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INSTITUI.Tamw.H.iA^
INSTITUTO FOLnrÈCNICO
Title
6th Workshop - Green Chemistry and Nanotechnologies in Polymer Chemistry
Edited by
M. F. Barreiro, O Ferreira, A. Pereira
Graphic Design
Soraia Maduro-CIPweb IPB
Firstedition 07/2015
ISBN 978-972-745-188-3
Edition
^'WORi:S'iOP
..' /" Green Chemislryand Nanotechnoiogies
(O inPolymer Chemislry
Commíttees
Scientific Committee
Aleksander Prociak, Cracow University ofTechnology, Poland
Alessandro Gandini, IQSC University of São Paulo, Brazil
Alfonso Jimenez, University o1 Alicante, Spain
Alírio Rodrigues, University of Porto, Portugal
Ana Vera Machado, University of Minho, Portugal
Andrea Lazzeri, University of Pisa, Italy
Arantxa Eceiza, University ofthe Basque Country, Spain
Armando Silvestre, University of Aveiro, Portugal
Bela Pukansky, Budapest University, Hungary
Fernão Magalhães, University of Porto, Portugal
Filomena Barreiro, Polytechnic Institute ot Bragança, Portugal
Helena Gil, University of Coimbra, Portugal
Janusz Datta, Gdansk University of Technology, Poland
Joanna Ryszkovróka, Warsaw University ofTechnology, Poland
João Mano, University of Minho, Portugal
José Vega Baudrit, Centro Nacional de Alta Tecnologia (CeNAT), Costa Rica
Juan Francisco Rodriguez, University of Castilla La Mancha, Spain
Luisa Carvalho, Polytechnic Institute of Viseu, Portugal
Mário Rui P. F. N. da Costa, University of Porto, Portugal
Mirta Aranguren, CONICET University of Mar de Plata, Argentina.
Naceur Belgacem, Grenoble INP-Pagora, France
Tomas Vlcek, TOSEDA S. R. O. Research & Development Center, Czech Republic
Tomasz Sterzyriski, Poznan University ofTechnology, Poland
Ugis Cabulis, Institute ofV/Vood Chemistry, Latvia
Organizing Committee
6th Workshop on Green Chemistry and Nanotechnologies in Polymer Chemistry
033. CORK COMPATIBILITY IN POLYMERS
S.P.M. Silva, P.S. Lima, J.M. Oliveira
.63
POSTERPRESENTATIONS...
65
P01. DEVELOPMENTOF BIOPLASTICS FROM AGRO-WASTES...66
MJ. Macedo, l. Moura, A.V. Machado
P02. THE USE OF BAMBOO POWDER AND GLASS MICROSPHERES TO REDUCETHE
HYDROPHILICIÏI' OF CASSAVA STARCH FILMS FOR POTENTIAL APPLICATION IN THE PACKAGING INDUSTRY... 68
L.C. G. S. Santos, E. Ayres, F.R. G. Padula
P03. PREPARATION OF (3-CYCLODEXTRIN / LATEX DISPERSION FOR COATING OF CELLULOSE FABRIC... 70
MA Cotrim, J.C.O. Villanova, E. Ayres
P04. EDIBLE FILMS OBTAINED FROM OKRA MUCILAGE (Abelmoschusesculentus)fiSSOC\WED WITH
LEMON GRASS OIL (Cymbopogon fíexuosus} WITH POTENTIAL ANTIMICROBIAL ACTIVITY... 72 MA Cotrim. V. Alves, E. Ayres
P05. PROMOTION OF SCIENTIFIC SKILLS IN SECONDARY EDUCATION FROM DIFFUSION OF
NANOSCIENCEANDNANOTECHNOLOGY... 74 K. Ramfrez, A. Rivera, J. Vega, R. Hernández, K. Montero, R. Granados
P06. NOVEL BIOCOMPOSITES FROM NATURAL RUBBER AND LIGNIN: THE EFFECT OF FILLER CONTENTON MORPHOLGOYAND MECHANICAL PROPERTIES ...76
P. Kopczyrtska, J. Datta, P. Parcheta
P07. PREPARATION AND PROPERTIES OF NATURAL RUBBER COMPOSITES FILLED BYMIXTURE OF
CALCIUM CARBONATE AND BARRIUM FERRITE ...,.,.,... 78 J. Datta, M. Wloch, P. Lis, P. Parcheta
P08. SYNTHESIS, STRUCTUREAND PROPERTIES OF POLY(ESTERURETHANE-UREA)S SYNTHESIZED
WITHUSINGBIO-BASEDDIAMINE...
