This document discusses materials for a sustainable future. It begins by asking whether the future will be a golden age or decline for humanity based on available materials. It then discusses using biomass for food, energy and raw materials historically. Current issues around using biomass for biofuels contributing to food insecurity are also examined. The document explores materials that can be produced from biomass like sugarcane and the potential of natural rubber composites and conductive materials made from cellulose and graphite. It argues that electrostatics and friction are fundamental topics that were neglected but are now seeing renewed interest for applications.
Joachim von Braun, Director, Center for Development Research (ZEF) and Professor, Economics and Technical Change, University of Bonn
POLICY SEMINAR
Bioeconomy – the new transformation of agriculture, food, and bio-based industries – implications for emerging economies
OCT 24, 2017 - 12:15 PM TO 01:15 PM EDT
2021 hidalgo et al. - development of an innovative process involving the us...Jokin Hidalgo
Development of an innovative process involving the use of
ionic liquids for the recovery and purification of rare earths
from permanent magnets and NIMH batteries
GT Briefing March 2012 Technologies Reshaping Our WorldTracey Keys
Technology is changing the way we live and work at exponential rates. Ponder this for a moment: your parents have lived through the entire development of the computing era while many five year olds have no concept of a world without technology – it is simply part of their lives. This month, we’d decided to look ahead – a long way ahead in some cases – at radical and innovative technologies that will potentially reshape our world in the decades to come. In today’s world, it’s easy to get swamped by short-term thinking and firefighting but we don’t like to encourage it…
From developments that allow us to overcome the resource challenges presented by population growth to advances that will reshape the production of goods and services, our environment and our humanity, technology will challenge us to rethink every aspect of what we do and how we do it. While some of the breakthroughs will be exciting and easy to embrace, others will challenge vested interests and the status quo. Our comfort zones will be disrupted. But, like it or not, these changes will come – sooner than we think in some cases. What is your organization doing to get ready? What will be the impact on your customers and consumers? What are YOU doing?
Municipal solid waste management (MSWM)
constitutes one of the most crucial health and environmental
problems facing authorities in the Khartoum State (Sudan). The
analysis showed that Khartoum State produced around
1,040,250 tons of solid municipal waste annually 12.7% of it
plastic which is 132,112 tons. Studies say that the liquid (oil)
yield of thermal pyrolysis of plastic waste is between 80-90%.
Modification made by Aspen Hysys program for thermofuel
process to improve the efficiency of the process.
O R I G I N A L P A P E RManagerial Preferences in Relatio.docxcherishwinsland
O R I G I N A L P A P E R
Managerial Preferences in Relation to Financial
Indicators Regarding the Mitigation of Global Change
Josef Maroušek • Simona Hašková • Robert Zeman •
Radka Vanı́čková
Received: 3 February 2014 / Accepted: 11 March 2014 / Published online: 20 March 2014
� Springer Science+Business Media Dordrecht 2014
Abstract Biochar is a soil—improving substrate made from phytomass pyrolysis. In
Southeast Asia, its application decreases due to the long-term growth of biochar cost
and thus caused further prolongation of the payback period. In the Euro-American
civilization the biochar application is already almost forgotten once it has been much
earlier recognized that the crop yields can be increased much faster with higher doses
of nutrients and other agrochemicals. The payback period can be expected in decades.
Such a long-time investment into soil fertility raises also many ethical questions. The
final decision combines issues of social responsibility, risk and other financial indi-
cators as well as personal preferences and more. The attitudes of Western and Central
European decision makers in the agriculture business segment were analyzed on the
basis of electronic questionnaire survey and a subsequent interview through their local
unions. According to the data, most of them did not know about the possibilities of a
more environmentally friendly approach to soil enhancement based on the addition of
a fertilizer in the form of biochar. Among others, the collected data also shows that the
decision makers from Western Europe have a much different ethical approach to the
land and financial indicators than the Central Europeans.
