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CONSERVATION OF WOOD

WITH ACRYLICS
- selected experiments
Ladislav Reinprecht

Technical University of Zvolen


Faculty of Wood Sciences and Technology
T.G.Masaryka 24, 960 53 Zvolen
Slovakia

Consolidation, reinforcement and stabilisation


of decorated wooden artefacts
COST ACTION IE0601, Prague, 30-31 March 2009

Substances for wood conservation

Natural
- beeswax, Montana wax, paraffin wax, colophony, mastic,
dammar, shellac, bone glue, drying vegetable oils, sucrose, etc.

Synthetic
- acrylics, unsaturated polyesters, epoxides, aminoplasts,
phenoplasts, polyurethanes, polyethylene-glycols, etc.

Substances for wood conservation


- General requirements

good penetration into wood


compatibility with materials

compatibility with technological operations good additional treatment

(e.g. materials used during the previous interventions)

protective chemicals, glues, paintings, ...

of conserved wood by gluing, painting, ...

minimal influence on sorption properties of wood


no dimensional changes of conserved wood

(e.g. swelling or shrinkage of wood during their penetration into wood, or during their hardening in wood)

long-term dimensional stability of wood (especially of the water-logged archaeological wood)


minimal influence on aesthetic appearance of conserved wooden object
strengthening of wood
integration of loose or broken parts of wood
stability against weathering, fire, and biological deterioration
no toxicity and minimal impact on environment
reversibility of the intervention (i.e. possibility to remove the conservation product from wood in the future)

Synthetic substances
- Advantages

Availability
Reasonable price
Stability (composition, polymerization degree, properties),
Possibility to prepare special polymers (according to the specific

needs of conservator)

Usually better properties (physical, physical-chemical, resistance

Disadvantage:

against weathering, resistance against biological agents)

Non-reversible process at using of thermosetting types


(e.g. unsaturated polyesters, epoxides, aminoplasts, phenoplasts)

Acrylics - polyacrylates

Preparation

Application forms

Important types for wood conservation

by polymerization of esters of acrylic and methacrylic acids


CH2=CH-COOR
CH2=C(CH3)-COOR
polymers and copolymers (polyacrylates)
monomers polymerized in wood by in situ method

polymethylmethacrylate PMMA (Acrylit X 20/5, Bedacryl L, etc.)


polyethylmethacrylate - PEMA (Acryloid B72, Paraloid B72, etc.)
polybutylmethacrylate - PBMA (Bedacryl 122X, Paraloid B67, Plexisol P 550,
Solakryl BT 55, etc.)
polymethylacrylate - PMA
polyethylacrylate - PEA
polybutylacrylate - PBA
copolymer - MMA/EA (Paraloid B82, Plextol B 500, etc.)
copolymer - MA/EMA
copolymer - MMA/BMA (Elvacite 2013, Osolan KL, Solakryl BMX, etc.)

Acrylics - polyacrylates

Characteristics colourless, transparent, hard but sufficiently elastic

Solubility in less-polar organic solvents (in toluene, xylene, or acetone)

Application 10-20 % solutions (high dynamic viscosity 5-30 mPa.s)


Advantages good resistance against weathering and high temperatures
reversible process
copolymers (MMA/BMA) specific properties of cons. wood

Disadvantage: The solvent evaporates slowly from the conserved wood

(several weeks even months), which can sometimes cause the backwards
migration of acrylic polymer to the wood surface.

Acrylics polyacrylates
- Selected experiments
Technical University of Zvolen, Slovakia

1) Influence on decay processes in wood


2) Strengthening of decayed wood
3) Stabilization of wood surfaces
4) Conservation of wooden sculptures

Acrylics polyacrylates

Influence on decay processes in wood

Acrylics - Influence on decay processes in wood


(Reinprecht et al. 2001, Tiralov and Reinprecht 2004)

Wood species
Beech (Fagus sylvatica L.)
Spruce (Picea abies /L./ Karst.)

15

50

25

Acrylics Influence on decay processes in wood


(Reinprecht et al. 2001, Tiralov and Reinprecht 2004)

Paraloid B-72

(copolymer of methylacrylate and

ethylmethacrylate)

transparent granules, soluble in toluene, acetone and some other organic solvents
filing of lumina and creation of films on S3 surfaces of wood cell walls

Modification of wood

1)
2)
3)

Paraloid B-72 (2 % or 10 % toluene solutions P2 or P10)