79
M. Wtoch, J. Datta
P09. ULTRASOUND-ASSISTED SYNTHESIS OF SUCROSE AND FRUCTOOLIGOSACCHARIDES ESTERS ASBIOPLASTICIZERS...80
D. Vassilev, N. Petkova, P. Denev, M. Koleva
PIO. CHITOSAN DERIVED FROM BEE ABDOM... 83 D. Malina, B. Tyliszczak, K. Biaiik-Wqs,A Sobczak-Kupiec
P11. FABRICATION AND PROPERTIES CHARACTERIZATION OF EPOXY POLYMER MODIFICATED WITHDIFFERENTCARBONNANOPARTICLES...85
L. Stiebra, S. Gaidukovs, A.Amautovs
P12. GAMMA IRRADIATION: AGREENTOOL FOR THE PREPARATION, MODIFICATION AND
FUNCTIONALIZATION OF POLYMERIC-BASED MATERIALS ...87 J.J. H. Lancastre, L.M. Ferreira, M. H. Casimiro, F. MA Margaça, AN. Falcão, I.M. Miranda Salvado
P13. ENCAPSULATION OF ROSMARINIC ACID INTO CHITOSAN AND MODIFIED CHITOSAN
MICROPARTICLES FOR TOPICALDELIVERY...89
F. Casanova, B. N. Estevinho, L. Santos
P14. RHEOLOGICAL BEHAV10R OF CELLULOSE NANOFIBER SUSPENSIONS FROM Posidonía oceânica: EFFECTOFOXIDATIONTREATMENT...S1
F. Bettaieb. O. Nechyporchuk, R. Khiari, M. F. enni, M. N. BeIgacem. A. Dufresne
P15. EFFICIENT FLUOROPHORES DERIVED FROMCITRIC ACID ... 92
W. Kasprzyk, S. Bednarz, P. Zmudzki, M. Galica, D. Bogdat
P16. VISUALIZATION OF A PMMA BLOOD ANALOGUE FLUID FLOWING THROUGH A HYPERBOLIC MICROCHANNEL...94
J. Calejo. D. Pinho, V. Garcia, F.J. Galindo-Rosales, R. Lima, L. Campo-Deafto
6thWorkshop on Green Chemistry and Nanotechnologies in Polymer Chemistry
-B P17. FLOW FOCUSING TECHNIQUE TO PRODUCEPDMS MICROPARTICLES FOR BLOOD ANALOGUE
FLUIDS... 96 S. F. Silva, E.J. Vega, D. Pinho, V. Garcia, R. Lima, J.M. Montanero
P18. GREENPOLYURETHANEPUMICES FOR COS^ETIC APPLICATIONS... 98 M. Kurartska. M. Zieleniewska, L. Szczepkowski, J. Ryszkowska,A. Prociak
P19. PHVSICOCHEMICAL PROPERTIES OF HYDROGEL MATRIX MODIFIED BYCHITOSAN ...100 A. Sobczak-Kupiec, B. Tyliszczak, K. Bialik-Wqs. M. Wójcik. A. Drabczyk, D. Malina
P20. HYDROTHERMAL METHOD OF PRODUCING HYDROXYAPATITE ...102 A. Sobczak-Kupiec, D. Malina, B. Tyliszczak
P21. INFLUENCEOF BIO-POLYOLS BASED ON RAPESEED OIL ON MECHANICAL PROPERTIES OF FLEXIBLEPOLYURETHANEFOAMS...103
S. Mchatowski, A. Prociak
P22. THE COMPOSITES OF RIGID POLYURETHANE FOAMS WITH NATURAL FILLERS FOR
APPLICATION IN THE COSMETIC INDUSTRY ...105 M. Zieleniewska, L. Szczepkowski, K. Satasirtska, J. Ryszkowska
P23. CO-PRECIPITATION SYNTHESIS OF MAGNETIC NANOPARTICLES...107 J. Jaékowska. B. Tyliszczak, K. Bialik-Wqs, D. Walczyk, A. Sobczak-Kupiec
P24. OPTIMIZATION OF THE SYNTHESIS OF /V-ACRYLOYLAMINOCAPROIC ACID (A6ACA) AS A
MONOMERFORTHEHYDROGELMATRIX...109 B. Tyliszczak, K. Bialik-Was. J. Jaékowska. A. Sobczak-Kupiec
P25. CORALINE HYDROXYAPATITE AS ABONE SUBSTITUTE...111 K. Bialik-Wqs. A. Sobczak-Kupiec, D. Malina, K. Pluta, B. Tyliszczak
