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History History: First there were Bio-Polymers

Animal Hides (Proteins): Fiber & FilmsLigaments (Collagen): HingesSilk Fibers (Protein): FibersPlant Fibers (Cellulose): Fibers

Yucca-fiber sandals Bison-Hide teepee

Structural Materials: High Modulus & StrongWood (Cellulose & Lignin): SAntlers (Keratin): Tools, jewelry & weaponsHorn (Keratin): Tools, jewelry & weaponsTusks (enamel & dentin): Tools, jewelry & weapons

Ivory lunar cycle charts 62

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History

1839 Vulcanized rubber (C. Goodyear) 1862 Celluloid (Parkes)1868 Nitrocellulose 합성 (J.W. Hyatt) 1885 Rayon, Cellopane1909 phenol-formaldehyde resin (L.H. Baekeland)

(1910 한일합병/을사보호조약)(1919 김성수, 국민 모금 경성방직 설립, 무명 옷감 제조)

1922 Polymer by H. Staudinger1927 Cellulose actate, Poly(vinyl chloride)

Buna S (butadiene-styrene rubber (Bayer Co.) 1928 Poly(methyl methacrylate)(O. Rohm). 1930 Polystyrene. 1931 Neoprene (DuPont Co. W. H. Carothers) 1935 Nylon 66 (W.H. Carothers). 1936 PAN, SAN, Poly(vinyl acetate) 1937 Polyethylene (O. Bayer). 1938 Nylon 6, Epoxy resin, LDPE

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History

1941 PET (J.R. Whinfield와 J.T. Dickinson).1942 PAN (commercialized by DuPont).

(1945 제2차세계대전 종전/대한민국 독립) (1943 국제고무 "말표" 고무신 생산)(1947 한국나이롱 나일론 66 방적)

1948 ABS resin. 1950 한국전쟁 발발/ 자동차 타이어의 노화 원인이 오존인 것

을 밝혀내고 antiozonant의 개발 시작1952 Catalyst for PE under low pressure (by K. Ziegler).1953 Nobel Prize winning of Hermann Staudinger

(Work on macromolecules) 1954 Polyurethane1955 Stereoregular polymer using Ziegler-Natta Catalyst(G. Natta)1956 Acetal1957 Polypropylene, Polycarbonate1964 Ionnmer, Polyimide

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History

SS

SS

SS

Sulfur crosslinking Vulcunization

1942 합성고무 프로젝트 (WWII)“우리가 대규모의 새로운 고무 공급이 이루어지지 않으면 전쟁노력과 국내경제도 모두 붕괴될 것이다.” – Baruch 위원회 보고서, 1942 (전선, 타이어 등의 수요 급증)

Rubber :

→ Vulcunization of natural rubber by Charles Goodyear, 1839

Poly-cis-isoprene

Enabled commercialization of natural rubber

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▶ Nitrocellulose :

- by Christian Schoenberg, Swiss Chemist, 1840’s- Applications : guncotton(면화약), film

History

Nitrocellulose was perceived as a possible "smokeless powder" and a propellant for artillery shells thus it received the name of guncotton.

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▶ Celluloid :The first man-made plastic- by Alexander Parkes, 1862, London

International fair- Parkesine: made from cellulosics materials,

can be molded by heating- Applications : Buttons, Cobs, Pens, Billiards

ballscf. J. Hyatt (1869, USA)

▶ Cellophane : Celluloid Photographic Film

- by George Eastman – 1885

History

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▶ Polystyrene : - by Eduard Simon, 1839- Applications : ; packaging (Styrofoam)

▶ Poly(vnylchloride) (PVC) :- by Eugen Baumann, 1872- Applications : pipe, toys, floor

▶ Rayon : - first man-made fibers, regenerated cellulose- applications : textiles, tire cord, cellophane,

History

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▶ Bakelite : first totally synthetic plastics (Thermoset resin; formaldehyde resin)

- by Leo Bakeland, 1907- applications : replaced rubber for insulation in electrics

History

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▶ Nylon : Nihil(허무)+Dupont- by Wallace H Carothers, 1830년대- Applications : packaging and stocking

Wallace Hume Carothers- 1929 : Concepts of Addition and Condensation polymers- Neoprene : First Synthetic Rubber- Polyester - Nylon (Polyamide)

History

Extract from "Fortune Magazine" about nylon circa 1938: "nylon breaks the basic elements like nitrogen and carbon out of coal, air and water to create a completely new molecular structure of its own. It flouts Solomon. It is an entirely new arrangement of matter under the sun, and the first completely new synthetic fiber made by man.

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Applications of Nylon

HistoryDuPont touted its new fiber as being "as strong as steel, as fine as a spider's web," and first announced and demonstrated nylon and nylon stockings to the American public at the 1939 New York World's Fair.