Keywords Biochar � Financial indicators � Discounted payback period �
Net present value
Introduction
Although we can not take the evidence from a scientific point of view to be sufficient, it
is assumed that the Amazonian Indians applied biochar (called as black soil) to increase
J. Maroušek (&) � S. Hašková � R. Zeman � R. Vanı́čková
The Institute of Technology and Businesses in České Budějovice, Okružnı́ 517/10,
370 01 České Budějovice, Czech Republic
e-mail: [email protected]
123
Sci Eng Ethics (2015) 21:203–207
DOI 10.1007/s11948-014-9531-2
the soil fertility more than a thousand years ago. Ancient Japanese text refers to biochar
(called fire manure) in 1697 (Lehmann and Joseph 2009). The positive effects of the
biochar were evidently observed a long time ago. However, its complex relationships
between production technology design and the parameters obtained as well as soil
interactions and the relation to the phytomass yields are a subject of many recent studies
(Lehman et al. 2006, 2011; Atkinson et al. 2010; Sohi et al. 2010). Interconnecting the
conclusions of these robust reviews it may be summarized that the mechanism that
underlies the efficacy of the biochar is strongly connected with the microporosity which
provides a high surface area to .
Plenary lecture of the XVIII B-MRS Meeting given by Prof. Alan Taub (University of Michigan, USA) on September 26, 2019 at Balneário Camboriú (Brazil).
Joachim von Braun, Director, Center for Development Research (ZEF) and Professor, Economics and Technical Change, University of Bonn
POLICY SEMINAR
Bioeconomy – the new transformation of agriculture, food, and bio-based industries – implications for emerging economies
OCT 24, 2017 - 12:15 PM TO 01:15 PM EDT
2021 hidalgo et al. - development of an innovative process involving the us...Jokin Hidalgo
Development of an innovative process involving the use of
ionic liquids for the recovery and purification of rare earths
from permanent magnets and NIMH batteries
GT Briefing March 2012 Technologies Reshaping Our WorldTracey Keys
Technology is changing the way we live and work at exponential rates. Ponder this for a moment: your parents have lived through the entire development of the computing era while many five year olds have no concept of a world without technology – it is simply part of their lives. This month, we’d decided to look ahead – a long way ahead in some cases – at radical and innovative technologies that will potentially reshape our world in the decades to come. In today’s world, it’s easy to get swamped by short-term thinking and firefighting but we don’t like to encourage it…
From developments that allow us to overcome the resource challenges presented by population growth to advances that will reshape the production of goods and services, our environment and our humanity, technology will challenge us to rethink every aspect of what we do and how we do it. While some of the breakthroughs will be exciting and easy to embrace, others will challenge vested interests and the status quo. Our comfort zones will be disrupted. But, like it or not, these changes will come – sooner than we think in some cases. What is your organization doing to get ready? What will be the impact on your customers and consumers? What are YOU doing?
Municipal solid waste management (MSWM)
constitutes one of the most crucial health and environmental
problems facing authorities in the Khartoum State (Sudan). The
analysis showed that Khartoum State produced around
1,040,250 tons of solid municipal waste annually 12.7% of it
plastic which is 132,112 tons. Studies say that the liquid (oil)
yield of thermal pyrolysis of plastic waste is between 80-90%.
Modification made by Aspen Hysys program for thermofuel
process to improve the efficiency of the process.
O R I G I N A L P A P E RManagerial Preferences in Relatio.docxcherishwinsland
O R I G I N A L P A P E R
Managerial Preferences in Relation to Financial
Indicators Regarding the Mitigation of Global Change
Josef Maroušek • Simona Hašková • Robert Zeman •
Radka Vanı́čková
Received: 3 February 2014 / Accepted: 11 March 2014 / Published online: 20 March 2014
� Springer Science+Business Media Dordrecht 2014
Abstract Biochar is a soil—improving substrate made from phytomass pyrolysis. In
Southeast Asia, its application decreases due to the long-term growth of biochar cost
and thus caused further prolongation of the payback period. In the Euro-American
civilization the biochar application is already almost forgotten once it has been much
earlier recognized that the crop yields can be increased much faster with higher doses
of nutrients and other agrochemicals. The payback period can be expected in decades.
Such a long-time investment into soil fertility raises also many ethical questions. The
final decision combines issues of social responsibility, risk and other financial indi-
cators as well as personal preferences and more. The attitudes of Western and Central
European decision makers in the agriculture business segment were analyzed on the
basis of electronic questionnaire survey and a subsequent interview through their local
unions. According to the data, most of them did not know about the possibilities of a
more environmentally friendly approach to soil enhancement based on the addition of
a fertilizer in the form of biochar. Among others, the collected data also shows that the
decision makers from Western Europe have a much different ethical approach to the
land and financial indicators than the Central Europeans.
