Upload
others
View
2
Download
0
Embed Size (px)
Citation preview
http://bercea300en.weebly.com/ http://www.icmpp.ro/projects
PN-II-ID-PCE-2011-3-0199
IDEI Program, Exploratory Research Project, contract nr. 300/05.10.2011
Project Leader: Dr. Maria BERCEA
Contracting Authority : Executive Unit for Financing Higher Education, Research Development and Innovation, Romania
Host Institution : PETRU PONI Institute of Macromolecular Chemistry, Iasi Romanian Academy
POLYMER MATERIALS WITH SMART PROPERTIES
Total Budget: 1.500.000 lei 2011: 200.000 lei 2012: 600.000 lei 2013: 191.883,61 lei 2014: 137.500 lei 2015: 370.616,39 lei
Team Members:
Dr. Simona MORARIU – senior researcher
Dr. Aurica CHIRIAC – senior researcher
Dr. Luminita GHIMICI – senior researcher
Dr. Cristina-Eliza BRUNCHI – PhD student (2011), PostDoc (2012-2014)
Dr. Luiza-Madalina GRADINARU – PhD student (2011-2012)
PostDoc (2013-2014)
Drd. Livia-Elena BIBIRE – PhD student (2012-2014)
Drd. Monica-Diana OLTEANU – PhD student (2012)
POLYMER MATERIALS WITH SMART PROPERTIES
2011
OBJECTIVES/Activities/Dissemination/New insights
2011 (5 October 2011 - 15 December 2011)
Objective
Evaluation of intra- and inter-molecular interactions of natural and synthetic polymers in binary polymer/solvent systems
Associated activities: -Types of interactions occurring in solutions of natural and synthetic polymers - Peculiar behaviors of natural or synthetic polymers in solution and how to model them
Morariu S., Brunchi C.-E., Bercea M. The behaviour of chitosan in solvents with different ionic strength Industrial & Engineering Chemistry Research, 51(39), 12959-12966 (2012) DOI: 10.1021/ie301309g IF = 2.237; SI: 1.91195, 4 citations
Dissemination: 1 paper was sent for publication and published in 2012:
New insights: - Exploring the properties of polysaccharides (chitosan, xanthan) and synthetic polymers (PEO, Pluronics)
- Application of new models for describing the behaviour of polymer systems
New insights:
Smart polymeric materials were designed and investigated:
- Thermoreversible hydrogels for biomedical applications
- Interpenetrated hybrid polymeric composites; magnetic field effect
- Polyelectrolyte complexes
2012
OBJECTIVES/Activities/New insights
2012 (16 December 2011 – 15 December 2012)
Objectives/Activities
1. Evaluation of interactions established in multicomponent polymer systems in solution - Studies concerning the compatibility of PVA/Pluronic mixtures in solution by considering the viscometric/rheological data - Correlation of the rheological data with turbidimetric and light scattering curves
2. Chemical gels based on natural and/or synthetic polymers - In-situ monitoring of the sol-gel transition for chemical gels in presence of natural or synthetic crosslinkers - Establishment of the optimal conditions of gelation for obtaining elastic hydrogels - Investigation of the properties of synthetic and natural hydrogels
3. Physical gels based on multicomponent polymer systems - Investigation of the conditions of gel formation (gelation point, kinetic aspects) - Elaboration of physical gels which present the sol-gel transition around 37°C - Influence of the environmental conditions on the gel properties
Dissemination: 4 papers (ISI journals), 8 papers in Proceedings of International Conferences 7 books chapters, 10 participations at scientific events
2012
Dissemination
1. Gradinaru L.M., Ciobanu C., Vlad S., Bercea M., Popa M. Thermoreversible poly(isopropyl lactate diol)-based polyurethane hydrogels: effect of isocyanate on some physical properties Industrial & Engineering Chemistry Research, 51(38), 12344-12354 (2012), DOI: 10.1021/ie301690e IF = 2.237; SI: 1.91195, 1 citation
