Additive manufacturing of porous carbons.ppsx

J. Ángel Menéndez
INCAR-CSIC
angelmd@incar.csic.es
Raúl Llamas-Unzueta, J Angel Menéndez, Luis A Ramírez-Montoya, Jaime Viña,
Antonio Argüelles, Miguel A Montes-Morán “3-D structured porous carbons
with virtually any shape from whey powders.” Carbon 175 (2021) 403-412.

Thank you Professor Carrot for
how much I have learned from
you and for the great moments
that we share.

 Now it is possible to design and manufacture prototypes, or other
objects, at very low cost using 3D printers.
 The power to design and manufacture is no longer in large
companies or research centers, but in people.
 Do It Yourself (but with the help of the community and helping others by
sharing).
 Its goal is to democratize access to Science, Technology, Engineering, Arts and
Mathematics (STEAM) by using collaborative digital media (social networks,
open source practices, crowdfunding…)

Our mothers were able to
make their own sweater.
Our children can make their own toys and
share them with the rest of the world.

3D-printed hands-free door
opener to help slow down
Coronavirus spread

Buildings
Fashion
Vehicles
Food
Mechanical Parts
3D Printers
Sports Equipment
https://doi.org/10.1016/j.ijlmm.2018.07.002
Implants, prosthesis and scaffolds
https://doi.org/10.1016/j.addma.2018.04.026

Carbon Black, Carbon Fiber, Carbon Nanotubes and Graphene
Composites (FDM) and Graphene Aerogels (Paste Extrusion 3D Printing)
https://doi.org/10.1002/adma.201405046
Adv.Mater.2015, 27, 1688–1693
500-100 μm
nozzles
YES
https://doi.org/10.1016/j.apmt.2017.04.003

Why not?
Our goal is to add design to active carbons by
producing porous carbon structures that can be
pre-engineered, not only in their porosity and
surface chemistry, but also in their morphology.
Idea  CAD  STL  Slicer  3DPrinter  Piece
GDCode
Internet
Ultimaker CURA
STL Finder
SD, USB




J. Ángel Menéndez, I. Martín-Gullón. Types of carbon adsorbents and their production
in Activated carbon surfaces in environmental remediation (Interface sci. and technol.
series, 7. T. Bandosz Ed. ELSEVIER 2006 (ISBN: 0-12-370536-3) Ch. 1, 1-48
https://doi.org/10.1016/S1573-4285(06)80010-4

Powder
750-1500 €/ ton
Granular
750-2000 €/ton
Cloths and felts
5-20 €/m2
Monoliths
500-1500 €/m3
Pellets
1000-2000 €/ton
And now?
When "design" is added to activated carbons, the price
by weight is no longer an issue and they are sold by
area or volume, increasing the price by weight.
Therefore, design adds value to the active carbons.
Average prices on
Alibaba.com (2020)

6DCarbons are porous carbons that can be shaped in customized 3D structures using casting or additive
manufacturing techniques. Besides, the walls of these carbon structures contain a hierarchical porous network
composed by pores from nanometers to microns.
6DCarbons
J. Ángel Menéndez, Miguel A. Montes-Morán, Ana Arenillas, Luis A. Ramírez-Montoya, Raúl Llamas-Unzueta. “Porous shaped carbon
monolith obtained from lactoserum, method of obtention and uses”. WO2021069770 Patent
("Custom 3D Porous Carbon Structures" is too long a name)
What are 6DCarbons?

https://www.alibaba.com/activated-carbon-monoliths-suppliers.html
High added value
https://www.sglcarbon.com/en/markets-solutions/material/carboprint/