Keywords Biochar � Financial indicators � Discounted payback period �
Net present value
Introduction
Although we can not take the evidence from a scientific point of view to be sufficient, it
is assumed that the Amazonian Indians applied biochar (called as black soil) to increase
J. Maroušek (&) � S. Hašková � R. Zeman � R. Vanı́čková
The Institute of Technology and Businesses in České Budějovice, Okružnı́ 517/10,
370 01 České Budějovice, Czech Republic
e-mail: [email protected]
123
Sci Eng Ethics (2015) 21:203–207
DOI 10.1007/s11948-014-9531-2
the soil fertility more than a thousand years ago. Ancient Japanese text refers to biochar
(called fire manure) in 1697 (Lehmann and Joseph 2009). The positive effects of the
biochar were evidently observed a long time ago. However, its complex relationships
between production technology design and the parameters obtained as well as soil
interactions and the relation to the phytomass yields are a subject of many recent studies
(Lehman et al. 2006, 2011; Atkinson et al. 2010; Sohi et al. 2010). Interconnecting the
conclusions of these robust reviews it may be summarized that the mechanism that
underlies the efficacy of the biochar is strongly connected with the microporosity which
provides a high surface area to .
Plenary lecture of the XVIII B-MRS Meeting given by Prof. Alan Taub (University of Michigan, USA) on September 26, 2019 at Balneário Camboriú (Brazil).
Plenary lecture of the XVIII B-MRS Meeting given by Prof. Antonio José Roque da Silva (CNPEM, Brazil) on September 24, 2019 at Balneário Camboriú (Brazil).
Tribute in honor of Prof. Ivo Alexander Hümmelgen, a member of the Brazilian materials research community, who died unexpectedly in March 2019. The tribute was made by Prof. Marco Cremona (PUC-Rio), on September 23, 2019 in Balneário Camboriú (Brazil), at the opening of symposium F, that was dedicated to Organic Electronics, the research area of Prof. Hümmelgen.
Memorial Lecture Joaquim da Costa Ribeiro, given by Prof. Yvonne P. Mascarenhas (IFSC and IEA/ USP, Brazil) in the Opening Ceremony of the XVIII B-MRS Meeting on September 22, 2019 at Balneário Camboriú (Brazil).
Presentation of the XVIII B-MRS Meeting (September 22 - 26, 2019, Balneario Camboriú), given by Prof. Ivan H. Bechtold, chair of the event, at the closing ceremony of the XVII B-MRS Meeting, on September 20, 2018.
Memorial lecture "Joaquim da Costa Ribeiro" given by Prof. João A. H. da Jornada (IF-UFRGS) on September 10, 2017 in Gramado (Brazil) during the opening of the XVI B-MRS Meeting.
Plenary lecture given by Prof. Kenneth Gonsalves (ITT Mandi, India) on September 12, 2017 in Gramado (Brazil) during the XVI B-MRS Meeting. Acknowledgment: ITT Mandi.
Plenary lecture given by Prof. Katsuhiko Ariga (WPI-MANA, NIMS and University of Tokyo, Japan) on September 12, 2017 in Gramado (Brazil) during the XVI B-MRS Meeting.
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1. Materials for a
Better Future
Fernando Galembeck
University of Campinas
Inomat (INCT for Complex Functional Materials)
GG & FG
Costa Ribeiro Memorial Lecture
17th B-MRS/SBPMat Meeting
8/16/16 1
2. Synopsis
• A Golden Age OR Decline of Humankind?
• Biomass: Food, energy and raw materials
• Materials from biomass
• Chemical Electrostatics
• Perspectives
8/16/16 2
3. What is ahead?
• Every epoch is marked by
transformation mediated by
materials.
• What are the upcoming new
materials and how will they
transform our lives?
• Will the needed materials still be
available, in the coming decades?
3
4. A Golden Age?
• Prospect: unlimited supply of energy
• Inexpensive solar energy, competitive wind power,
biomass…
• Fusion, in twenty years (?)