P26. STUDYON SYS TE MS CONTAINING PROTEIN-CHITIN-MELANIN COMPLEXES ...113 K. Bialik-Wqs. B. Tyliszczak, Dorota Walczyk, A Sobczak-Kupiec, D. Malina, A Drabczyk
P27. PREPARATION OFPROTEIN-CHITIN-MELANIN COMPLEXES ATTAINED BYEXTRACTION ...115 B. Tyliszczak, K. Bialik-Wqs. D. Malina, SoniaKudtacik. A Sobczak-Kupiec
P28. BIOCOMPATIBLE POLYMERIC MATRICES - AN OVERVIEW ...117
A Sobczak-Kupiec.D. Walcqfk, K. Bialik-Wqs, B. Tyliszczak
P29. STUDYON MECHANICAL PROPERTIES OF HYBRID EPOW-POLYURETHANE BIO-BASED MWERIALS...^
A Sienkiewicz, P. Czub
P30. BIONANOCOMPOSITE HYDROGELS FROMCROSS-LINKED CELLULOSE NANOCRYSTALS ...120 C. García-Astrain, K. González, T. Gurrea, A. Eceiza, N. Gabilondo
P31. SYNTHESIS OF RIGID POLYURETHANE FOAMS FROM Stfpa tenacfSS/maL. OXYPROPYLATED LIGNIN... 122
B. Berrima, G. Mortha, S. Boufi, L. El Aloui, M. N. Belgacem
P32. ISOLATION OF NANOCELLULOSES BY SUCCESSIVE CHEMICAL TREATMENTS ...123 G. Mondragon, C. Pena, A. Orne, A. Arbelaiz, A. Eceiza
P33. HYBRID BIONANOCOMPOSITES BY m-s/ÏuASSEMBLING OF BACTERIAL
CELLULOSE/MONTMORILLONITECLAY...125
l. Algar, C. Garcia-Astrain.A Gonzalez, L. Martin, O. Guaresti, N. Gabilondo. A. Retegi, A. Eceiza
P34. MINIEMULSION POLYMERIZATION: A SIMPLE AND VERSATILE WAY TO LUMINESCENT
NANOSPHERES...127 M. Galica. D. Buguai
P35. GREEN SYNTHESIS OF METALLIC NANOPARTICLES BY A VEGETAL EXTRACT ...129
M.M. Sánchez-Navarro, MÁ Pérez-Limifiana.F. Arán-As, C. Orgilés-Barceló
P36. 1NFLUENCEOFTHE EXTRACTION TEMPERATURE ON THEGELATINE MICROENCAPSULATING PROPERTIES OBTAINED FROMTANNERYWASTES BY AN ENZYMATIC PROCESS ...131
MA Pérez-Limifiana,M.M. Sánchez-Navarro, MJ. Escoto-Palados, F. Arán-Aís, C. Orgilés-Barceló
6th Workshop on Green Chemistry and Nanotechnologies in Polymer Chemistry
PI 7. FLOWFOCUSING TECHNIQUE TO PRODUCE PDMS
MICROPARTICLES FOR BLOOD ANALOGUE FLUIDS
S. F. Silva1, E.J. Vega2, D. Pinho1'3. V. Garcia1, R. Lima1-3-4'*, J.M. Montanero2
1Polytechnic Institute of Bragança, Campus de Santa Apolónia, Bragança, Portugal
2Extremadura University, Avda. Eivas s/n, Badajoz, Spain
3CEFT, FEUP, R. Dr. Roberto Frias, 4200-465 Porto, Portugal, Portugal
4Minho Uniwrsity, MED, Guimarães, Portugal
*ruimec@ipb. pt
Introduction
Tlie study of the blood flow behaviour through microchannels is crucial to improve our understanding
about blood flow phenomena happening in the human microcirculatory system. Howewr, the difficulties
associated with the use of in vitro blood, such as coagulation and sample storage, have promoted the
increasing interest to devslop fluids with rtieological properties similar to real blood [1].
Polydimethysiloxane (PDMS), due its remarkable properties such as good optical transparency,
biocompatibility and permeability to gases, is widety used to fabricate microfluidic devices for in vitro
blood experiments [2]. Recently, this inert elastomer hás been used to produce monodisperee PDMS