2. Nita L.E., Chiriac A.P., Bercea M., Neamtu I. The magnetic field effect during preparation of an interpenetrated hybrid polymeric composite Polymer Composites, 33(10), 1816-1823 (2012), DOI: 10.1002/pc IF = 1.231; SI: 1.12671
3. Bercea M., Nita L.E., Eckelt J., Wolf B.A. Polyelectrolyte complexes: phase diagram and intrinsic viscosities of the system water/poly(2-vinylpyridinium-Br)/poly(styrene sulfonate-Na) Macromolecular Chemistry and Physics 213 (23), 2504-2513 (2012), DOI: 10.1002/macp.201200445 IF = 2.361; SI: 2.11533, 6 citations
4. Gradinaru L.M., Ciobanu C., Vlad S., Bercea M., Popa M. Synthesis and rheology of thermoreversible polyurethane hydrogels Central European Journal of Chemistry, 10(6), 1859-1866 (2012), DOI: 10.102478/s11532-012-0100-8 IF = 1.073; SI: 0.65569, 1 citation
New insights:
Smart polymeric materials were designed and investigated:
- Polymer/clay hybrid hydrogels
- Physical PVA hydrogels for biomaterials and actuators
- Sensitive (pH, temperature) semi-interpenetrated polymeric networks
- TiO2 separation from water by using PEG and its copolymers (Pluronics)
2013 OBJECTIVES/Activities/New insights
2013 (16 December 2012 – 15 December 2013)
Objectives/Activities
1. Physical gels based on polymer/clay mixtures in aqueous medium - Preparation and investigation of gels based on synthetic polymer/clay mixtures - Preparation and investigation of gels based on natural polymer/clay mixtures
2. Evaluation of specific interactions which determine the formation of the interpolymeric complexes for polymer mixtures in solution - Investigation of the thermodynamic and viscoelastic properties for aqueous solutions of natural and synthetic polymers; - Evaluation of polymer-polymer compatibility for natural and synthetic polymers in aqueous solutions at 37°C
3. Evaluation of specific interactions which determine the formation of supramolecular structures from copolymers in solution - Thermodynamic and rheological studies for copolymers in solution
2013 Dissemination
1. Bercea M., Morariu S., Rusu D. In-situ Gelation of aqueous solutions of entangled poly(vinyl alcohol), Soft Matter, 9, 1244-1253 (2013), DOI:10.1039/C2SM26094H, IF = 4.39; SI: 5.30501, 6 citations
2. Nita L.E., Chiriac A.P., Bercea M., Wolf B.A. Synergistic behavior of poly(aspartic acid) and Pluronic F127 in aqueous solution as studied by viscometry and dynamic light scattering, Colloids and Surfaces B: Biointerfaces, 103, 544–549 (2013), DOI: 10.1016/j.colsurfb.2012.10.054 IF = 3.456; SI: 1.06991, 3 citations
3. Ghimici L., Brunchi C.-E. Titanium dioxide separation from water by PEG and Pluronic type polymers, Separation and Purification Technology, 103, 306-312 (2013), DOI: 10.1016/j.seppur.2012.10.045 IF = 2.921; SI: 2.53774, 1 citation
4. Nistor M.T., Chiriac A.P., Nita L.E., Vasile C., Bercea M. Semi-interpenetrated polymer networks of hyaluronic acid modified with poly(aspartic acid), Journal of Polymer Research, 20(2), Nr. 86 (2013) DOI: 10.1007/s10965-013-0086-8, IF = 2.019; SI = 1.06222, 3 citations
5. Brunchi C.-E., Ghimici L. PEG in aqueous salt solutions. Viscosity and separation ability in a TiO2
suspension, Revue Roumaine de Chimie, 58, 183-188 (2013) WOS:000331782400011, IF = 0.418; SI = 0.15269
6. Morariu S., Bercea M. Thixotropy and yield stress evaluation for clay aqueous dispersions Revue Roumaine de Chimie, 58(2-3), 145-152 (2013) WOS:000331782400006, IF = 0.418; SI = 0.15269
7. Nistor M.T., Chiriac A.P., Nita L.E., Neamtu I., Vasile C. Semi-interpenetrated network with improved sensitivity based on poly(N-isopropylacrylamide) and poly(aspartic acid), Polymer Engineering and Science, 53(11), 2345-2352 (2013) DOI: 10.1002/pen.23488, IF = 1.243; SI = 1.34906