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O

OMe

MeO

O OH

HO

O

O

O

OO O

OO OO O

O

▶ Polyester : - by Dupont, Dacron® cf. Terylene ® (by ICI)- Applications : Leisure wear

▶ Teflon- by Roy Plunke, 1938 - Applications : Artillery shell cover

History

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▶ Polyethylene (PE): - by E.W. Fawcett & R.O. Gibson, 1933

- Applications : First used for underwater cable coatings and insulation for radarnow, most versatile plastic

LDPE, 1939 HDPE, Ziggler-Natta catalyst, 1943

Ziegler & Natta:(Cowinner of Nobel Prize, 1963)

▶ Polypropylene (PP): - by Guilier Natta, 1957

- Applications : packaging film, tape, fiber, pipe, toy, and miscellaneous

History

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▶ Acrylics▶ Spandex▶ High performance Textiles: Aramid (ex. Kevlar)

▶ Polymer Blend▶ Compoiste: ex. Fiber-reinforeced plastics, FRP섬유강화복합재료)▶ Nanocomposite▶ High performance & Novel functionality

History

Applications : Part of an automobile

WiperPolyisoprene

BobyABS (bumper)All for Saturn

Headlight canPolycarbonate

Air filterCellulose,

polyisoprene

InteriorNylon, PP (carpet)

PET, leather (seats)SBS (dashboard)

TireSBS, Polyisoprene,

Polyisobutene, Kevlar

HosePolyisoprene

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Applications : electronics

Housings

Polystyrene, ABS

Speakers

Cellulose, PP, PVDF

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Applications : electronics

Epoxy, Polyimide (packaging)

PHS (photoresist)

Polyimide, silicon polymer

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Applications : electronics

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Applications Applications: Flexible display

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Applications:

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Applications:

82

Tyvek - a brand of flashspun high-density polyethylene fibers, a synthetic material; commercialized by DuPont. - very strong; difficult to tear but can easily be cut with scissors or a knife. Water vapor can pass through Tyvek (highly breathable), but not liquid water.- Applications : envelopes, car covers, air and water intrusion barriers(housewrap) under house siding, labels, coveralls, wristbands, mycology, and graphics.

Applications:

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An artificial organ

is a man-made device that is implanted or integrated into a human to replace a natural organ, for the purpose of restoring a specific function or a group of related functions so the patient may return to as normal a life as possible.

Ex. Heart, bone, skin, blood vessel, joint

Applications:

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MOTO W233 Renew Blue Earth

Recycling symbols

O

O*

O

OO

*n

Poly(ethylene terephthalate) or PETE

**

nhigh density polyethylene

**

nlow density polyethylene

**

n

polyvinyl chlorideCl

**

n

poly(propylene)Me

**n

polystyrene

Not recyclable

Sustainable Development

“ that meets the needs of the present without compromising the ability of future generations to meet their own needs” 

(Brundtland Commission, 1987)since the 1980s sustainability has been used more in the sense of human sustainability on planet Earth and this has resulted in the most widely quoted definition of sustainability as a part of the concept sustainable development

the relationship between the three pillars of sustainability suggestingthat both economy and society are constrained by environmental limits

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The world is gradually running short of oil

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a vegetable oil- or animal fat-based diesel fuel consisting of long-chain alkyl (methyl, propyl or ethyl) esters. Biodiesel is typically made by chemically reacting lipids (e.g., vegetable oil, animal fat) with an alcohol producing fatty acid esters.

Bus run by biodiesel

Renewable sources of energy : Green sources

Bio-diesel

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Wind power plant

Solar power

Tidal power

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Synthetic Materials from Petroleum

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Environmental Demands

When plastics made from petroleum are burned, they release the carbon dioxide contained in the petroleum into the atmosphere, leading to global warming.

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Greenhouse Effect

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- Visible energy from the sun passes through the glass and heats the ground

- Infra-red heat energy from the ground is partly reflected by the glass, and some is trapped inside the greenhouse

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- Thermal radiation from a planetary surface is absorbed by atmospheric greenhouse gases, and is re-radiated in all directions.

- Since part of this re-radiation is back towards the surface and the lower atmosphere, it results in an elevation of the average surface temperature(14◦C) above what it would be in the absence of the gases (-19◦C)

Greenhouse Effect

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- The Greenhouse Effect is a warming of the Earth’s surface and the lower atmosphere.

- greenhouse effect make life on Earth possible – and could destroy life as we know it.

- Greenhouse gases : Water vapor, 36-70%, Carbon dioxide, 9-26%, methane, 4-9%, ozone, 3-7%

Greenhouse Effect

Carbon footprint

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- The total sets of greenhouse gas(GHG)(CO2, CH4) emissions caused by an organization, event, product or person.

- Almost everything we do involves burning fossil fuels at some point, either directly or indirectly.

