Disinfection and consolidation by irradiation of wooden samples from three Romanian churches

Mihalis Cutrubinis1, Khôi Tran2, Eugen Bratu1, Loic Caillat2, Daniel Negut1 and Gheorghe Niculescu3 IRASM Irradiation Technology Center, “Horia Hulubei” National Institute for Physics and Nuclear Engineering, Magurele-Bucharest, Romania 2 Regional Conservation Workshop - Nucléart, Atomic Energy Commission, Grenoble, France 3 National Institute of Research for Conservation and Restoration of National Movable Cultural Heritage, Bucharest, Romania Abstract Studies on application of ionizing radiation for disinfection and consolidation have revealed that wood objects, lacquer, textiles, paper, objects made of stone and gypsum can be considered for conservation purposes. In this work, first were assessed the biodeterioration factors (insects and moulds) and their effects, and properties of wooden samples from three Romanian churches. After treatment, the properties of the impregnated samples were assessed in order to prove that the gamma irradiation process brings a real improvement in wood condition, in terms of disinfection and structure consolidation. As conclusion, the irradiation treatment is considered proper to be applied to different wooden cultural heritage objects only for their disinfection or both for their disinfection and consolidation.
1

1. INTRODUCTION
Disinfection and conservation of archaeological artifacts and art objects by radiation treatment (gamma rays or electron beam) appears to have perspective. Studies on application of ionizing radiation for consolidation have revealed that wood objects, lacquer, textiles, paper, objects made of stone and gypsum can be considered for conservation purposes. Radiation treatment of cellulose materials for disinfection is well known and proven. Additional extensive research is needed to develop treatment methods to lower the radiation dose (1). The susceptibility to the microbial attack of wood is depending on its moisture content. Microbial deterioration, operated mainly by moulds, can start when the water content is above 20%. These can develop on surface or within internal structures inducing, through the production of exoenzymes, change in cell integrity. The role of bacteria and actinomycetes in deterioration of wood is less important because they require higher water content. They have been found mainly in outdoor and marine environments. Insects, however, are the most serious source of damage for wooden objects kept in museums, in indoor or outdoor environments. They use wood as a nutrient source, for shelter and egg deposit. In feeding, some insects utilize only the compounds obtained from the cell contents (sugars and starch) while others utilize even the cellulose. Waterlogged wood is the term used to describe wood kept under wet soil or water, for example archaeological wood such as shipwrecks or pile-dwellings. Under these particular conditions (high water content and lowered oxygen pressure), wood can easily be attacked by microaerophilic and anaerobic heterotrophic microorganisms and, in sea sites, by some marine organisms (2). Gamma rays, a form of electromagnetic radiation, are extensively used for sterilizing micro flora and killing insects, especially on organic materials. A dose of at least 500 Gy is required to kill larvae and to prevent the emergence of adult insects. Moulds are less sensitive to ionizing radiation than insects, and different strains show different levels of sensitivity. Generally most fungi are killed by a total dose of 10 kGy (3). Despite its power, gamma irradiation does not induce any secondary radioactivity and penetrates completely into the objects. Moreover, a large quantity of materials can be treated at one time. Gamma rays have also been employed for the polymerization of resins used to consolidate decayed wooden objects by impregnation. For the complete polymerization of the resin, the requested dose is about 20-30 kGy. Radiation polymerization has a great advantage over conventional polymerization by chemical catalysts as the heat rise can be perfectly controlled by varying the radiation dose rate.

The other advantage of radiation polymerization is that the excess resin from an impregnation can be reused, due to the absence of chemical catalysts in the resin storage. The disadvantage of this consolidation treatment in comparison to other consolidation methods of cultural heritage objects is that the process is not reversible. However, it can save from destruction artifacts which present a very high degree of deterioration (4).