Dissemination: 1 book, 7 papers (ISI journals), 15 participations at scientific events
Book: POLYMER MATERIALS WITH SMART PROPERTIES, Editor: Maria Bercea Nova Science Publishers, Inc., 2013, ISBN: 978-1-62808-876-2
New insights:
Smart polymeric materials were designed and investigated:
- Thermoreversible hydrogels for biomedical applications – investigation of sol-gel transition
- Hybrid hydrogels natural polymer/synthetic polymer/clay mixtures
- Temperature and pH effect on self-assembling process
- Thermodynamics of copolymers – under investigation
2014
OBJECTIVES/Activities
2014 (16 December 2013 – 15 December2014)
Objectives/Activities 1. Physical and chemical gels from natural and synthetic polymers - Description of viscoelastic behaviour near the gelation point; investigation of the sol-gel transition - Gels based on natural polymer/synthetic polymer/clay mixtures. Preparation and investigation of their properties - The effect of copolymer composition and solvent quality on the thermodynamic properties in perturbed and unperturbed state
1. Nita L.E., Chiriac A.P., Bercea M., Effect of pH and temperature upon self-assembling process between poly(aspartic acid) and Pluronic F127, Colloids and Surfaces B: Biointerfaces 119 (2014) 47–54, DOI: 10.1016/j.colsurfb.2014.04.023, IF = 3.456; SI: 1.06991
2. Bercea M., Morariu S., Nita L.E., Darie R., Investigation of Poly(vinyl alcohol)/Pluronic F127 Physical Gels, Polymer-Plastics Technology and Engineering, 00, 1-8 (2014) DOI: 10.1080/03602559.2014.909460, IF = 1.481; SI: 0.41275
3. Brunchi C.-E, Morariu S., Bercea M., Intrinsic viscosity and conformational parameters of xanthan in aqueous solutions: Salt addition effect, Colloids and Surfaces B: Biointerfaces, (2014) IF = 3.456; SI: 1.06991
4. Ciobanu C., Gradinaru L.M., Drobota M., Vlad S., Bercea M., Popa M., Influence of diisocyanate structure on properties of some thermoreversible polyurethane hydrogels, Journal of Hydrogels, accepted for publication, 2014
5. Ciobanu C., Gradinaru L.M., Drobota M., Quaini F., Falco A., Frati C., Graiani G., Madeddu D., Lagrasta C., Vlad S., Bercea M., Sacarescu L. Injectable thermoreversible hydrogels based on amphiphilic polyurethanes: structure-property correlations, Journal of Hydrogels, accepted for publication, 2014
6. Morariu S., Bercea M., Sacarescu L., Tailoring of clay/poly(ethylene oxide) hydrogels properties by chitosan incorporation, Industrial & Engineering Chemistry Research, submitted
7. Morariu S., Bibire L., Brunchi C.-E, Carja G., Bercea M., Chitosan/poly(vinyl alcohol) mixtures for designing physical hydrogels, prepared for publication
8. Bercea M., Bibire L., Morariu S., Carja G., Chitosan/poly(vinyl alcohol)/LDH biocomposites with pH-sensitive properties, prepared for publication
2014
Dissemination
2015
OBJECTIVES/Activities
2015 (16 December 2014 – 4 October 2015)
Objective: Constitutive response of the obtained materials in different using conditions
Associated activities: - Correlation between the thermodynamic parameters and phase separation phenomena - Correlation between the thermodynamic properties and rheological data; establishing the conditions in which the supramolecular structures appear - Dissemination the constitutive response of materials at different external stimuli
New insights at the end of the project:
- Design of smart polymeric materials with predictable response at different external stimuli
- A better understanding of phenomena and processes involving polymer materials
- A deeper knowledge of bioresurces (natural polymers, clay) and how to use them for tailoring new materials of both scientific and practical interest