- For the typical household, there are five main sources of emissions:

Carbon footprint

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- The natural ecosystem has ways to absorb the increase in CO2 via natural carbon ‘sinks’ such as trees and the ocean, but these natural balances are unable to keep pace with the amount of carbon we are emitting into the atmosphere(one-way process).

- By having a big carbon footprint, you are contributing to global warming.

Atmosphere

BiomassCarbon

Biogen

ic CO

2

CO2

Foss

il Fu

el

Atmosphere

Non

-bio

geni

c C

O2

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Carbon footprintglobal warming will lead to some serious problems in the next few years:

- increasing the spread of disease,

- more extreme weather events such as hurricanes and tornados,

- an increase in droughts and deadly heatwaves,

- increased animal extinctions,

all of which will then lead to severe economic consequences.

Earth’s climate is warming and human activitiesare primarily responsible (>90% certainty)

280 to 430ppm concentration between 1850 and 2000 (0.5‐0.8oC increase)

550ppm likely by 2035 with

77‐99% chance of 2oC increase

50% chance of 5oC increase

Climate Change

AVG: 1990 - 5.2%

GH

G E

mis

sions

ton/

year

1990

:

Bas

e Ye

ar

2012

2008

First Commitment Period: 2008-2012

The Demand:Kyoto ProjectsEU ETS Allowances

Kyoto Protocol38 Developed Countries and Economies in Transition (Annex I countries) took on reduction commitments in 1997

The industrialised countries commit themselves to reduce their collective GHG emissions by at least 5% below 1990 emission levels

Certified Emission Reduction

Annex ICountry

(Developed Nations)

commit themselves to reduce their collective GHG emissions by at least 5% below 1990 emission levels

Non-Annex I CountryFunding

TechnologyProjects to reduce GHG

emissions

*Certified Emission Reduction (CER)

Emission reduction compared to an existing baseline

Clean Development Mechanism (CDM)

- Contribute to sustainable development- Facilitate technology transfer- Improve financial returns

*CER : a type of emissions unit (or carbon credits) issued by the CDM Executive Board for emission reductions achieved by CDM projects

Certified Emission Reduction

Certified Emission Reduction (CER)

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► CO2 neutral

Certified Emission Reduction

102

having a net zero carbon footprint, refers to achieving net zero carbon emissions by balancing a measured amount of carbon released with an equivalent amount sequestered or offset, or buying enough carbon credits to make up the difference

► CO2 neutral

Certified Emission Reduction

103

Materials from Natural Resources

104

Biomaterials are from renewable resources.

They are also biodegradable, meaning that the material returns to its natural state when buried in the ground.

Fiber Reinforced Composites (FRP)+

• Reduced weight • Increased flexibility • Greater moldability• Less expensive • Sound insulation • Renewable resource • Self-healing properties

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Fibers :• Glass fibers• Carbon fibers• Aramid fibers• Biofibers

(cellulose, protein, …)

Matrix :• Petroleum‐based 

polymers• Metals• Ceramics• Biopolymers

(starch, PLA, …)

FRP• Biocomposites

•Growing at 9.9% per year•Substituting glass fiber  

•The current Benz A‐Class has 26 components containing renewable raw materials such as abaca, flax, and hemp.

Biocomposites and Automobiles

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Building Materials : ex. Hemp

‐ Extremely high thermal resistance , acoustic properties ‐ It has an ability to absorb & release moisture without effecting thermal performance. ‐ It is not affected by mould growth or insect attack as the fiber does not contain proteins.‐ It does not cause irritation.‐ Lightweight, easy to handle

107 108

► biodegradable and recyclable

► CO2 neutral

Bioplastics

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Packaging Materials

Biodegradable replacements for plastic bags of all kinds

Add fiber to recycled paper to extend life

After their initial use they can be reused as bags for organic waste and then be composted. .

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Polymers vs. Macromolecules

A macromolecule is a very large molecule commonly created by polymerization of smaller subunits.

In biochemistry, the term is applied to the three conventional biopolymers (nucleic acids, proteins and carbohydrates), as well as non-polymeric molecules with large molecular mass such as lipids and macrocycles.

111a polypeptide macromolecule

Hexameric Palladium(II) Terpyridyl

Metallomacrocycles

Polymers vs. Macromolecules

Which macromolecule is not a polymer?

Answer:

Lipids are macromolecules that aren't polymers, as their structure does not consist of a repeating chain of monomers.

112

A protein is an example of a macromolecule. Each amino acid in the chain (the monomers) can be different and the macromolecule has a definitive shape that is controlled by the monomers in it. Unlike plastic where the monomers are all the same. Every amino acid has the same backbone N-C-C=O but has different "R" groups on it depending on it function.

Polymers vs. Macromolecules

DNA

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Polymers vs. Macromolecules

a polyphenylene dendrimer macromolecule

114

Dendrimers : repetitively branched molecules