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Characterization of hybrid

inorganic-organic polymers for


Wood and Paper protection
Giovanni Predieri(1)*, Laura Bergamonti(1), Claudia Graiff(1),
Clelia Isca(1), Pier Paolo Lottici(2)
(1) Chemistry Department, University of Parma, Parco Area delle
Scienze 17/a, 43124 Parma, Italy
(2) Physics and Earth Sciences Department, University of Parma,
Parco Area delle Scienze 7/a, 43124 Parma, Italy
giovanni.predieri@unipr.it
2015 E-MRS Spring Meeting - LILLE
Workshop on Sustainable solutions for restoration & conservation of
cultural heritage

Layout
Introduction
Polyamidoamines
Characterization
Wood
Paper

Nanomaterials for consolidation and


protection of wood from biotic decay

WOOD

Major
components
90-95%

Polysaccharides
60-70%

Cellulose
40-50%

Wood
constituents

Minor
components
5-10%

Lignin
20-35%

Organic
2-4%

Inorganic
0.2-0.6%

Hemicellulose
15-35%

Hemicellulose
Cellulose
Lignin

Wood cells

Cell wall

Fibrils

Polymerics chains

Interactions among lignocellulosic polymers


at the molecular level
Crystalline region

Paracrystalline region

Cellulose

Hemicellulose

Lignine

lignine-hemicellulose
cellulose-hemicellulose
lignine-hemicellulose covalent bonds
H-bonds
H-bonds

Functionalising wood by nanosol


application

B. Mahltig et al., J. Mater. Chem., 2008; doi: 10.1039/b718903f

The sol-gel process

The sol-gel process with silicon alkoxides

Wood fossilization

Petrified Wood Log Tumble Petrified Forest National Park

Additives and properties

Types of nanosol application


and the protective effects

Uptake of silica nanosols

Protection against
fungi and insects

Copper and boron grafting


onto amino-functionalized silica xerogel inside the wood

ionic interactions

WOOD

coordinative interactions

sensible to water leaching;


nevertheless enbedding into wood would improve resistence to leaching

X-rays maps

SEM image

Si map

Cu map

SEM image of area map into a treated wood cross section

Palanti S, Predieri G, Vignali F, Feci E, Casoli A, Conti E (2011). Wood Sci Technol.
DOI: 10.1007/s00226-010-0396.

Polyamidoamines (PAA or PAMAM)


Polyamidoamine (PAA) are synthetic tertamino polymers
containing amido and amino groups regularly arranged along the
polymer chains, obtained by addition of primary or secondary
mono or diamines to bisacrylamides in protic polar solvents.

Recent developments
Poly(amidoamine)s: Past, Present, and Perspectives
by Paolo Ferruti, UniMi
JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2013, 51, 23192353

.PAAs are per se highly functional polymers and, in addition, can be further
functionalized giving rise to an endless variety of polymeric structures meeting the
requisites for applications in such apparently disparate fields as inorganic water
pollutants scavengers, sensors, drug and protein intracellular carriers, transfection
promoters, peptidomimetic antiviral and antimalarial agents

..PAMAM dendrimers exhibit greater biocompatibility than other dendrimer


families, perhaps due to the combination of surface amines and interior amide bonds;
these bonding motifs are highly reminiscent of innate biological chemistry and
endow PAMAM dendrimers with properties similar to that of globular proteins.The
relative ease/low cost of synthesis of PAMAM dendrimers, along with their
biocompatibility, structural control, and functionalizability, have made PAMAMs
viable candidates for application in drug development, biochemistry, and
nanotechnology..