Porogen
It uses a photoresin and an organic porogen that is removed by
extraction from the green monolith
https://doi.org/10.1002/advs.201901340
It uses a UV-curable photoresin
to print a structure with pores of
250-1000 mm that after
carbonization are reduced to
pores of 100-500 mm. During
carbonization, 2-5 mm secondary
pores are also formed.
https://doi.org/10.1016/j.nanoen.2017.11.070
Thermoplastic polymers cannot be
carbonized without losing their shape.
Therefore, to obtain porous structures,
it is necessary to use complex processes
that use sophisticated (i) thermoset
precursors like photopolymers and/or
(ii) templates that need to be removed
or (iii) mixtures of thermoplastic resins
and phenolic resins.
It uses a thermoplastic resin that after 3D printing is
coated with a resorcinol-formaldehyde resin and
hydrothermally carbonized. The structures are
macro/meso porous.
https://doi.org/10.1016/j.carbon.2015.02.069
It uses a thermoplastic resin
mixed with graphite and a
phenolic resin to print a
lattice that is impregnated
with nano-silica. Subsequent
pyrolysis eliminates the
thermoplastic giving rise to
macropores and subsequent
dissolution of the silica
produces micropores.
https://doi.org/10.1007/s10934-011-9501-x
Monodispersed
SiO2 spheres
https://doi.org/10.1016/j.cattod.2018.05.044
It uses a starch + gelatin + silica spheres in an extrusion
printer. Dissolution of the silica after carbonization
produces micropores.
(i)
(i+ii)
(i+ii) (ii+ iii) (iii)

https://doi.org/10.1016/j.est.2017.12.020
https://doi.org/10.1016/j.jmapro.2016.12.020
A more straightforward strategy is to use activated carbon
and Carboxymethyl cellulose (CMC) as a binder to produce
a paste that is extruded on a paste extrusion 3D printer.
https://doi.org/10.1016/j.micromeso.2019.01.009
(v)

 In 2011, world whey production was estimated to be around 180
to 190 × 106 ton/year ; of this amount only 50% is processed.
 Whey is a very difficult residue to dispose because its high
BOD/COD and water content (ca. 90 wt%).
 It may be interesting to find new ways to valorize whey.
 Whey is 100% sustainable natural product.
https://doi.org/10.1016/j.idairyj.2008.03.008
https://doi.org/10.1016/j.desal.2011.05.055
https://doi.org/10.1007/s11157-016-9402-1
https://www.clal.it/en/index.php?section=whey
https://doi.org/10.1016/j.energy.2018.01.066
https://doi.org/10.1016/j.energy.2016.01.059
Whey has been investigated to produce N-rich powdered active carbons.
Environmental reasons

Two simple methods to produce complex
structures of porous carbon.
Whey powders experiment a “pseudo-sintering
process” at ca. 150 ºC
After carbonization a
porous carbon structure,
that maintains the initial
shape, is obtained.
Green structures
Porous carbon
Structures with
high mechanical
resistance
At around 150 ºC, the whey releases a
mixture of sugars and proteins that bind
the particles together.
Maillard reaction
Extrusion-based 3D Printing
Selective laser sintering
(SLS)
WHEY
90 wt%
H2O
H2O content adjustment
Partial Dehydration
Spray Drying
3wt% H2O
Powders of whey
Rehydration
Sintratec kit
1b
By controlling the water content
an extrudable paste can be
obtained
20 -30 wt% H2O
Sinter by heating
in a mold
Molds can be
prototyped with
3D printing
Extruder

2 2
http://dx.doi.org/10.6036/10054
http://dx.doi.org/10.1016/j.carbon.2021.01.021

* Considered as a residue.
Replacing 10 wt% of
traditional binders with
whey would represent
170,000 t/year of
recycled whey
Extruded pellets of coconut shell
char and liquid (partially
dehydrated) whey* (as a binder)
(*)N2 / (**)CO2  Molecular Sieve Properties?
Carbonized
450 ºC
Activated
CO2/800ºC
Commercial
( from coal)
Commercial
(from char)
Yield (%) 71.8 49.8 -- --
ρr (g/cm3) 1.56 2.04 2.09 2.05
ρbulk (g/cm3) 0.60 0.56 0.77 0.70
Porosity (%) 62.47 72.98 63.30 65.74
Ia (%) <1 <1 1.7 <1
SBET (m2/g)* 0 991 1095 809
Vmicro (cm3/g)* 0* / 0.0743** 0.4029 0.3808 0.326
Vmeso (cm3/g)* -- 0.0305 0.1727 0.07
Vp (cm3/g)* -- 0.4334 0.5535 0.396

Other Possibilities
 Carbon Black
 C Nanotubes
 Graphene
 Metals
 Oxides
 Infiltration
SiC
Intensity
(cps)
6DCarbons with High
Porosity and High
Electrical Conductivity
50 wt% SiO2
50 wt% Whey
Up to 75% by weight of SiO2 can be
mixed with whey and processed
without losing shape and with
acceptable mechanical properties of
the resulting monoliths.