• Inexpensive energy is the key to abundant raw
materials
• e.g. lithium
• Largest reserves in the world are in: Argentina, Bolivia,
Chile, China, US, Australia, Canada.
• Largest current producers are Australia, Chille,
Argentina, China, Zimbabwe…
• Mg from seawater, Au from “urban mining”…
• H2O from seawater
8/16/16 4
Materials for a
Sustainable Future
Scott, J. L. (ed.) &
Letcher, T.
(ed.) 2012 Cambridge:
Royal Society of
Chemistry. 828
p.Research
output: Book/Report ›
Book
5. In the past: biomass provided food, energy
and raw materials
Food: 100%
Energy: wood
Raw materials: wood,
natural fibers + minerals
Consequence: land
change
8/16/16 5
by Sir Mark Walport,
Dec 2013
http://www.slideshare.net/bis_foresight/natural-history-museum-annual-science-lecture-2013
6. Then came coal, oil and gas
8/16/16 6https://notable.files.wordpress.com/2007/04/energy-per-capita.png
7. Abundant oil? Make food 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
8/16/16 7
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
9. Solution: energy from
renewable resources. Biofuels
8/16/16 9
https://media5.picsearch.com/is?H6ocSV7tIiUeAfGxI4BIToSfopEZjZSEhfqT6DjV5ac&height=341
10. Solution: energy from
renewable resources. Biofuels
8/16/16 10
https://media5.picsearch.com/is?H6ocSV7tIiUeAfGxI4BIToSfopEZjZSEhfqT6DjV5ac&height=341
New Problem
11. 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
8/16/16 11
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
12. FAO Hunger Map, 2015
8/16/16 12
Legend
Target achieved
Target not
achieved, slow
progress
Target not
achieved, lack of
progress or
deterioration
http://www.fao.org/3/a-i4674e.pdf
13. Nassar, A. M., Moreira, M. Evidences on sugarcane expansion and agricultural land use changes in
Brazil. Institute for International Trade Negociations
Total recoverable sugar: +39 % from 1990 to 2012.
Electricity surplus: 1 to 11 Twh/year, from 2005 to 2012
Production and efficiency gains: sugarcane
8/16/16 13
Ton/ha
Ton/ha
14. Products from
sugarcane
8/16/16
• Introduced in South and Central America in the
16th century, to produce sugar.
• Sugar crystallization residues were fermented to
produce ethanol.
• In 1976: subsidized fuel ethanol production.
• In 1990: subsidies were eliminated in 90% of the
producing areas.
• 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.
• Galembeck, Csordas “Chemicals from Sugarcane”, in
Fletcher and Scott “Materials for a Better Future”, RSC
2012
14
15. 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.”
8/16/16 15
C. Arndt et al., Fueling the path to food security, IFPRI Global Food Policy Report 2016 p.63
F. Galembeck, Synergy in food, energy and advanced materials production from biomass.
Energy and Environmental Science 2010 and Pure and Applied Chemistry 2018.
Galembeck, Fernando. Synergy in food, energy and advanced materials production from biomass. PURE AND APPLIED CHEMISTRY , v. 90, p. 109-119, 2018
16. A note on policy
• What do policymakers expect from scientists?
• Not much.
• Few citations in “The UN Sustainable Development Goals
Report” 2018. “science” 3 times; “scientific”: 1; “research”: 2“:
technology/ical/ies”: 21.
• Brazilian science concentrates on explaining, modelling,
theorizing…
• Much smaller effort on making.
• Result: small number of significant new products and
processes,
• …although all the competitive economic sectors rely heavily on
S&T.
8/16/16 16
18. Natural Rubber
• Accounts for 42% of global elastomer
consumption
• Essential in transportation and many
industrial products Rubber Statistical Bulletin April-
June edition, quoted by S. Rolere, et al. in European
Polymer Journal (2016)
• The “mistery of natural rubber”
• “…as the tire size increases and the level of
punishment the tire will take goes up, the
amount of natural rubber increases…” (Josh
Velson)
• Which is the role of the non-rubber
constituents (inorganics, proteins and
phospholipids NR properties?
