Materials from renewable resources: new properties and functions

Abstract: Sustainable production requires increasing use of raw materials from renewable sources, processed under mild conditions with minimal effluent production. These requirements are satisfied by using materials derived from biomass, in synergy with food and energy production. The possibilities of biomass are continuously enlarged by new findings, as in the intrinsic nanocomposite properties of natural rubber and the amphiphile behavior of cellulose that translated into new functional materials, including high-performance, flexible and conductive non-metallic materials. Other findings are allowing a better understanding of electrostatic phenomena that play a positive role in electrostatic adhesion and cohesion of nanocomposites made from biomass products. Moreover, this should allow the development of safe electrostatic separation techniques, suitable for the fractionation of crude mixtures of biomass residues. A current study on rubber electrostatics is showing its capabilities as a transducer of mechanical energy while providing clues to understand the performance of the dielectric elastomers used in robotic self-sensing actuators.

Key words
cellulose; electrostatics; nanocomposites; natural rubber

Authorship

FERNANDO GALEMBECK

Instituto de Química, Universidade Estadual de Campinas, Rua Josué de Castro, s/n, 13083-970 Campinas, SP, Brazil Universidade Estadual de CampinasBrazilCampinas, SP, BrazilInstituto de Química, Universidade Estadual de Campinas, Rua Josué de Castro, s/n, 13083-970 Campinas, SP, Brazil

http://orcid.org/0000-0003-4778-5442

THIAGO A.L. BURGO

Departamento de Física, Universidade Federal de Santa Maria, Av. Roraima, 1000, Camobi, 97105-900 Santa Maria, RS, Brazil Universidade Federal de Santa MariaBrazilSanta Maria, RS, BrazilDepartamento de Física, Universidade Federal de Santa Maria, Av. Roraima, 1000, Camobi, 97105-900 Santa Maria, RS, Brazil

DOUGLAS S. DA SILVA

LEANDRA P. SANTOS

Correspondence to: Fernando Galembeck E-mail: fernagal@unicamp.br ORCID: http://orcid.org/0000-0003-4778-5442

AUTHOR CONTRIBUTIONS

F.G. outlined the paper and wrote parts of the manuscript, with research and writing support from T.A.L.B, D.S.S and L.P.S. All authors provided critical feedback and contributed to its final version.

SCIMAGO INSTITUTIONS RANKINGS

Figures

Figures (9)

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Figure 1
Transmission electron micrographs of thin graphite sheets exfoliated in cellulose aqueous solutions. (a, c): brightfield and (b, d): 25 eV EELS filtered images from small graphite particles separated by zonal sedimentation. Particle thickness measured in the marked circles in (c) is: 1, 20 nm; 2, 33 nm; 3, 64 nm. Reproduced (adapted) from (Ferreira et al. 2017) with permission from The Royal Society of Chemistry.

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Figure 2
Left: Representation of cellulose and graphite structures. Right: Disassembly of graphene stacks due to cellulose adsorption that pushes single or multiple lamellae towards the aqueous solution. Cellulose aggregates may also participate in these events (not shown). Reproduced (adapted) from (Ferreira et al. 2017) with permission from The Royal Society of Chemistry.

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Figure 3
Secondary electron micrographs showing results of the application of dissolved cellulose to filter paper: (a) as-received filter paper surface; (b) filter paper strips bonded with cellulose adhesive, single lap joint surface; (c) cross-section view of b; (d) single lap joint prepared with wet paper strips; (e) butt joint; (f) impregnated single strip. Reprinted (adapted) with permission from (Ferreira et al. 2015). Copyright 2015 American Chemical Society.

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Figure 4
SEI micrographs of the freeze-cast foamed poly(styrene-butyl acrylate-acrylic acid) latex show (a) pore distribution and (b) inter- connected pore details. Note the intricate structure of the pore walls in b). Reproduced (adapted) from (Da Silva and Galembeck 2015DA SILVA LL and GALEMBECK F. 2015. Morphology of latex and nanocomposite adsorbents prepared by freeze-casting. J Mater Chem A 3: 7263-7272.) with permission from The Royal Society of Chemistry.

