITE Ltd was formed in 1927 to exploit Baekeland’s patents in the UK by merging: Damard Lacquer Co., Baekeland Inc., Mouldensite Ltd (a leading moulding company) and Redmanol Ltd (the UK arm of an American sales company)

PVC was discovered in 1912 by Fritz Klatte, a German chemist.

• Klatte reacted acetylene with hydrochloric acid to produce vinyl chloride. Thinking he'd failed, he put it on a shelf, where it went solid (formed PVC). He

patented it in Germany. His company never did anything with it.

Ten years later, the patent expired. 1926, Waldo Semon, American chemist with B.F.Goodrich, “discovered” PVC, without knowledge of Klatte's discovery. He showed it to his boss, who patented it in America. They thought it would make good shower curtains. The waterproof material soon found more creative uses, and Goodrich made a fortune. Klatte never saw a penny.

PVC wire and cable jacketing has much better durability than natural rubber. Less re-wiring!

It’s also usedfor pipe, buildings,shoes, etc, etc

“Pay with plastic”

PVC Extrusions ---continuous “profiles” such as gutters, hose, sheet, curtain rails,conveyer belts for mining, window frames.

PVC windowframes weremade on alarge-scale inthe early 1970sin Germany

Recorded music 1880s Shellac used for records by Emil Berliner. First to use discs (rather than “phonograph” cylinders) despite earlier work by Edison, Bell and Cros. Even with cotton reinforcement it was brittle, but it could reproduce fine detail. Other companies used ebonite.

78 rpm was standard by late 1920s.1952 PVC (“vinyl”). Known as “unbreakable” because shellac resin cracked so easily.

Abba’s song “The Visitors” was the first commercial CD, in 1982. Made of polycarbonate.

Others say Billy Joel’s 52nd St, madein Japan; or Beethoven’s 9th, others say “Born in the USA”1982 is probably right.

Polythene (“Polyethylene”)

• invented by Fawcett and Gibson (ICI) 1933, production 1 Sept 1939;

• first use -- military radar (WW2)

• 6 different types later invented

Later: stiffer type made, used for Fairy Liquid bottles; swing-top bins; pipes

Postwar: shopping bags, wire insulation, packaging, (failed) washing-up bowls

“Dyneema” polyethylene has extra long molecules

Fishing line

21st Century a rmoured vehicles

Rapid development

• Unsaturated polyesters (“fibre glass boats”) 1940s and 1950s

• Epoxy resins (“Araldite” etc) 1939

• Nylons; saturated polyester (“polyester-cotton shirts”) 1930s; (first textiles, then plastics)

William H Carothers

Started as a junior accountant, then chemistry student, then head of college dept.,Worked at DuPont

Invented Neoprene rubber, Polyester textiles, (1930s)(Dacron etc)Invented nylon, Committed

suicide at age 41.

Nylon is used for gears, low voltage switchgear (top left); fishing lines,under-bonnet car parts, toothbrushes; but was invented as a textile.

Semi-finished nylon productsBottom left)

Polypropylene (invented 1954) is versatile

Stackable chairs

Drinking water bottles (not huge ones)

Banknotes

Rope

Vehicle parts

Garden membranes for weed control

Polycarbonate (1953) is tough and can be transparent…discovered by Daniel Fox at GE (Lexan) and by Hermann Schnell at Bayer (Makrolon) (both in 1953)

Uses: riot shields, visors, greenhouses, conservatories, lenses, CDs, DVDs, headlamp glasses...30% of all US spectacle lenses are made of polycarbonate, because of lawsuits about eye injuries from lenses breaking

.

Polycarbonatefor long riot shields and jet fightercockpit canopies

American footballhelmet

Australian-designed polycarbonate beer glass

In 2009, the UK Home Office says that glass beer mugs and bottles cost the NHS and police £100 million a year through 87,000 reported injuries

Basic injection moulding machine for makingthermoplastic articles (from combs to chairs) A screw was first used instead of a ram in 1946.

Close-up of a mould for making paper clips

SOME APPLICATIONS

• Vehicles

• Packaging

• Medical

• Aircraft

• Electronic

• Solar energy

Air ductsAir distributor

Windscreen washer

tankElbows, ducts and connectors

Some mouldings for road transport

Electric Bicycle

Toyota Prius (August 2009) uses plastics from plants

e.g. seat cushion foam, cowl side trim, inner and outer scuff

plates. Special Prius “A” for Japan uses air conditioning outlet made from sugar. Other raw materials: polylactic acid from starch, polyester, kenaf fibre, and polyols from castor oil.

NEXT :POLYCARBONATECAR WINDOWS!

Polycarbonate glazing is 50% lighter than glass and has high impact resistance.

Suppliers claim a weight reduction of more than 20kg (50%) is possible when replacing all glass windows (except the windshield) in a minivan. Vehicle manufacturers can now try 3D-shaped windows and new opening mechanisms.

Polycarbonate can now be made from carbon dioxide (and propylene oxide) instead of the hazardous use of phosgene reacted with bisphenol A. The last-named chemical is under suspicion as a health hazard to foetuses and children

Lithium ion batteries• A separator is a plastic film (often specially

modified polypropylene, or a polyimide) preventing the electrodes from touching, but letting lithium ions pass between them to allow the charge and discharge of the battery.

• A hybrid car has between 50 and 70 batteries. • plug-in hybrids-- 80 to 200• fully electric cars at least 150.