19. ESI-TEM thin film elemental maps of dialyzed
natural rubber latex film
BF 200 nm
•Adherent mineral nanoparticles in natural rubber
• C, N densification around the inorganic particles: adhesion
Rippel, M.M. et al. Analytical Chemistry, 2002
19
20. Learning from Nature
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.
20
22. Strong polymer – clay
adhesion
Formation of a polymer-particle
network
Resistance to solvents
Valadares, L. F., Leite, C. A. P., Galembeck, F., Polymer, 2006, 47, 672.
22
x
y
z
1cm
30 phr Natural
rubber
23. • 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 et al.. J. Phys Chem C (2008); Bragença, F. C. ; et al. Chemistry of Materials, (2007)
11/9/16
24. Kelvin micrograph from PVC / natural rubber blend
Electrostatic contribution to cohesion
Linares et al., Langmuir 2008
26. Conductive inks, paints and adhesives
• Usually made of silver
• Also: copper, PEDOT, graphite, carbon nanotubes, graphene.
• US$ 3 Billion/year market
• CAGR = 4 – 6 %, depending on the market or product segment
• Broad range of users
• Auto industry: window and seat heaters
• Hardware and displays: screens, contacts
• Touch screens: ITO, graphene, carbon nanotubes
•
• Rao R, V. K., Abhinav K, V. et al. (2015).Conductive silver inks and their applications in printed and flexible
electronics. RSC Adv. 5, 77760–60.
• Yang, W. and Wang, C. (2016) Graphene and the related conductive inks for flexible electronics. J. Mater.
Chem. C 4, 7193– 207.
27. Material Resistivity
(.m)
Resistance
(/sq)
Thickness
(m)
graphene monolayer 10-8 33 3. 10-10 (single sheet)
graphene nanosheet 10-6 33 (1) 3. 10-8 (100 sheets)
graphite (basal) 2.10-6 0.3 6. 10-6 (20K sheets)
graphite (microfluidized) 2.5x10-4 2 (2)
silver 1x10-8 10-3 10-5
silver ink 12.5x10-8 5x10-3 2.5x10-5
THE MAIN PLAYERS
(1) Fang, X. Y., Yu, X. X. et al. (2015) Temperature and thickness-dependent electrical conductivity of few-layer
graphene and graphene nanosheets, Physics Letters A, 379, 2245-51.
(2) P. G. Karagiannidis, S. A. Hodge, L. Lombardi et al., Microfluidization of Graphite and Formulation of Graphene-
Based Conductive Inks, ACS Nano 2017, 11, 2742-2755.
28. Cellulose is soluble in water + alkali
• Simple procedure: Isogai et al.
Cellulose, 5 (1998) 309
• Insolubility in pure liquids
derives from its amphiphilic
structure (the Lindman
hypothesis)
• Shows the usual properties of
polyelectrolytes. Adhesive for
paper, cloth, wood.
• E. S. Ferreira et al, ACS Applied
Materials & Interfaces (2015)
• Excellent dispersant and
exfoliating agent for
graphite.
• E. S. Ferreira et al, Nanoscale
(2017)
.
29. Black particles,
do not settle
Shiny particles
Graphite exfoliated
in alkaline aqueous
cellulose solution
E. S. Ferreira et al, Nanoscale (2017)
30. FILTRATION
LITHOGRAPHY
SCALING UP - SPRAY
5 cm
Typical thickness: 10 – 100 μm
Broad resistance range
depending on cellulose/graphite
ratio
Graphite coatings on
paper, cloth and
ceramics
33. Electrostatics and Friction: Fundamental but
Snubbed
Well-stablished knowledge
OR
Unsolved problems?
Neglected as scientific topics in the 20th century
Disconnected from atomic-molecular theory
Revived interest since the first decade of this century
8/16/16 33
34. Electrostatics is Alive, Again
• We live in an electrified environment
• Electricity is produced within the Earth capacitor
• Electroneutrality is the exception, anywhere
• The charge carriers
• Chemical electrostatics
• The atmosphere is a charge reservoir
• Fires, explosions, safety
• Outlook: new science, new technology
34
35. An electrified environment:
the Global Electric Circuit
Galactic Cosmic Rays
Fair weather
return
currents
Transient
luminous events
Thunder
Clouds
Field-aligned currents
Solar energetic protons
Auroral currents
Electrified
Clouds
Magnetic
Field Lines
Geomagnetically
induced currents
Electric potential gradients at Kew Observatory, London, 1966 to 1979):
50 – 1200 V m -1
Rycroft and Harrison, Space Sci Rev 2008
36. “…current geophysical research has not yet disclosed
effective models for atmospheric cloud electrification.”