The Michael reaction


via the Michael reaction,
addition of nucleophiles
(amines)
to
electron
deficient alkenes (MDA)

MDA and a diamine C6

PAMs from primary amines

MDA and ethanolamine


H2NCH2CH2OH

PAMs from primary amines


MDA and aminopropyltriethoxysilane H2NCH2CH2CH2Si(OEt)3

POSS cage
Polyhedral
Oligomeric
SilSesquioxanes

Synthesis of model molecules


AADETA
MBADETA

AAETA

Monitoring the
AA and PAA
syntheses by
Raman
Spectroscopy

Monitoring the formation of AADETA

NMR characterization

Monitoring the formation of polymers


vs

NMR spectra of PAA

ESI mass spectra of PAA


708, EMEMEME

EtOH

61, E
215, EM

H2O

PAA paper treatment


Application methods
immersion (I)
brush (B)
Agar gel (G)

FTIR spectra before and after the treatment

FT-IR spectrum of filter paper before (blue) and after (black)


treatment with PAA 1M (1:1) (IMMERSION TREATMENT)

FTIR spectra before and after the treatment

FT-IR spectra of 18th century paper before (green) and after


the treatment with PAA 0,3M (1:05:05) (IMMERSION TREATMENT)

Anhydrous mass gain 1


FILTER PAPER

(samples are the average of 7 replicates)

Set of Samples
Ib_1 (30 min)
Ib_0.5 (30 min)

W anhydrous %

Treatment
PAA 1M (1:1)
by immersion (30 min)
PAA 0,5 M (1:1)
by immersion (30 min)

35,25%

conc.

Gel_n (60 min.)

PAA 0,15M (1:1)


by immersion (30 min)
PAA 0,1M (1:1)
by immersion (30 min)
PAA 1M (1:1) Boric ac.
by immersion (30 min)
PAAOH 0,5M (1:1) ac. Borico
by immersion (30 min)
PAA 0,15M (1:1) ac. Boric
by immersion (30 min)
PAA 0,1 M (1:1) ac. Boric
by immersion (30 min)
PAA 0,1M in Agar gel 2% (w/v)
Application for 60 minutes
PAA 0,1M in Agar gel 2% (w/v)
Application for 30 minutes
PAA 0,1M-ac.Boric in Agar gel 2% (w/v)
Application for 60 minutes

Gel_n (30 min.)

PAA 0,1M-ac.Boric in Agar gel 2% (w/v)


Application for 30 minutes

Ib_0.15 (30 min.)


Ib_0.1 (30 min)
In_1 (30 min)
In_0.5 (30 min)

In_0.15 (30 min.)


In_0.1 (30 min)
Gel_b (60 min.)
Gel_b (30 min.)

16,64%
6,20%
3,19%
40,94%
19,56%

9,87%
4,87%

time

3,86%
3,84%

time

7,50%
6,45%

Anhydrous mass gain 2


18th CENTURY PAPER

(samples are the average of three replicates)

Set of Samples

Treatment

W anhydrous %

Br7_ MEA_0.3

PAA 0.3M (1:05:05) (MBA-EA-APTES)

8,36%

by brush
I7_MEA_0.3

PAA 0.3M (1:05:05) (MBA-EA-APTES) by


immersion (30 min)

23,81%

Ib7_0.15 (30 min.)

PAA 0,15M (1:1)


by immersion (30 min)
PAA 0,15 M (1:1) ac. Boric
by immersion (30 min)
PAA 0.1M in Agar gel 2% (w/v)
Application for 30 minutes
PAA 0.1M in Agar gel 2% (w/v)
Application for 45 minutes
PAA 0.1M in Agar gel 2% (w/v)
Application for 60 minutes
PAA 0.1M-ac.Boric in Agar gel 2% (w/v)
Application for 30 minutes

6,90%

In7_0.15 (30 min.)


Gel_1b7 (30 min.)
Gel_2b7 (45 min.)
Gel_3b7 (60 min.)
Gel_1n7 (30 min.)

13,23%
1,47%

time

2,15%
1,36%
6,05%

Gel_2n7 (45 min.)

PAA 0.1M-ac.Boric in Agar gel 2% (w/v)


Application for 45 minutes

5,58%

Gel_3n7 (60 min.)

PAA 0.1M-ac.Boric in Agar gel 2% (w/v)


Application for 60 minutes

5,18%

11.25

pH values of paper before and after


treatments

9.

