Singularidades da Borracha Natural e Celulose Abrem Novas

Perspectivas

Fernando Galembeck University of Campinas

IPT – Institute for Technological Research (São Paulo) GG&FG Consultores

11/9/16 1

Synopsis

• Biomass: food, energy and raw materials • in the past

• present situation

• scenarios

• a matter of policy

• Materials from biomass • Natural rubber

• Cellulose

• Prospects and Needs

2 11/9/16

In the past: biomass provided food, energy and raw materials

Food: 100%

Energy: wood

Raw materials: wood, natural fibers + minerals

Consequence: land change

11/9/16 3

by Sir Mark Walport, Dec 2013

http://www.slideshare.net/bis_foresight/natural-history-museum-annual-science-lecture-2013

Current losses and gains

11/9/16 4 http://www.caithness.org/photos/nature/millenniumecosystem/14.jpg

Then came coal, oil and gas

11/9/16 5 https://notable.files.wordpress.com/2007/04/energy-per-capita.png

Abundant oil? Make protein from oil!

• Use of hydrocarbon fractions for production of single-cell protein • Nine plants in the Soviet Union ranged from 50 to 240,000 tons/year. • http://www.nytimes.com/1973/11/10/archives/soviet-plant-to-convert-oil-to-protein-for-feed-use-of-yeast.htm

• Unesco Science Prize, 1976

11/9/16 6

France Alfred Champagnat BP's Lavera Oil Refinery in France

“pour ses conclusions sur la production à la chaîne et à bas coût de nouveaux proteines provenant du pétrole”

“for his findings on the low-cost mass production of new proteins from petroleum”

http://unesdoc.unesco.org/images/0011/001111/111158E.pdf

Produção industrial

População POPULATION

POLLUTION

SERVICES INDUSTRIAL PRODUCTION

FOOD

NATURAL RESOURCES

http://polynomial.me.uk/tag/science/

Concern: resource depletion. World 3 model

11/9/16 7

Nuclear 2.5%

(*) RENEWABLES 2016- Global Status Report. Renewable Energy Policy Network for 21st Century, p. 28. http://www.ren21.net/wp-content/uploads/2016/06/GSR_2016_Full_Report.pdf, accessed, on 12 July, 2016.

New policies favored renewable sources 2014: Estimated renewable energy share of global final

energy consumption.

All renewables 19.2%

Fossil fuels

Nuclear 2.5%

Modern renewables 10.3%

Traditional biomass 8.9%

11/9/16 8

The Food Crisis (2007)

• The ”Food riots” • FAO Food Price Index rose to 220 (Jul 2008) and 238(2011)

• Causes: • Rising biofuel production from corn, sugarcane, palm oil

• Wild commodity speculation, pre 2008 financial crisis

• Climate, drought

11/9/16 9

By Jashuah - Own work by uploader, data from Food and Agriculture Organization, CC BY-SA 3.0, https://commons.wikimedia.org/w/index.php?curid=19394247

Speculation on commodities

• Food price increase fueled by wild commodity speculation, pre-2008 financial crisis

• Phosphate rock prices: 50 to 460 US$/tonne (Jan 2007 to July 2008)

11/9/16 10

http://en.mercopress.com/data/cache/noticias/37399/0x0/food-protesters.jpg

http://www.australianminesatlas.gov.au/aimr/images/phosphate-figure3.jpg

FAO Food Price Index

Phosphate rock price

Jan 2007 Jan 2009

FAO Hunger Map, 2015

11/9/16 11

Legend

Target achieved

Target not achieved, slow

progress

Target not achieved, lack of

progress or deterioration

http://www.fao.org/3/a-i4674e.pdf

A matter of policy: Global Hunger Index scores

1990 1995 2000 2005 2013

Brazil 8.7 7.6 6.4 <5 <5

Angola 39.5 38.5 31.6 22.7 19.1

India 32.6 27.1 24.8 24.0 21.3

China 13.0 10.4 8.4 6.7 5.5

Vietnam 30.9 25.1 18.1 13.7 7.7

11/9/16 12

≥ 30.0 extremely alarming

20.0–29.9 alarming 10.0–19.9 serious 5.0–9.9 moderate

< 5.0 – low http://dx.doi.org/10.7910/DVN/22795

Compound index based on: (1) the percentage of people who are under- nourished, (2) the percentage of children younger than age five who are underweight, and (3) the mortality rate of children younger than age five

Products from sugarcane

• Sugarcane was introduced in South and Central America in the 16th century, to produce sugar.