Helsdon Jr., J. H.; Gattaleeradapan, S., Farley, R. D.; Waits, C. C.
J. Geophys. Res. 2002, 107, 4630.
How electricity is produced, in the atmosphere?
36
37. polishing
powder
handling
aerosol
water splash
37
milling
We add electricity to the environment
(beyond power plants and the grid)
Charge separation/ interfacial effects:
Maxwell-Wagner-Sillars
Costa Ribeiro
Workman-Reynolds R
u
b
b
e
r
s
t
r
e
t
c
h
i
n
g
crystal
formation,
phase
transition
chemical
process plants
38. Unexpected: Complex charge distribution in dielectric solids
A Galembeck, CAR Costa, et al., Polymer, 2001, 42, 4845; F Galembeck, CAR Costa, et al., An. Acad. Bras. Cienc., 2001,
73, 495; FG, C Rezende, RF Gouveia, MA da Silva Journal of Physics – Condensed Matter, 21, 2009, 26300
EFM KFM
Polypropylene Natural
rubber
Poly(hydroxyethy
l methacrylate)
Polyethylene PP Silica PSAAM
on mica
Natural rubber
+
sodium
polyphosphate
film
Polyester
printing film
PE
Poly(styrene-butyl acrylate-
acrylic acid)
aging
Alumin
a
TiO2 on mica
Styrene-butyl
acrylate latex
38
Why? Water ion partition/adsorption and mechanochemical reactions
39. Charge carriers are electrons or ions?
Critical analysis: Meurig W. Williams (2012)
American Scientist 2012, 100(4), 316-325.
Feature Article: What Creates Static Electricity?
”Traditionally considered a physics problem, the answer is beginning to
emerge from chemistry and other sciences.”
39
Ions: McCarty and Whitesides, Electrostatic Charging due to Separation of Ions at
Interfaces: Contact Electrification of Ionic Electrets, Angew. Chem. Int. Ed. 2008,
47, 2188-2207. Ions, Baytekin, Grzybowski, et al., The Mosaic of Surface Charge in
Contact Electrification, Science 2011, 333, 308-312.
Electrons: Liu and Bard, Electrostatic electrochemistry at insulators, Nat.
Mater. 2008, 7, 505–509.
Ions, Mass Transfer: Burgo, Galembeck et al., Triboelectricity: Macroscopic
charge patterns formed by self-arraying ions on polymer surfaces. Langmuir 2012.
40. Electroneutrality: exception, not
the rule
• “Electroneutrality principle: The principle expresses the fact that all
pure substances carry a net charge of zero.” (IUPAC Gold Book)
• Can only happen under zero electric potential: μ- = μ-° + RT (ln x-) + zFV
• Pauling’s Electroneutrality Principle of molecular structure: unduly
extrapolated to macroscopic matter in introductory science courses.
• Charge partition and accumulation are expected in any interface:
Maxwell-Wagner-Sillars effect.
• Charge patterns are observed in any material system.
• The discovery tools: Kelvin electrode, Kelvin force microscopy and
other techniques derived from AFM.
DV = 250 kV
40
41. Is water
electroneutral?
Seldom.
• Ovchinnikova, K.; Pollack, G. H. Langmuir 2009, 25, 542: Can water
store charge?
• Corti, H. R.; Colussi, A. J. Langmuir 2009, 25, 6587: criticism to Pollack.
• Amin, M. S.; Peterson, T. F.; Zahn, M. J. Electrostatics 2006, 64, 424:
water from different sources carries excess negative charge.
• McCarty, L. S.; Whitesides, G. M. Angew. Chem. Int. Ed. 2008, 47, 2188:
non-electroneutrality should be considered.
• I. Bhattacharyya, J. T. Maze, G. E. Ewing,* and M. F. Jarrold*, J. Phys.
Chem. A, 2011, 115, 5723: bursting droplets are negative.