Fungicide TCMTB (0.1 % or 0.33 % T0.1 or T0.33)
Paraloid B-72 + Fungicide TCMTB

BEECH WOOD
SPRUCE WOOD

MODIFICATION
METHODS
Paraloid B-72 was applied

drying
IMPREGNATION
0,8MPa, 180 min, 20 C

PARALOID

TCMTB

R1
RTCMTB
RPARALOID

TCMTB

1) separately
2) together with the TCMTB
fungicide (Busan 1160)
a)
b)

impregnation with mixture


(Paraloid + TCMTB)
double impregnation

weighting
mixture

stabilisation
IMPREGNATION
0,8MPa, 180 min, 20 C

PARALOID

weighting, stabilisation
drying

R2
RPARALOID

Acrylics Influence on decay processes in wood


(Reinprecht et al. 2001, Tiralov and Reinprecht 2004)

Mycological test of modified wood samples


Standard EN 113 - duration 16 weeks
Resistance against the brown-rot fungi:
Coniophora puteana (Schum. ex. Fr.)
Gloeophyllum trabeum (Pers. ex Fr.)
Evaluation by the losses of mass - mF (%)

Acrylics Influence on decay processes in wood


(Reinprecht et al. 2001, Tiralov and Reinprecht 2004)

Mycological test

losses of mass of modified beech samples

BEECH WOOD
Coniophora puteana

Gloeophyllum trabeum

40
30
20
10

D0.1 and 2
D0.1 and 10
D0.33 and 2
D0.33 and 10
M 0.1 + 2
M 0.1 + 10
M 0.33 + 2
M 0.33 + 10
N

P2
P10
T0.1
T0.33

D0.1 and 2
D0.1 and 10
D0.33 and 2
D0.33 and 10
M 0.1 + 2
M 0.1 + 10
M 0.33 + 2
M 0.33 + 10
N

0
P2
P10
T0.1
T0.33

mF [%]

Acrylics Influence on decay processes in wood


(Reinprecht et al. 2001, Tiralov and Reinprecht 2004)

Mycological test

losses of mass of modified spruce samples

SPRUCE WOOD
Coniophora puteana

Gloeophyllum trabeum

40

1.96*Std. Err.
1.00*Std. Err.

30

Mean

20
10

D0.1 and 2
D0.1 and 10
D0.33 and 2
D0.33 and 10
M 0.1 + 2
M 0.1 + 10
M 0.33 + 2
M 0.33 + 10
N

P2
P10
T0.1
T0.33

D0.1 and 2
D0.1 and 10
D0.33 and 2
D0.33 and 10
M 0.1 + 2
M 0.1 + 10
M 0.33 + 2
M 0.33 + 10
N

0
P2
P10
T0.1
T0.33

mF [%]

Acrylics Influence on decay processes in wood


(Reinprecht et al. 2001, Tiralov and Reinprecht 2004)

Conclusions
Polyacrylate (Paraloid B-72) do not increased
resistance of wood against brown-rot fungi.
Hypothesis: The fungi (C. puteana, G. trabeum) and their enzymes were able to penetrate
through the polyacrylate film on the S3 surface of wood cell walls.

Better results have been achieved if the polyacrylate


was combined with the TCMTB fungicide.
Double impregnation very good effect of the TCMTB. The mass losses of

modified beech and spruce wood were obviously close to zero.


Mixture impregnation worse effect of the TCMTB. It was caused probably
by blocking of the TCMTB fungicide molecules with the larger polyacrylate
macromolecules.

Acrylics polyacrylates

Strengthening of decayed wood

Acrylics Strengthening of decayed wood


(Reinprecht and Varnska 1998, 1999)

Decayed wood species


1) Spruce naturally damaged in roof structure
- specimens 500 x 30 x 30 mm (bending test) and 30 x 20 x 20 mm (compression and
hardness tests) have been prepared from one 125-year old beam from roof structure in
the historical town of Bansk tiavnica, Slovakia
- more or less homogeneously damaged by insect galleries (diameter from 0.5 mm to 2 mm
from the family of Anobiidae), and by medium fungal decay due to brown-rot fungi

2) Spruce damaged in laboratory by C. puteana


- specimens 120 x 8.5 x 8.5 mm (bending test) have been intentionally damaged by the
brown-rot fungus Coniophora puteana during defined time intervals: 2, 4, 6, 8, or 10
weeks various losses of mass m

Acrylics Strengthening of decayed wood


(Reinprecht and Varnska 1998, 1999)

Solakryl BT 55

(polybutylmethacrylate)

Its efficiency compared with some other conservation agents


(shellac, epoxy, MF-resin, PEG 1000)

Conservation method
Solution:
27.5 % toluene solution of Solakryl BT 55
Moisture of wood: w ~ 8 %
Impregnation: p = 0.8 MPa, t = 20 C, = 3 hours