6.75
post

pH

pre

4.5

2.25

0.
b 60 min

AGAR+PAA
On filter paper
(60 min
30 min)

b 30 min 1b7 30 min 2b7 45min 3b7 60 min Ib 30 min Ib7 30 min n 60 min

AGAR+PAA
On XVIII century
paper
(30 min
45 min
60 min)

IMMERSION IN PAA
filter paper
(30 min)

n 30 min

In 30 min

IMMERSION IN PAA
XVIII paper
(30 min)

AGAR+PAA+ boric ac.


filter paper
(60 min
30 min)

Chromatic changes
Whatman filter paper
2.50

Samples
E

1.88

b
L

1.25

b 60 min
b 30 min
n 60 min
n 30 min
Ib
In

0.63

a
0.00
-0.63

Gel b 30
min
Gel b 60
min
Ib
Gel n 30
min
Gel n 60
min
In

0,41

-0,11

1,13

1,70

0,84

-0,28

0,96

1,84

0,44

-0,02

0,65

0,87

0,56

0,02

0,60

0,92

0,85

0,01

0,62

1,23

0,83

-0,12

0,10

0,85

XVIII century paper


22.50

16.88
11.25

yellowing decrease
L

5.63
0.00
-5.63

b7
n7
Ib7
In7

Samples
b7
Ib7
n7
In7

L
1,63
1,71
1,81
1,83

a
0,38
0,43
0,23
0,43

b
-1,77
-3,00
-1,86
-3,86

L = lightness
a = red/green color opponent
b = yellow/blue color opponent
E = total color difference

E
4,91
10,87
5,33
16,93

FT-IR ANALYSIS BEFORE AND AFTER ACCELERATED AGING (80C; 65%


RH)

No significant chromatic changes

XVIII century paper treated by immersion in PAA 0.15M before and after aging

Leaching test in water


ESI-MS analysis of paper treated with PAA (MBA-EA)

paper blank

MMFF calculations

H-bond interaction between 4 cellobiosic


units and a PAA (MBA + 2 DEA) fragment

Biocidal activity tests


Cladosporium cladosporioides, Penicillium rugulosum, Chaetomium globosum and
Eurotium chevalieri fungi have been used for the biocidal in-vitro tests

PAAOH polymer at basic pH high biocidal activity against all


species (in particular for Eurotium and Penicillium)
Penicillium MEA growth

Spore germination

160.
120.
80.
40.
0.
B

Eurotium spore germination on control MEA growth


medium (sx) after 7 days.

Cu2+ ions
coordination and
dispersion of Ag
NP in SiPAA

50

Counts

40
30
20
10
0
5

10

15

20

Diameter (nm)

25

Characterization of treated wood:


ESEM-EDS penetration depth
Micrograph and relative microanalysis along the cross section of the sample
treated by dip coating with PAA polymer functionalized with siloxane groups.
Si is detected up to 1200 mm of depth.

UNI EN 113
Evaluation of preservative effectiveness

Coniophora puteana

Trametes versicolor
Poria placenta

Mass loss for SiPAA treatment: 3.1%


Mass loss for SiPAA treatment: 0.4 %
Mass loss for control samples: 38%
Mass loss for SiPAA treatment: 13 %
Mass loss for control samples: 58 %
Mass loss for control samples: 21.6 %

Cu-SiPAA
AgNP-SiPAA

UNI EN 113
Evaluation of preservative effectiveness

Reticulitermes lucifugus: worker (left) and soldier (right)

Kalotermes flavicollis: false workers and Queen (left); soldier (right)

NO-CHOICE TEST

Control

Reticulitermes lucifugus

SiPAA (A)

SiPAAOH
Treated Sample Weight Loss Visual Rating Mortality
SiPAA (A)
0.3%
1
74%
SiPAAOH (S)
0.2%
1
73%
PAAOH (P)
0.03%
0.5
75%
Control (E)
7%
4
48%
PAAOH (P)

Kalotermes flavicollis

Control (E)
SiPAAOH (S)

SiPAA (A)

Treated Sample Weight Loss Visual Rating Mortality


SiPAA (A)
0.3%
1
98%
SiPAAOH (S)
0.2%
2
95%
PAAOH (P)
0.03%
1.5
91%
Control (E)
7%
4
33%

PAAOH (P)

CONCLUSIONS

Copper and boron active forms in water

insoluble fraction
insoluble but not too much !

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