41
42. Water and electricity
• Steam electricity
• Discovered in 1840 by Lord Armstrong: vapor is charged opposite to the remaining
liquid.
• M. Faraday, Phil. Trans. 1843, 133, 17.
• Schrödinger (Ph.D. Thesis)
• Passive role for water in static electricity dissipation
• Water ion partition at interfaces
• Gas bubbles and pure hydrocarbon drops in water hold negative charge
• Beattie, J. K. Angew. Chem. Int. Ed. 2004, 43, 3568. Marinova, K. G. Langmuir 1996, 12, 2045.
Healy, T. W.; Fuerstenau, D. W. J. Colloid Interface Sci. 2007, 309, 181. I. Bhattacharyya et al., J.
Phys. Chem. A, 2011, 115, 5723.
• Kelvin dropper
• http://ocw.mit.edu/...demonstration: kelvin water dropper
42
43. Charge separation due
to H2O partition at
interfaces
• expansion of wet steam:
• J. Finke, J. Electrostat. 1989, 23, 69.
• adsorption-desorption:
• R. F. Gouveia and F. Galembeck, J. Am. Chem. Soc. 2005;
J. Phys. Chem C 2005, 2008; Anal. Chem. 2011.
• water ion partition:
• T. A. L. Burgo, F. Galembeck, G. H. Pollack, J. Electrost.
2016, 80, 30–33; T. R. D. Ducati, L. H. Simões, F.
Galembeck, Langmuir 2010, 26, 13763–13766; T. A. L.
Burgo, F. Galembeck, J. Braz. Chem. Soc. 2016, 27, 229–
238; T. A. L. Burgo, T. T. D. Ducati, K. R. Francisco, K. J.
Clinckspoor, F. Galembeck, S. E. Galembeck, Langmuir
2012, 28, 7407–7416
• splashing and bubble breaking:
• P. Lenard, Ann. Phys. 46, 584, 1892; Z. Levin, P. V. Hobbs,
Phil. Trans. 269, 555, 1971. P. Kolarž et al., Atmos. Chem.
Phys. 2012, 12, 3687. I. Bhattacharyya et al., J. Phys.
Chem. A 2011, 115, 5723. T. L. Burgo et al., Coll. Interf.
Sci. Comm. 2015, 7, 7-11
45. Water vapor adsorption contributes
charge to solids
Stöber silica is more negative under high humidity. Reversible.
Atmosphere is a charge reservoir for insulators.
Gouveia, R. F.; Galembeck, F. J. Am. Chem. Soc. 131(32), 2009, 11381
0 100 200 300 400
-2.2
-2.1
-2.0
-1.9
-1.8
-1.7
-1.6
-1.5
-1.4
Relative humidity (RH):
30%
50%
70%
Back to
30% (obtained immediately)
30% (after 90 min)
Electricpotential(V)
Distance (nm)
10 kV m-1
45
46. Water vapor adsorption contributes charge to
isolated metals
Chrome-plated brass cylinders acquire negative charge under high humidity
46
“Charge Partitioning at Gas-Solid Interfaces: Humidity Causes Electricity Buildup on Metals”
Telma R. D. Ducati, Luís H. Simões, Fernando Galembeck. Langmuir, 2010, 26, 13763-13766.
47. Chargechangerate/10-8C/s
Relative humidity/ %
Chrome-plated brass
Stainless steel
Cu, brass, silicone-
coated Al
Charge pick-up by isolated metals
within a Faraday cup
“Charge Partitioning at Gas-Solid Interfaces: Humidity Causes Electricity Buildup on Metals”
Telma R. D. Ducati, Luís H. Simões, Fernando Galembeck. Langmuir, 2010, 26, 13763-13766.
47
Water vapor adsorption contributes charge to
isolated metals
48. Acidic surfaces become more negative when the
humidity changes from 30 to 70%
Basic surfaces become more positive.