Acrylics Strengthening of decayed wood


(Reinprecht and Varnska 1998)

Conservation of naturally damaged spruce


Bending MOE

Compression II

Brinell hardness

160

140

120
[%] 100
80

160
140
[%] 120
100
80

450
400
[%] 350
300
250

60
40
20
0
-20
-40

60
40
20
0
-20
-40

200
150
100
50
0
-50

MF - resin

Solakryl
BT 55

PEG 1000

MF - resin

Solakryl
BT 55

PEG 1000

MF - resin

Solakryl
BT 55

PEG 1000

Acrylics Strengthening of decayed wood


(Reinprecht and Varnska 1998)

Conclusions No 1
Solakryl BT 55,
R-[CH2-C(CH3)-COOC4H9]n -X
had a slightly positive effect on the mechanical
properties of biodamaged spruce wood:
- modulus of elasticity,
- compression strength parallel to grain,
- hardness.

Acrylics Strengthening of decayed wood


(Reinprecht and Varnska 1999)

Conservation of spruce decayed by C. puteana


MOEd [%]

SPRUCE DEGRADED BY CONIOPHORA PUTEANA


n = 50
MOEd = 3.4497 m (R = 0.8165)
80
70
60

Modulus of elasticity decrease -

50
40
30
20
10
0

10

Loss of mass -

15

m [%]

20

25

Acrylics Strengthening of decayed wood


(Reinprecht and Varnska 1999)

Conservation of spruce decayed by C. puteana

Acrylics Strengthening of decayed wood


(Reinprecht and Varnska 1999)

Conclusions No 2
Solakryl BT 55,
R-[CH2-C(CH3)-COOC4H9]n -X
slightly increased the MOE of spruce wood
intentionally damaged by the brown-rot fungus
Coniophora puteana.

Acrylics polyacrylates

Stabilization of wood surfaces

Acrylics Stabilization of wood surfaces


(Mamoov and Reinprecht 2008)

Wood species
Larch wood (Larix decidua Mill.)
Spruce wood (Picea abies /L./ Karst.)

Acrylic coatings
Tikkurila OY Finland
Valtti Colour Card
1) Basic layer
2) 2 x Surface layers

Acrylics Stabilization of wood surfaces


(Mamoov and Reinprecht 2008)

Natural ageing
1) One year exposition in exterior under 90
2) One year exposition in interior

Evaluation
I.) Microscopic analyses REM

(TESCAN VEGA TS 5130)

a) penetration of the coatings into wood


b) defects in the coatings
c) changes in the thickness of the coatings

II.) Colour analyses - spectrophotometer

(MINOLTA CM2600d)

a) CIELAB changes in the L*a*b* colour space


b) Spectra and differential spectra

Acrylics Stabilization of wood surfaces


(Mamoov and Reinprecht 2008)

Microscopic analyses

penetration, defects, thickness of coatings

Fig. 1 Detail of the sample T3 = T/(3147) / Picea

abies penetration of the coating into early wood

tracheids; cross-section of the coating is inconsistent

Fig. 2 The surface and the cross-section of the

sample T4 = T/(Interior)/ Picea abies bubbles in


the coating; penetration into early wood tracheids;
Thickness: h ~ 130 m

Acrylics Stabilization of wood surfaces


(Mamoov and Reinprecht 2008)

Microscopic analyses

penetration, defects, thickness of coatings

Fig. 3 The cross-section of the sample T2 =

T/(3151 - Exterior) / Picea abies bubbles in


the coating;
Thickness: h ~ 95 m

Fig. 4 Surface of the sample T2 = T/(3151 -

Exterior)/ Picea abies smooth surface of the


coating with frequent bubble occurrence;
edges of the bubbles are sharply defined

Acrylics Stabilization of wood surfaces


(Mamoov and Reinprecht 2008)

Microscopic analyses

THICKNESS OF THE
COATING
AFTER
1-YEAR AGEING
[m]
Mean value

thickness of coatings after 1-year ageing

TYPE OF SURFACE TREATMENT WITH ACRYLICS


T1(3151)

T2(3151)

T3(3147)

T4(Interior)

95,53

94,83

87,24

129,10

Standard deviation

7,46

5,67

9,05

9,03

Minimal value

86,29

86,26

75,09

104,5

Maximal value

108,1

103,8

100,1

141,3

10

12

10

13

7,81

5,98

10,37

Object Count
Coefficient of variation
[%]

Acrylics Stabilization of wood surfaces


(Mamoov and Reinprecht 2008)

Colour analyses

differential spectra of acrylics after 1-year ageing

T1 acrylic on larch in exterior


T2, T3 acrylics on spruce in exterior
T4 acrylic on spruce in interior
Pohltivos nterovm systmom [%]