microbeads through a microfluidic approach [3]. Jiang et. al. haw proposed a flow-focusing technique
where a PDMS precursor was dispersed into microdroplets within an aqueous continuous phase [3]. By
using this method they were able to produce PDMS microbeads with an average dimension of 80
microns. However, to dewlop blood analogue fluids it is essential to have PDMS microparticles with
dimensions more dose to the blood cells, i. e., the microparticles should have dimensions smaller than
20 microns. Hence, in this study a novel flow focusing technique was used to produce PDMS
microparticles with dimensions more dose to real blood cells. This technique was recently proposed to
produce jets, droplets, and emulsions with sizes ranging from tens of microns down to the
submicrometer scale [4]. This procedure is also based on the flow focusing principie which the above
mentioned method relies on. Nevertheless, our technique makes use of the breakage of a steady jet to
form the microparticles, which can lead to much higher production rates.
In our technique, liquid is injected at a constant flow rate through a hypodermic needle to form a film
over the needle's outer surface. This film flows toward the needle tip until a liquid ligament is steadily
ejected. Both the film motion and the liquid ejection are driven by the viscous and pressure forces
exerted by a coflowing fluid stream. The outcome is a capillaryjet which breaks up into droplets.
Experimental
We used a hypodermic needle with an inner (outer) diameter of about 160 (300) pm, and with an outer
hydraulic radius of afew microns in the tip. The needle used in this study was not subjected toany kind
oftreatment. The needle was located inside a converging-diverging nozzle with a neck about 150 pm
in diameter by using high-precision orientation-translation systems. The nozzle was formed at one of
the ends of a borosilicate capillary, and its shape was characterized with the procedure described
elsewhere [5]. We used a common PDMS elastomer kit consisting of two parts: a base of
vinyl-terminated siloxane oligomers (Part A) and a curing agent of siloxane oligomers and catalyst (Part B).
The proportion Part A:Part B of the mixture was 6:4, whose viscosity was around 827 cSt [3]. The
mixture was injected through the needle at a constant flow rate by means of a syringe pump connected
to a stepping motor. The needle anri the nczzle were immersed in a bath of s mixture of giycerine and
surfactant Brij 30 (to awid the coalescence of the droplets), which is immiscible with the PDMS
precursor. The outer bath was suctioned across the nozzle at a constant flow rate with another syringe
pump to produce the focusing effect (see figure 1).