Substance DVm (DV)2
m (DVm)2/(DV)2
m
Iron oxide@Fe -0.464 0.004 0.217 0.004 0.99 Acid
Magnesium sulfate -0.229 0.008 0.063 0.009 0.83 Acid
Silica -0.172 0.015 0.033 0.005 0.90 Acid
Cellulose -0.104 0.007 0.011 0.001 0.98 Acid
Aluminum
oxide@Al
-0.055 0.016 0.004 0.002 0.76 Acid
Calcium oxide +1.657 0.11 2.811 0.33 0.98 Base
MgO (30- 50% RH) +0.195 0.062 0.096 0.021 0.40 Base
Nickel oxide +0.060 0.017 0.005 0.002 0.72 Base
Aluminum
phosphate
+0.039 0.007 0.002 0.001 0.76 Base
R. Gouveia et al. Analytical Chemistry 2012
48
49. Charge transfer during H2O adsorption
“Charge Partitioning at Gas-Solid Interfaces: Humidity Causes Electricity Buildup
on Metals” Telma R. D. Ducati, Luís H. Simões, Fernando Galembeck. Langmuir,
2010, 26, 13763-13766.
49
50. Elastoelectricity
Periodically stretched rubber tubing
shows potential variation in phase
with length.
- 3 kV
Stretching rubber exposes and hides sub-
surface groups that adsorb water acquiring
excess charge.
A capacitor is charged.
Burgo, Batista, Galembeck, ACS Omega (2018).
50
51. Charge produced by friction: PTFE rubbed
with LDPE foam
51
Formation of positive AND negative charges on the same surface.
Chalenges the paradigm of unidirectional charge transfer in
contacting solids.
53. 8/16/16 53
Feeding back: friction creates charge that increases
friction coefficients
T. A. L. Burgo, C. A. Silva, L. B. S.
Balestrin & F. Galembeck
Scientific Reports 3 (2013)
2384
55. Electrostatics is Alive, Again
• We live in an electrified environment
• Electricity is produced within the Earth
capacitor
• Electroneutrality is the exception,
anywhere
• The charge carriers
• Chemical electrostatics
• The atmosphere is a charge reservoir
• Fires, explosions, safety
• Outlook: new science, new technology
55
56. The first dust explosion that was outlined in a world literature occurred in 14 December 1785 in Italy.
Turin Science Academy noticed that it was an explosion of flour dust in the centre of Turin.
According to literature all building was destroyed.
Reported by Rafal Porowski from HQ of SFS. http://www.ppoz.pl/wwwold/current.htm
Explosions triggered by electrostatic
discharge
56
57. Can we better understand and achieve
controlled interaction with atmospheric
electricity?
57
cuvette wrapped
with stainless
steel screen
water
contacting a
stainless-steel
electrode
water level
water-
mediated
discharge
Ejection of electrified water produces sustained discharge.
Consistent with the fractal geometry of lightning.
58. Acknowledgements
André Herzog
André Galembeck
Bruno Batista
Carlos Alberto Costa
Camila Resende
Carlos Alberto Leite
Douglas Soares
Elisa Ferreira
Fabio Bragança
Jeferson Santos
João Paulo Bertacchi
Juliana Bernardes
Juliane Santos
Leandra Santos
Leonardo Valadares
Lia Beraldo Balestrin
Lucimara Lopes
Lucas Soares
Márcia Rippel
Melissa Braga
Pompeu Abreu Filho
Rubia Gouveia
Telma Doi Ducati
Thiago Burgo
Victor Chida
Maria do Carmo da
Silva
58
Aldo Zarbin (UFPr), Steven Armes
(Sussex), Gerd Kaupp (Oldenburg),
P. Somasundaran (Columbia), K.
Kurihara (Tohoku), Lay-Theng Lee
(Gif), B. Vincent (Bristol)
INCT Program grant to Inomat
(Institute for Functional Complex
Materials)
Grants and fellowships from
Fapesp, CNPq, Finep and Capes
Bunge, Cameron, Odebrecht Agro,
Orbys, Oxiteno, Pirelli, Unilever.
SBQ, SBPMat/BMRS, ABPol, IACIS,
ABC, ESA, RSC, ACS, IOP
59. A note on policy (II)
8/16/16 59
• Is money being spent where it should?
• Little, poor diagnosis. Poor decisions on project implementation.
• Lack of assessment.
• Results of the largest funding body in the country (FNDCT) do
not even have a definite assessment methodology.
• Poor planning
• Result: huge sums spent in facilities and equipment that
do not provide the basis for the introduction of much-
needed public policies.