4 reports advanced to contracting authority in 2011, 2012, 2013(2)
20 papers, cited 24 times (Web of Science, Scopus) (in the project proposal: 7 papers with IF in 3 years)
Cumulated Impact Factor (IF): 32.4 Cumulated Influence Score (SI): 21.9
1 book – 7 chapters with acknowledgements to this project 8 papers published in Proceedings of International Conferences 25 participations at National and International Conferences
Some results are included in 3 PhD Thesis: Brunchi CE: Macromolecular interactions of complex polymeric structures in solution Gradinaru LM: Polyurethane hydrogels: synthesis, characterization, applications Bibire LE: Hybrid materials based on polymer/layered double hydroxides
2011 - 2014
Overview: Project Results and Performances
Progress towards objectives: 100%
Young researchers involved in the project activities
4 senior researchers (including the project manager)
4 PhD students/post-doctoral positions - 50% from human resources
20 papers elaborated: 10 papers have young members as coauthors - 50% from total papers involved students and postdoctoral fellows
Allocated percent of full working time to the project activities 2011-2013 Senior Researchers: average = 20% Young Researchers: average = 33%
Financial and human resources
Repartition of financial resources (2011-2015)
37.6%
29.6%
32.8%
Senior Researchers
PhD Students
PD Fellows
Human resources involved (total number of hours)
2011-2013
New infrastructure Osmometer OSMOMAT 090 Modular Rheometer COMPACT PHYSICA MCR 302
Most important scientific achievements 1. Elastic hydrogels for biomedical applications PVA hydrogels obtined by freezing/thawing
Bercea M., Morariu S., Rusu D. In-situ gelation of aqueous solutions of entangled poly(vinyl alcohol), Soft Matter, 9, 1244-1253 (2013)
0.001
0.01
0.1
1
10
100
1000
10000
0.001 0.01 0.1 1 10 100c[h]
hsp
PVA 5
PVA 4
PVA 3
PVA 2
PVA 1
isolated PVA coils
in water
entangled PVA chains
in water
slope 3.5
slope 1.0
(c.[h])overlap = 2.05
10
100
1000
10000
0 2 4 6 8 10n
tA = 0
tA = 50 min
G' (Pa)
PVA solution PVA gel
0.0001
0.001
0.01
0.1
1
10
100
1000
10000
100000
0.1 1 10 100
G' (P
a)
c × [h]
isolated PVA
coils in aqueous
solution
physical
PVA gel
(c[h])overlap
2. pH-responsive physical hydrogels PVA/Chitosan hydrogels obtined by freezing/thawing
Morariu S., Bibire L., Brunchi C.-E,
Carja G., Bercea M.,
Chitosan/PVA mixtures for
designing physical hydrogels (2014)
0 10 20 30 40 50 60 70 8010
-1
101
103
105
107
sol
Tgel
=48.50C
Tgel
=340C
gelcycle 3
a=3
cycle 2
a=1
cycle 1
a=0
G',G
'' x
10
a (
Pa)
t (oC)
0 10 20 30 40 50 60 70 8010
-2
100
102
104
106
108
gel
G"
G'
Tgel
=43.80C
sol
Tgel
=56.60C
cycle 3
a=4
cycle 2
a=2
cycle 1
a=0
G',G
'' x 1
0a (
Pa)
t (oC)
3 6 9 1210
1
102
103
104
G'
G''
G', G
'' (P
a)
Polymer concentration (%)
0 3 6 9 120.01
0.1
1
gel state
tan
Polymer concentration (%)
3. pH-responsive crosslinked hydrogels PVA/Chitosan/LDH
Bercea M., Bibire L., Morariu S., Carja G., Chitosan/poly(vinyl alcohol)/LDH biocomposites with pH-sensitive properties (2014)
4. Hybrid hydrogels PEO/Chitosan/Laponit RD
Morariu S., Bercea M., Sacarescu L., Tailoring of clay/poly(ethylene oxide) hydrogels properties by chitosan incorporation, Industrial & Engineering Chemistry Research (2014)
10-2
10-1
100
101
102
103
10-3
10-1
101
103
105
LRD/PEO
LRD/PEO/CS-0.007
LRD/PEO/CS-0.146
LRD/PEO/CS-0.453
o (Pa)
h (P
as
)
(Pa)
0.0 0.1 0.2 0.3 0.4 0.5 0.60
30
60
90
120
150
o (P
a)
cCS
(%)
0.0 0.1 0.2 0.3 0.4 0.50
1000
2000
3000
4000
G', G
''
(Pa
)
cCS
(%)10
-210
-110
0
101
102
103
104
105
LRD
LRD/PEO
LRD/PEO/CS-0.007
q (Å-1)
q-1.86
q-4
q-1.54
q-3.74
I(q
) (
a.u
.)