Digital images ofthe fluid configuration were acquired using a digital camera which allowed us toacquire
images with an exposure time of 25 ps. The camera was equipped with a set of optical lenses. The
optical lenses were selected depending on the size of the imaged object, with a magnification ranging
from 0. 076 to 0. 52 /ym/pixel. The camera could be displaced both horizontally and wrtically using a
triaxial translation stage to focus thejet. The fluid configuration was illuminated from the back side by
6thWorkshop on Green Chemistry ana Nanotechnologies in Polymer Chemistry
cool white light proyded by an optical fiber connected to a light source. We also acquired images ofthe needle by using an auxiliary camera with an optical axis perpendicular to that of the main camera. The use ofthe two cameras allowed us to check thatthe needle was correctly positioned. Ali these elements were mounted on an optical table with a pneumatic anti-vibration isolation system todamp the vibrations coming from the building.
Results and discussion
Our preiiminary results indicate that the technique described in this work allows us to produce particles
ofPDMS ranging 1-100 microns indiameter. Wecheckedthat thecollectionsofdrops had a high degree
of monodispersity and we can reach high production rates (see figure 1).
^ l
Fig. 1. (Left) Precursor jet ofPDMS particles. (Right) Stream of droplets, about 5 microns in diameter,
behind the nozzle.
Once the droplets are accumulated in the syringe, the emulsion can be transferred to an oven at 70 °C to thermally cure the droplets into solid particles. After that, these PDMS microparticles can be either stored in the same glycerine solution or centrifuged, rinsed and dried under vacuum to a powder. Dried particles can be re-dispersed in various media depending on the application.
Conclusions
In this work, we have applied a novel flow focusing technique to produce microparticles of PDMS with diameters down to the micrometer scale, and high degree of monodispersity and production rates. The results are very promising and we beliew that the produced PDMS microparticles can be used to dewlop a blood analogue fluid with rheological properties similar to real blood.
One of the features of the present technique is the fact that the variation of the needle position in the nozzle enables one to select the size of the resulting droplets, which confers the method on both flexibility and robustness. The droplet sizewill be measured systematically to determine its dependence not only on the needle position but also on the rest of the contrai parameters of the problem.
Acknowledgements
The authors acknowledge the financiai support proyded by Fundação para a Ciência e a Tecnologia
(FCT), COMPETE and FEDER through projects PTDC/SAU-ENB/116929/2010,
EXPL/EMS-SIS/2215/2013 and fellowship SFRH/BD/89077/2012. Partial support from the Ministry of Sciénce and Education, and Junta de Extremadura (Spain) through Grants Nos. DPI2013-46485, and GR10047, respectiwly, is gratefully acknowledged too.
References
[1] P. C. Sousa, F. T. Pinho, M. S. N. Oliwira, and M. A. Alves, Biomicrofluidics 5 (2011), 014108. [2] R. Lima, T. Ishikawa, Y. Imai, and T. Yamaguchi, In: Single and two-Phase Flows on Chemical and
Biomedical Engineering, Bentham Science Publishers, Netheriands, ( 2012) pp. 513-547.
[3] K. Jiang, P. C. Thomas, S. P. Forry, D. L DeVoe, S. R. Ragha^n, Microfluidic synthesis of monodisperse PDMS microbeads as discrete oxygen sensors, Soft Matter, 8 (2012) 923.
[4] A. J. Acero, N. Rebollo-Munoz, J. M. Montanero, A. M. Ganán-Calvo, L. J. Vega, A new flow
focusing technique to produce very thin jets, Journal of Micromechanics and Microengineering, 23
(2013) 065009.
[5] J. M. Montanero, A. M. Ganán-Calvo, A. J. Acero, E. J. Vega, Micrometer glass nozzles for flow focusing, J. Micromech. Microeng., 20 (2010) 075035.