SUPERBUS MADE IN AN OVEN

This 15 metre long, Dutch-made battery-powered bus –with gull-wing doors – is made from a carbon fibre reinforced plastic chassis, glass reinforced polypropylene bodywork, and polycarbonate windows.

THE PACKAGING INDUSTRY SAYS:

Packaging is high–tech (multi-layered, can incorporate anti-piracy watermarks for designer label goods, exclude oxygen, retain

moisture, stop meat discoloration, control CO2 access)

Food packaging prolongs food life, saves more than 25% food from the waste bin. Plastic bottles save on fuel, don’t break, and can be recycled. Plastic packaging uses only 2% of all oil produced.

Collapsiblewater bottle

This food packaging by Linpac won a European prize in 2009 for products containing over 50% recycled plastics

MEDICAL PLASTICS• Tubing; IV accessories; blood bags

• Syringes; catheters

• Implants

• Temporary heart

• Radiation shielding (instead of lead)

• blood glucose meters; pumps; drug packaging

Note: plastic components can incorporateantimicrobial additives (biocides) to combat infection

Papworth.900 of theseworldwide

Only a few reinforced plastics parts shown here

Aileron (fibreglass)

Centre wing box

Engine cowlings

Galleys and lavatories

Main-wing box

Boeing 787 Dreamliner(Based on Flight International drawing)

Rear fuselage

Cabin floor

50% reinforced plastic (CFRP) so 20% less fuel

Clever Stuff

• Space suits; Moon rover vehicles• Electrically conducting plastics• Electronic paper• “Smart” materials change colour in response

to pressure, temperature, light, “remember” their previous shape and go back to it;

• blood clot warning devices for air travellers; Heal any scratches by themselves*

(*An additive is used:--short polymer molecules containing zinc or lanthanum ions; it melts and repairs the scratch in 1 minute under UV light, provided the sample is thin enough)

“Ultra-cheap solar energy panels will one day be made on a large scale. Rather than using complex and expensive fabrication methods to create a specific semiconductor nanostructure, high-volume printing will produce nano-scale (60nm) polymer films of solar cells to make solar panels."

When Charles 3 is king: cheap solar energy?

"In 2 hours, enough energy from sunlight falls on the Earth to satisfy the energy needs of its population for a whole year, but we need cheap and efficient solar cells that can cover huge areas to move us into a new age of renewable energy.”

Edited quotes from researchers at Sheffield University, July 2011

LAST SECTION:

SOME RECENT ENVIRONMENTAL ISSUES

Conversion to chemicals or fuel oil can bemore economic than simply re-shaping

Most plastics can be recycled (even PVC!) but to be economic, different types should not be mixed up

Recycling bottles

Recycling one plastic bottle can save enough energy to light a 60W bulb for 6 hours

•Detergent, other cleaning fluids, shampoos,

pills, soft drinks --REMOVE LIDS FIRST

This boat was made from 16,000 recycled PET bottles, to sail from San Francisco to Sydney.

Recycled polyethylene walkway in Bracknell. The Domesday Book copse is low-lying and prone to flooding; so a wooden structure would have quickly rotted

Courtesy of Tech Wood

This building is made of 70% waste sawdust and 30% resin (such as polyethylene)

A UK Environment Agency document, Life Cycle Assessment of Supermarket Carrier Bags, asserts that polythene bags have less impact on the environment than many supposedly ‘green’ alternatives;the so-called single use plastic bag is around 200 times less damaging than multi-use cotton bags.

Feb 2011

Some biodegradable bags generate methane rapidly during landfill

The UK Environment Agency (EA) has temporarily withdrawn its report while a legal query is resolved. The report shows that re-use of bags rather than the material of which they are made per se is the critical factor in reducing environmental impact. A cotton bag would have to be used at least 131 times to ensure that it has a lower global warming potential than a conventional “single use” lightweight HDPE carrier bag that is not reused. Paper and compostable bioplastic bags also show higher global warming potential than the conventional plastic bag. US students have identified polyurethane-eating organisms from the Amazon area.

The oceans have big “islands” of plastic rubbishdelivered to a central point by converging ocean currents

The Pacific one was once said to be 14 times the size of Holland, or twice that of Texas

Other oceanographers disagree; they say if you just measure the area of the plastic, rather thanthe area affected by merging currents, it is a small fraction of the state of Texas, say 1% . A 22 year study has found no increase in size over that time.

According to the Germans, 80% of all marine waste reaches the sea from the land because of poor waste management. Germany alreadyrecovers 97% of its plastic waste.

Whim Architecture has proposed making an island the size of Hawaii from Pacific ocean plastic waste, to create a floating home for 500,000 people, powered by solar energy and wave motion. Electrolux has launched a “Vac from the sea” initiative to suck waste out of the ocean to use it tomake sustainable vacuum cleaners.

2 of the first 5 vacuum cleaners!!

The European Union offers fishermen cash for catchingplastic rubbish instead of fish!

Recycled plastic“reefs” protect Dubai coast from erosion

“The results of our study clearly show that scampi in the Clyde (estuary) are consuming plastics and that one of the sources of this plastic is that used by the scampi fishery itself.” (that is, the nets!)

----Researchers from London and Aberdeen Universitieswrote in the Marine Pollution Bulletin, 2011:--

What does scampi have in its stomach?Four fifths of them have plastic

THE END!

THANKS FOR STAYING AWAKE!