357 – 390 Å
Clay aggregates: 203 Å partially exfoliated
4. Hybrid hydrogels PEO/Chitosan/Laponit RD
Morariu S., Bercea M., Sacarescu L., Tailoring of clay/poly(ethylene oxide) hydrogels properties by chitosan incorporation Industrial & Engineering Chemistry Research (2014)
0 20 40 60 80 100 120 1400
1x10-3
2x10-3
3x10-3
4x10-3
5x10-3
6x10-3
7x10-3
Jmax
J0 J
J0
Jd
JR J
C
recoverycreep
J
Time
LRD/PEO/CS-0.007
LRD/PEO/CS-0.096
LRD/PEO/CS-0.146
LRD/PEO/CS-0.266
LRD/PEO/CS-0.453
JC ,
JR
(Pa
-1)
Time (s)
4. Temperature-responsive physical hydrogels PVA/Pluronic F127
Bercea M., Morariu S., Nita L.E., Darie R., Investigation of Poly(vinyl alcohol)/Pluronic F127 Physical Gels, Polymer-Plastics Technology and Engineering, 00, 1-8 (2014)
Pluronic F127
PVA
BSA
0.01
0.1
1
10
100
1000
10000
100000
0 1000 2000 3000 4000time (s)
h(Pas)
5oC
5oC37
oC
(c)
4. Temperature-responsive physical hydrogels Polyurethanes
Gradinaru L.M., Ciobanu C., Vlad S., Bercea M., Popa M., Synthesis and rheology of thermoreversible polyurethane hydrogels, Central European Journal of Chemistry, 10(6), 1859-1866 (2012)
Gradinaru L.M., Ciobanu C., Vlad S., Bercea M., Popa M., Thermoreversible poly(isopropyl lactate diol)-based polyurethane hydrogels: effect of isocyanate on some physical properties, Industrial&Engineering Chemistry Research, 51, 12344-12354 (2012)
4. Temperature-responsive physical hydrogels Polyurethanes
10 20 30 40 50
1E-4
1E-3
0.01
0.1
1
10
100
1000
G' (P
a)
Temperature (o
C)
PU-BDI
PU-HDI
PU-LDI
0 10 20 30 40 50
0.01
0.1
1
10
100
1000
h (
Pa.s
)
Temperature (o
C)
PU-BDI
PU-HDI
PU-LDI
Ciobanu C., Gradinaru L.M., Drobota M., Vlad S.,
Bercea M., Popa M.,
Influence of diisocyanate structure on properties of
some thermoreversible polyurethane hydrogels
Journal of Hydrogels, accepted for publication,
(2014)
5. Dual sensitive semi-interpenetrated networks Poly(N-isopropylacrylamide) and Poly(aspartic acid)
Nistor M.T., Chiriac A.P., Nita L.E., Neamtu I., Vasile C. Semi-interpenetrated network with improved sensitivity based on poly(N-isopropylacrylamide) and
poly(aspartic acid), Polymer Engineering and Science, 53(11), 2345-2352 (2013)
5. Semi-interpenetrated networks Hyaluronic acid and Poly(aspartic acid)
Nistor M.T., Chiriac A.P., Nita L.E., Vasile C., Bercea M., Semi-interpenetrated polymer networks of hyaluronic acid modified with poly(aspartic acid) Journal of Polymer Research, 20(2), Nr. 86 (2013)
5. Semi-interpenetrated networks – magnetic field effect Poly(aspartic acid), Poly(ethylene glycol) and Collagen
Nita L.E., Chiriac A.P., Bercea M., Neamtu I. The magnetic field effect during preparation of an interpenetrated polymeric composite Polymer Composites, 33(10), 1816-1823 (2012)