• Sugar crystallization residues were fermented to produce ethanol.

• In 1976: 2nd oil crisis led the government to create subsidies for fuel ethanol production.

• In 1990: subsidies were eliminated in 90% of the producing areas.

• Today: sugarcane is the biomass input for making ethanol, butanol, polyethylene, wax, green solvents and surfactants, nanosilica, cellulose, paper and pulp, microcrystalline cellulose, PHB-and other thermoplastics, lysine (>600,000 tons/year), electricity.

11/9/16 13

New products

Amyris Inc. (US): Myralene™-10 – New high-performance, sustainably sourced and cost-competitive solvent made from β-farnesene New high-performance, cost-competitive solvent made from β-farnesene

Produced in Brazil on a commercial scale by fermentation of sugarcane juice using special strains of baker's yeast.

SIP Ltd (UK): SIPDRILL RS – First renewable, hydrocarbon drilling base fluid for high performance drilling mud systems. Renewable alkene designed for use in high performance drilling mud systems. SIPDRILL RS is 100% hydrocarbon, manufactured via the proprietary fermentation of sustainable sugar, producing farnesane, ß-farnesene and n-hexadecene.

• www.biowerkstoff-kongress.de

11/9/16 14

Biofuels contribute to food security

“…biofuels may offer an opportunity to improve food security.

Yet, for many poorer countries in Africa and elsewhere, biofuels may be better viewed as a potential export or as a means for reducing fossil fuel imports.

…producing conventional biofuels in low-income countries could raise rural incomes beyond what is required to offset rising food prices.

Studies in Ethiopia: … farmers’ participation in biofuel programs encouraged greater use of fertilizers and improved farming technologies, leading to higher food-crop productivity and better food security during the year. One precondition for success, however, was farmers’ access to high-quality, productive biofuel crops.”

11/9/16 15

C. Arndt, S. Msangi and J. Thurlow, Fueling the path to food security, IFPRI Global Food Policy Report 2016 p.63

Unique properties of materials derived from biomass

• Natural Rubber, Cellulose

• Electrostatic Adhesion

• Natural Rubber accounts for 42% of global elastomer consumption

• Essential to tire and anti-vibration industries

Rubber Statistical Bulletin April-June edition, quoted by S. Rolere, C. Cazevielle, J. Saint-Beuve and F. Bonfils in European Polymer Journal (2016)

16 11/9/16

The “mistery of natural rubber”

• Synthetic rubber does not show the same properties as natural rubber

• ”In general, as the tire size increases and the level of punishment the tire will take goes up, the amount of natural rubber increases due to natural rubber's good shear resistance, load bearing capability, and high level of resistance to cuts.” Josh Velson in https://www.quora.com/Is-natural-rubber-a-substitute-for-synthetic-rubber-in-tire-manufacturing

• Which is the role of the non-rubber constituents (inorganics, proteins and phospholipids NR properties?

• Yasuyuki Tanaka - Structural Characterization of Natural Polyisoprenes-Solve the Mystery of Natural Rubber Based on Structural Study, RC&T 74 (3) 355 (2001)

17 11/9/16

Adherent mineral nanoparticles in natural rubber

Al

C

PN

SBF 200 nm

• ESI-TEM thin film elemental maps of dialyzed natural rubber latex film

• C, N densification around the inorganic particles: adhesion

• Rippel, M.M. et al. Analytical Chemistry, 2002

18 11/9/16

Preparation of nanocomposites in aqueous media using latex

Varghese, S., Karger-Kocsis, J., Polymer, 2003, 44, 4921. Wu, Y.P., Wang, Y.Q., Zhang H.F. et al. J. Compos. Sci. Tech. 2005, 65, 1195 Valadares, L. F., Leite, C. A. P., Galembeck, F., Polymer, 2006, 47, 672. Valadares, L. F., Murakami, M. M., Rippel, M. M., Galembeck, F., PI0301193-3, INPI, 2003.