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Figure 5
Schematic representation of the role of positive counterions (small circles) on the adhesion between clay lamellae and polymer. (1) Latex and clay dispersion, (2) polymer-clay particles approach during dispersion drying, (3) hydrated counterions bridging clay and the dry polymer matrix, and (4) dehydrated counterions bridge clay lamellae and the polymer matrix. Reprinted (adapted) with permission from Bragança et al. 2007BRAGANÇA FC, VALADARES LF, LEITE CAP and GALEMBECK F. 2007. Counterion effect on the morphological and mechanical properties of polymer-clay nanocomposites prepared in an aqueous medium. Chem Mater 19: 3334.. Copyright (2007) American Chemical Society.

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Figure 6
How water contributes charge to solid surfaces (hygroelectricity). Upper: a cluster of water molecules approaches a basic surface of stainless steel or other chromium alloy that contains basic chromium oxide at the surface. The oxide picks H+ ions, acquiring positive charge. Aluminum metal is coated with acidic oxide that picks up OH- ions, acquiring negative charge. Reprinted (adapted) with permission from (Ducati et al. 2010). Copyright 2010 American Chemical Society.

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Figure 7
Electrostatic potential of (a) natural and (b) silicone rubber under stretching−relaxation cycles. A Kelvin electrode recorded the initial electrostatic potential, for 60 s. The stretching−relaxation cycles followed for 180 s and then ceased, leaving the material at the starting position. Zooms from (a,b) are shown in the inset graphs. (c,d) voltage vs distance for natural and silicone rubber, respectively. Experiments were performed at 60% RH. Reprinted (adapted) with permission from (Burgo et al. 2017BURGO TAL, BATISTA BC and GALEMBECK F. 2017. Electricity on rubber surfaces: a new energy conversion effect. ACS Omega 2: 8940-8947.). Copyright 2017 American Chemical Society.

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Figure 8
Mechanism for contact triboelectrification of insulating polymers. Shearing the polymer interface heats both surfaces unevenly forming hot spots, due to forced contact on surface hills. Plasticization and melting take place added to chain breakdown and fragmentation. Homolytic scission produces free radicals with markedly different electronegativities that are converted into fluorocarbanions and hydrocarbocations by electron transfer. Ions are segregated due to the chain size, following Flory−Huggins theory and superseding weak electrostatic interactions between highly spaced charges. Reprinted (adapted) with permission from (Burgo et al. 2012BURGO TAL, DUCATI TRD, FRANCISCO KR, CLINCKSPOOR KJ, GALEMBECK F and GALEMBECK SE. 2012. Triboelectricity: Macroscopic Charge Patterns Formed by Self Arraying Ions on Polymer Surfaces. Langmuir 28: 7407-7416.). Copyright 2012 American Chemical Society.

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Figure 9
(a) Potential maps of PTFE plates tribocharged by friction with polyethylene. (b) CoRR (coefficient of rolling resistance) versus average surface potential of tribocharged PTFE plates (Burgo et al. 2013BURGO TAL, SILVA CA, BALESTRIN LBS and GALEMBECK F. 2013. Friction coefficient dependence on electrostatic tribocharging. Sci Rep 3: 2384.).

Figure 1 Transmission electron micrographs of thin graphite sheets exfoliated in cellulose aqueous solutions. (a, c): brightfield and (b, d): 25 eV EELS filtered images from small graphite particles separated by zonal sedimentation. Particle thickness measured in the marked circles in (c) is: 1, 20 nm; 2, 33 nm; 3, 64 nm. Reproduced (adapted) from (Ferreira et al. 2017) with permission from The Royal Society of Chemistry.

Figure 2 Left: Representation of cellulose and graphite structures. Right: Disassembly of graphene stacks due to cellulose adsorption that pushes single or multiple lamellae towards the aqueous solution. Cellulose aggregates may also participate in these events (not shown). Reproduced (adapted) from (Ferreira et al. 2017) with permission from The Royal Society of Chemistry.

