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

2013 Dissemination

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

The financial support: - offers the opportunity to improve the research activities - stimulate team members to report results accepted by scientific community - motivate researchers to be more creative and to work harder

PROJECT TEAM