19 11/9/16

Rubber-clay nanocomposite mechanical properties

• Tensile testing:

Modulus increases to 250 times

Maximum stress increases up to 3.5 times

0 100 200 300 400 500 600 700 800 900 1000 1100 1200

0

1

2

3

4

5

6

7

8

9

10

0 100 200 300 400 500 600 700 800 900 1000 1100 1200

0

1

2

3

4

5

6

7

8

9

10

0 100 200 300 400 500 600 700 800 900 1000 1100 1200

0

2

4

6

8

10

0 200 400 600 800 1000 1200

0

2

4

6

8

10

30 phr

E = 223 MPa

10 phr

E = 31 MPa

20 phr

E = 109 MPa

5 phr

E = 6.5 MPa

Natural rubber

E = 0.9 MPa

Str

ess [M

Pa]

Strain [%]

Valadares, L. F., Leite, C. A. P., Galembeck, F., Polymer, 2006, 47, 672.

20 11/9/16

Clay within rubber: strong polymer – clay adhesion

Valadares, L. F., Leite, C. A. P., Galembeck, F., Polymer, 2006, 47, 672.

21 11/9/16

Lower xylene swelling

0 20 40 60 80 100 120

0

500

1000

1500

2000

2500

0 20 40 60 80 100 120

0

1

2

3

4

5

0 20 40 60 80 100 120

0

1

2

3

4

5

0 20 40 60 80 100 120

0

1

2

3

4

5

Ma

ss u

pta

ke

[%

]

Time [min]

Natural rubber

10 phr clay

30 phr clay

x/x

y/y

z/z

Time [min]

x/x

y/y

z/z

x

y

z 1cm

30 phr Natural rubber

(phr = per hundred rubber)

22 11/9/16

• Capillary adhesion during drying

• Electrostatic adhesion in the dry monolith

• Both are controlled by interfacial properties

• Water-based processes for making composites from incompatible

materials

23

Composite formation and stability

Valadares, L.F; Bragança, F.D.; Linares, E.; Galembeck, F. J. Phys Chem C 112 (2008) 8534-8544.

11/9/16

A styrene-acrylic resin cast on polyethylene: poor film,

poor adhesion

The same but with clay: good film, good adhesion

to PE

24

Water is a general-purpose cohesive agent

11/9/16

Starch/rubber/clay

Starch/rubber

SEI

SEI

•Good compatibility between rubber and starch.

•Clay modifies starch/rubber blend morphology.

BEI

Morphology – SEM

25 11/9/16

Electrostatic contributions

• Latex blends and nanocomposites display complex charge patterns.

• Charge patterns are modified due to ion transfer.

• Charge distribution contributes to increased compatibility between phases. • Compatibility independent on bulk phase properties.

• Unique combinations of mechanical properties are obtained.

• Nanoparticles produce more pronounced effects.

26 11/9/16

Alkaline cellulose solutions

•Cellulose is amphiphilic and this is the reason for its insolubility.

•Cellulose alkaline solutions are excellent adhesives for wet and dry cellulosic substrates.

•Cellulose alkaline solutions exfoliate graphite • useful for making multi-layer graphene.

27

*Medronho, B. et al. Cellulose 2012, 19 (3), 581–587. Source: Glasser, W. G. et al. Cellulose 2012, 19, 589–598.

11/9/16

Repulping performance

Repulpability tests

Wet-milled adhesive joints and filter paper, after 30 min

PVA adhesive cellulose adhesive

without adhesives

Stable dispersion

Decanted pulp

five filter paper lap joints wet-milled in a blender 30 min

28 11/9/16

Graphite and cellulose dispersion in aqueous media

Hydrophobic powder

Homogeneous hydrophilic sediment

Graphite + water: Graphite + water + alkaline cellulose

(different concentrations):

Solids on the plastic surface

Stable dispersion

Stable viscous dispersion

29 11/9/16

Graphite - cellulose particles

500 nm

TEM

Energy loss 25 eV

Cellulose cover:

Graphite exfoliation:

graphene and nanographite

stable and water dispersible

500 nm

30 11/9/16

Agradecimentos

• Márcia Maria Rippel

• Leonardo Valadares

• Fabio Bragança

• Elisângela Linares

• Sérgio Jannuzzi

• Carlos Alberto Paula Leite

• Douglas Soares

• Carlos Costa

• Érico Teixeira Soares

• Melissa Braga

• Maria do Carmo V. M. da Silva

• Projetos do MCTI: Instituto do Milênio de Materiais Complexos, INCT de Materiais Complexos Funcionais

• Fapesp (Temático e INCT)

• Finep

• Petrobras

• Orbys

11/9/16 31

11/9/16 32