Experimental conditions (route 1: sintering)
Carbonization
CO2 activation
KOH activation
H3PO4 activation
W: whey, S: stabilized monolith CW: carbonized whey,
TAW: thermally activated with CO2, CAS: chemically activated
N2
N2
Impregnation
KOH
H3PO4
N2
CO2
S
S
S
The shape is preserved after carbonization
or activation and the pieces obtained are
compact and resistant to machining.

SEM
6DCarbon structures have a hierarchical porosity composed of
micropores, mesopores, and large macropores (up to 400 mm),
which gives them a high permeability (≈ 1 - 4 darcy, 10-12 m).
Hg Porosimetry
N2 Isotherms
CO2 activation
H3PO4 activation
Carbonization
KOH activation
MEGALOPORES
MACROPORES
MESOPORES &
MICROPORES

The shape is preserved during carbonization, however the pieces experience an shrinkage of ca. 22%
(at Tº > 750 ºC) in each direction (XYZ) regardless of the method used in their manufacture. Yields
vary from 33 wt% to 25 wt%, depending on the temperature used in the carbonization.

Ibeh, P. et al. "Activated carbon monoliths from lignocellulosic biomass waste for electrochemical applications." Journal of the Taiwan Institute of Chemical Engineers, 2019
https://doi.org/10.1016/j.jtice.2019.02.019
Taubert M. et al. “Attempts to design porous carbon monoliths using porous concrete as a template”, Microporous and Mesoporous Materials, 2014 https://doi.org/10.1016/j.micromeso.2014.06.005
Zhong Y. et al. “Synthesis of a novel porous material comprising carbon/alumina composite aerogels monoliths with high compressive strength”, Microporous and Mesoporous Materials, 2013
https://doi.org/10.1016/j.micromeso.2013.01.021
Wang S. et al. “Fabricating Mechanically Robust Binder‐Free Structured Zeolites by 3D Printing Coupled with Zeolite Soldering: A Superior Configuration for CO2 Capture”, Advanced Science, 2019
Woodard P. et al. “The mechanical properties and osteoconductivity of hydroxyapatite bone scaffolds with multi-scale porosity”, Biomaterials, 2007
https://doi.org/10.1016/j.biomaterials.2006.08.021
Bose S, Roy M, and Bandyopadhyay A. "Recent advances in bone tissue engineering scaffolds." Trends in biotechnology, 2012, https://doi.org/10.1016/j.tibtech.2012.07.005
Yan Y. et al. “Vascularized 3D printed scaffolds for promoting bone regeneration”. Biomaterials, 2019. https://doi.org/10.1016/j.biomaterials.2018.10.033
Carboprint® https://www.sglcarbon.com/en/markets-solutions/material/carboprint

https://www.monash.edu/__data/assets/pdf_file/0009/14
63778/Carbon-monoliths-water-purification.pdf
The HEPA filters does not
filter the VOCs and the
activated carbon filters do
not filter the microparticles.
Would it be possible to
print an activated carbon
filter with an optimized
geometry?
https://doi.org/10.1038/d41586-018-02704-9
Environmental applications
https://doi.org/10.1155/2019/7134309
https://doi.org/10.1080/02726351.2019.1607637

https://doi.org/10.1016/j.nanoen.2017.08.037
Most of these technologies are designed
to print graphene or carbon nanotubes (to
increase electrical conductivity), but the
combination with activated carbon would
also offer a much larger surface area.
M Canal-Rodríguez, A Arenillas, N Rey-Raap, G Ramos-
Fernández, I Martín-Gullón, J A Menéndez (2017) Graphene-
doped carbon xerogel combining high electrical conductivity
and surface area for optimized aqueous supercapacitors
Carbon 118: 291-298.
https://doi.org/10.1016/j.carbon.2017.03.059
https://doi.org/10.1002/adma.201603486
Electrochemical applications