Figure 3 Secondary electron micrographs showing results of the application of dissolved cellulose to filter paper: (a) as-received filter paper surface; (b) filter paper strips bonded with cellulose adhesive, single lap joint surface; (c) cross-section view of b; (d) single lap joint prepared with wet paper strips; (e) butt joint; (f) impregnated single strip. Reprinted (adapted) with permission from (Ferreira et al. 2015). Copyright 2015 American Chemical Society.

Figure 4 SEI micrographs of the freeze-cast foamed poly(styrene-butyl acrylate-acrylic acid) latex show (a) pore distribution and (b) inter- connected pore details. Note the intricate structure of the pore walls in b). Reproduced (adapted) from (Da Silva and Galembeck 2015DA SILVA LL and GALEMBECK F. 2015. Morphology of latex and nanocomposite adsorbents prepared by freeze-casting. J Mater Chem A 3: 7263-7272.) with permission from The Royal Society of Chemistry.

Figure 5 Schematic representation of the role of positive counterions (small circles) on the adhesion between clay lamellae and polymer. (1) Latex and clay dispersion, (2) polymer-clay particles approach during dispersion drying, (3) hydrated counterions bridging clay and the dry polymer matrix, and (4) dehydrated counterions bridge clay lamellae and the polymer matrix. Reprinted (adapted) with permission from Bragança et al. 2007BRAGANÇA FC, VALADARES LF, LEITE CAP and GALEMBECK F. 2007. Counterion effect on the morphological and mechanical properties of polymer-clay nanocomposites prepared in an aqueous medium. Chem Mater 19: 3334.. Copyright (2007) American Chemical Society.

Figure 6 How water contributes charge to solid surfaces (hygroelectricity). Upper: a cluster of water molecules approaches a basic surface of stainless steel or other chromium alloy that contains basic chromium oxide at the surface. The oxide picks H+ ions, acquiring positive charge. Aluminum metal is coated with acidic oxide that picks up OH- ions, acquiring negative charge. Reprinted (adapted) with permission from (Ducati et al. 2010). Copyright 2010 American Chemical Society.

Figure 7 Electrostatic potential of (a) natural and (b) silicone rubber under stretching−relaxation cycles. A Kelvin electrode recorded the initial electrostatic potential, for 60 s. The stretching−relaxation cycles followed for 180 s and then ceased, leaving the material at the starting position. Zooms from (a,b) are shown in the inset graphs. (c,d) voltage vs distance for natural and silicone rubber, respectively. Experiments were performed at 60% RH. Reprinted (adapted) with permission from (Burgo et al. 2017BURGO TAL, BATISTA BC and GALEMBECK F. 2017. Electricity on rubber surfaces: a new energy conversion effect. ACS Omega 2: 8940-8947.). Copyright 2017 American Chemical Society.

Figure 8 Mechanism for contact triboelectrification of insulating polymers. Shearing the polymer interface heats both surfaces unevenly forming hot spots, due to forced contact on surface hills. Plasticization and melting take place added to chain breakdown and fragmentation. Homolytic scission produces free radicals with markedly different electronegativities that are converted into fluorocarbanions and hydrocarbocations by electron transfer. Ions are segregated due to the chain size, following Flory−Huggins theory and superseding weak electrostatic interactions between highly spaced charges. Reprinted (adapted) with permission from (Burgo et al. 2012BURGO TAL, DUCATI TRD, FRANCISCO KR, CLINCKSPOOR KJ, GALEMBECK F and GALEMBECK SE. 2012. Triboelectricity: Macroscopic Charge Patterns Formed by Self Arraying Ions on Polymer Surfaces. Langmuir 28: 7407-7416.). Copyright 2012 American Chemical Society.

Figure 9 (a) Potential maps of PTFE plates tribocharged by friction with polyethylene. (b) CoRR (coefficient of rolling resistance) versus average surface potential of tribocharged PTFE plates (Burgo et al. 2013BURGO TAL, SILVA CA, BALESTRIN LBS and GALEMBECK F. 2013. Friction coefficient dependence on electrostatic tribocharging. Sci Rep 3: 2384.).

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Materials from renewable resources: new properties and functions

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[1] Correspondence to: Fernando Galembeck E-mail: fernagal@unicamp.br ORCID: http://orcid.org/0000-0003-4778-5442