Nita L.E., Chiriac A.P., Bercea M., Wolf B.A., Synergistic behavior of poly(aspartic acid) and Pluronic F127 in aqueous solution as studied by viscometry and dynamic light scattering Colloids and Surfaces B: Biointerfaces, 103, 544–549 (2013)
6. Self-assembling phenomena (25oC, pH = 7) Pluronic F127 and Poly(aspartic acid)
1
1.1
1.2
1.3
1.4
0 0.2 0.4 0.6 0.8 1
w*
shear viscosity
capillary viscosity
h (
mP
a.s
)
PLU PAS
-26
-21
-16
-11
-6
-1 0 0.2 0.4 0.6 0.8 1
w *
Zeta
po
ten
tial (m
V)
PLU PAS
6. Self-assembling phenomena - pH and temperature effect
Pluronic F127 and Poly(aspartic acid)
Nita L.E., Chiriac A.P., Bercea M., Effect of pH and temperature upon self-assembling process between poly(aspartic acid) and Pluronic F127 Colloids and Surfaces B: Biointerfaces 119, 47–54, (2014)
Nita L.E., Chiriac A.P., Bercea M., Wolf B.A., Synergistic behavior of poly(aspartic acid) and Pluronic F127 in aqueous solution as studied by viscometry and dynamic light scattering Colloids and Surfaces B: Biointerfaces, 103, 544–549 (2013)
6. Self-assembling phenomena Pluronic F127 and Poly(aspartic acid)
7. Separation processes from wasted water TiO2 Separation ability in the presence of polymers
Ghimici L., Brunchi C.-E., Titanium dioxide separation from water by PEG and Pluronic type polymers, Separation and Purification Technology, 103, 306-312 (2013)
C.-E. Brunchi, L. Ghimici, PEG in aqueous salt solutions. Viscosity and separation ability in a TiO2 Suspension, Revue Roumaine de Chimie, 58(2-3), 183-188 (2013)
0 6 12 18
-50
-40
-30
-20
-10
0
10
NaCl 2M, in the presence of clay
NaCl 2M
NaCl 1M
polymer dose (mg/L)
mv
)
Pluronic F127
0 100 200 3000
20
40
60
80
100 water
0.01M NaCl
0.01M KCl
polymer dose (mg/L)
Tu
rbid
ity
(%
)
PEG, 20h
0 4 8 12 16 200
20
40
60
80
100
water, 30min
water, 20h
NaCl 1M, 30min
NaCl 2M, 30min
NaCl 1M, 20h
NaCl 2M, 20h
polymer dose (mg/L)
Turb
idit
y (
%)
Pluronic F127
Aknowledgements
Contracting Authority for financial support : Executive Unit for Financing Higher Education, Research Development and Innovation, Romania
Host Institution : “PETRU PONI” Institute of Macromolecular Chemistry, Iasi Our coworkers:
Prof. Bernhard A. Wolf, Johannes Gutenberg Universitat, Mainz, Germany Prof. Daniela Rusu, Ecole des Mines de Douai, France Prof. Gabriela Carja, Technical University “Gh. Asachi”, Iasi, Romania
From “PETRU PONI” Institute of Macromolecular Chemistry:
Acad. Bogdan C. Simionescu Dr. Constantin Ciobanu Dr. Stelian Vlad Dr. Loredana Nita Dr. Iordana Neamtu Dr. Tatiana Nistor Dr. Liviu Sacarescu
Financial and Administrative Department Ec. Lucia Mocanu Ec. Stela Chirila Ec. Daniel Condrea Ec. Tinuta Terlescu Ing. Ramona Simeria Legal Advisor: Jurist Dr. Raluca-Oana Andone