The detection layer is printed on a 3D printer
that extrudes a mixture of thermoplastic
polyurethane, microporous carbon black
and NaCl, which leaves micron-sized pores
after dissolving with H2O.
https://doi.org/10.1002/adfm.201807569
3D printed porous
carbons structures
are also possible to
design rigid, but
much easier to
manufacture,
sensors .
An inkjet printer is used to print a sugar
template, which is infiltrated with silicone
elastomers. Then the sugar is dissolved
with H2O and the resulting porous
structure is coated with SWCNT.
Electrochemical applications

Enhanced heat transfer properties
https://doi.org/10.1016/j.matlet.2018.10.133
https://doi.org/10.1016/j.jcou.2019.07.013
https://doi.org/10.1126/sciadv.aas9459
https://doi.org/10.1002/cctc.201700829
If we can do similar
structures with a porous
carbon, we could have
the advantages that
activated carbons offer;
such as a high specific
surface area or versatile
surface chemistry.
Chemical engineering applications

These are relatively simple
reactors. Other designs would
be possible that maximize the
area exposed to light and
minimize volume.
Why not a Sunflower-inspired photoreactor?
3D Design taken from Cults. “Tournesol-Numerique”. Author: OASISK
https://doi.org/10.1021/ie900859z
https://doi.org/10.1016/j.cep.2004.06.009
Journal of Water Chemistry and Technology
https://doi.org/10.3103/S1063455X09040043
Lab Scale
Large Scale
Gemasolar, Very Large Scale
https://doi.org/10.1016/j.solener.2011.12.007

https://doi.org/10.1039/C7CS00631D
https://doi.org/10.1016/j.cjche.2018.12.013
Reactors or parts could be
manufactured using 3D printed
porous carbon structures.
https://doi.org/10.1680/nme/13.00021
3D printed gas-liquid contactor
https://doi.org/10.1016/j.ceramint.2015.05.016
6DC as membranes
or membrane
supports?
 Custom shape and wall thickness
 Hierarchical and tunable porosity
 Pressure, acid and temperature resistant
 Can be coated or infiltrated

Biomedical engineering applications
https://doi.org/10.1556/1846.2017.00013
https://doi.org/10.1021/acssuschemeng.8b04471
https://doi.org/10.1021/acssuschemeng.9b04980
ACS Sustainable Chem. Eng
Bioreactors combining scaffolds
for enzyme or bacteria
immobilization and membranes
require versatile porous materials.
https://doi.org/10.1002/elsc.201800030
3D Design of a “Continuous Flow Reactor Mold”.
Taken from thingiverse. Author: J. Langner
A mold for a continuous flow reactor can be
built using a 3D printer. This mold can be
used to make a porous carbon reactor,
which offers a large surface area and
multiple sites for the support of enzymes or
bacteria, following the process based on
sintering of whey powder and subsequent
carbonization.

https://doi.org/10.1016/j.actbio.2018.08.026
 Scaffolds must have an interconnected pore structure and high porosity.
 An average pore size of 325 mm is considered optimal for bone tissue engineering.
6DCarbons

Viability > 70% indicates that
the material is not cytotoxic.
http://dx.doi.org/10.3390/biomedicines9091091
 Non-cytotoxic and bioactive behavior.
 Porosity between 48% and 58%, with a hierarchical pore
size distribution ranging from 1 to 400 mm.
 Elastic modulus up to three times better than those of
traditional Hydroxyapatite (HA) or Tricalcium Phosphate
(TCP) scaffolds with similar porosities.
3D printing of Whey/HA /TCP mixtures
Next

Adding design to activated carbons makes
them more versatile materials increasing their
applications and value.
Idea  CAD  STL  Slicer  3DPrinter  Piece
GDCode
Internet
Ultimaker CURA
Cults, STL finder
SD, USB




Thanks for your attention
angelmd@incar.csic.es
Contact:

Additive manufacturing of porous carbons.ppsx

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