0
350

400

450

500

550

600

650

700

-10

-20

-30

-40

-50

-60

Vlnov dka [nm]


DIF_T1
AVG_DIF_T1

DIF_T2
AVG_DIF_T2

DIF_T3
AVG_DIF_T3

DIF_T4
AVG_DIF_T4

750

Acrylics Stabilization of wood surfaces


(Mamoov and Reinprecht 2008)

Conclusions
Acrylic paints partly penetrated into tracheids of early
wood of coniferous.
Quality of the aged paints valued by their:
- microscopic structure (bubbles, cracks),
- thickness decreases,
- colour changes,

was influenced by more factors:


- the wood species,
- the type of basic paints,
- the interior or exterior exposition.

Acrylics polyacrylates

Conservation of wooden sculptures

Acrylics Conservation of wooden sculptures


(Reinprecht 1991)

Two icons
Lime tree (Tillia sp.)
Polychromy
Length: 620 or 670 mm
Weight: 2 873 or 2 608 g
Damaged by insect galleries

(Anobium punctatum)

and brown-rot

Acrylics Conservation of wooden sculptures


(Reinprecht 1991)

Acrylics Conservation of wooden sculptures


(Reinprecht 1991)

Solakryl BT 55

filing of lumina and creation of films on S3 surfaces of wood cell walls

22,5 % toluene solution

Conservation method

Impregnation: p = 0.6 MPa, t = 20 C, = 90 min

(polybutylmethacrylate)

(1 = 15 min, 2 = 30 min, 3 = 45 min)

Conditioning: = 45 days, t = 20 2 C, = 50 3 %

Acrylics Conservation of wooden sculptures


(Reinprecht 1991)

Retention m (%)

of 22.5 % Solakryl BT 55

into icons

_________________________________________________
1. icon
2. icon
Impregnation:
1 = 15 min
2 = 30 min
3 = 45 min

107.3
133.7
141.0

125.3
137.8
144.3

Conditioning:
15 days
45 days

66.0
36.6

43.6
34.0

Theoretical solids

31.7

32.5

Acrylics Conservation of wooden sculptures


(Reinprecht 1991)

Microscopic analyses
The polyacrylate integrated the wooden spilling dust inside the corridors and prevented it
from falling out, and partially also strengthened the cells damaged with rot.

Acrylics Conservation of wooden sculptures


(Reinprecht 1991)

Conclusions
Polyacrylate (Solakryl BT 55) integrated and
partly strengthened the bio-damaged sculptures
from lime tree.
Evaporation of toluene from conserved sculptures
is a long process it can last 2 months.

References to experiments

Reinprecht L (1991): Retaurovanie pokodenho dreva polyakryltmi, epoxidmi, fenoplatmi a


aminoplastmi. (Restoring of damaged wood with polyacrylates, epoxides, phenoplasts and
aminoplasts) In: Pokroky vo vrobe a pouit lepidiel v drevopriemysle, 10. Sympzium, VLD Zvolen
Czechoslovakia, p. 312-325.
Reinprecht L, Varnska S (1998): Bending properties, compression strength and hardness of wood
modified with synthetic polymers. In: Wood Structure and Properties, 3rd International Symposium,
Arbora Publishers Zvolen Slovakia, p. 157-162.
Reinprecht L, Varnska S (1999): Bending properties of wood after its decay with Coniophora puteana
and subsequent modification with selected chemicals. In: International Research Group on Wood
Preservation, Section 4 Wood Protecting Chemicals, 30th Annual Meeting in Rosenheim - Germany,
IRG/WP/99-40146, 11 p.
Reinprecht L, Tiralov Z, imekov M (2001): Hniloba dreva konzervovanho akryltmi. (The rot of
wood conserved by acrylates). In: Sbornk z konzervtorskho a restaurtorskho semine, esk
Budjovice - Czech Republic, p. 46-49.
Tiralov Z, Reinprecht L (2004): Fungal decay of acrylate treated wood. In: International Research
Group on Wood Preservation, 35th Annual Meeting, Section 3 Wood Protecting Chemicals, Ljubljana
- Slovenia, IRG/WP/04-30357, 7 p.
Mamoov M, Reinprecht L. (2008): truktra a farba akryltovch nterov po ronej expozcii v
exteriri a interiri. (Structure and colour of acrylate coating after inner and outer yearlong
exposition) In: Interaction of Wood with Various Forms of Energy, TU Zvolen - Slovakia, p. 91-97.

Ladislav Reinprecht:
CONSERVATION OF WOOD WITH ACRYLICS - selected experiments

Thank you for your attention

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