2. MATERIALS AND METHODS
Samples. There were studied wooden samples from three Romanian churches: A. piece from wooden ceiling of an evangelical church in Sibiu county, B. piece of sycamore maple from resistance structure of an orthodox wooden church, C. piece of fir from resistance structure of an orthodox wooden church in Dretea, Cluj county, which was build in 1690, painted in 1770 and now is rebuild at “Astra” Traditional Civilization Museum in Sibiu. Treatment. The consolidation of the studied samples was carried out using a standard resin of styreneunsaturated polyester type tetrahydrophtalic. The samples were treated at the irradiation facility of Regional Conservation Workshop Nucléart (ARC-Nucléart), using a gamma source of Co-60. The irradiation was done at room temperature in open air. The delivered mean irradiation dose was about 24 kGy, enough to disinfect the samples from insects and moulds, and consolidate them through polymerization of the resin. The irradiation dose rate was set up as to not exceed a polymerization temperature of 50-60 °C. After treatment, different properties of the impregnated samples were assessed in order to prove that the gamma irradiation process brings a real improvement in wood condition, in terms of disinfection and structure consolidation. Characterization and testing. First were assessed the biodeterioration factors (insects and moulds) and their effects. Using a photo camera and a stereomicroscope, were taken pictures before and after treatment and assessed the biodeterioration factors (insects and moulds) and their effects on wooden samples. Samples were also weighed before and after consolidation treatment. A HunterLab Miniscan XE Plus portable spectrophotometer has been used for colour measurements. The geometry of measurement is d/8° with a view area of 6 mm in diameter, specular component is included, combination illuminant - standard observer is D65/10°. All values are reported in CIELAB and CIELCh colour spaces. Every value is obtained averaging 30 measurements. Mechanical testing has been carried out using Zwick / Roell equipments. For dynamical test (impact test) has been used a Zwick / Roell Pendulum model 5113. The test parameters were: pendulum of 25 J, Charpy impact test, distance between sample holders 35 mm, impact speed 3.85 m/s and angle of pendulum launching 160°. Through Charpy impact test has been measured the impact energy E (J). For statically tests (penetration and bending) it has been used a Zwick / Roell Universal Testing Device model Z005. The penetration test has measured the force F (N) necessary to push 1 mm in the sample a metallic ball of 6 mm diameter. The bending test has measured the bending tensile strength σ (MPa) necessary to bend 2 mm a sample. The distance between sample holders was 60 mm. For electron spin resonance (ESR) testing was used a Magnettech Miniscan MS200 X band spectrometer. The measurement parameters were: Microwave radiation – 9,3-9,6 GHz, Power – 0.8 mW, Centre field – 335 mT, Sweep width – 15 mT, Modulation amplitude – 0.5 mT, Sweep time – 60 s, Steps – 4096, Pass number – 5, Temperature – room temperature. Gain varied according to the signal intensity of the measured sample. A single signal (gsymm=2,004) is observed in the ESR spectra of all samples containing cellulose, including unirradiated samples. In the case of irradiated samples, the intensity of this signal is usually much greater. The intensity of signal is proportional with the quantity of cellulose free radicals present in the sample.

3. RESULTS AND DISCUSSION
At examination of samples with a stereomicroscope there were established the biodeterioration factors taking relevant pictures of samples. After impregnation treatment there were taken pictures of treated samples in order to evaluate the consolidation treatment. In Figure 1 there are presented different pictures taken from samples before and after consolidation treatment.

Figure 1. Pictures of samples for biodeterioration assessment and consolidation evaluation

The samples have been weighed before and after consolidation treatment. Table 1 shows their masses. It can be seen from the table that sample A increased its weight more than 3 times, samples B almost doubled their mass and samples C had more than double mass.

Table 1. Masses of samples before and after consolidation treatment

Before After

A2 22.0 73.6

B2 11.6 20.2

B4 10.3 17.5

Mass of samples (g) B5 C2 79.6 109.4 140.4 245.5

C4 71.1 167.9

C7 95.7 200.7

C9 91.9 210.3

In Figure 2 there are presented pictures of samples before and after impregnation treatment. It can be seen easy the color change of samples.

A before

A after

B before

B after

C before C after Figure 2. Pictures of samples before and after impregnation treatment

As can be seen from the Table 2, for the colorimetric measurements all samples showed a decrease in lightness (L*) after treatment. The colour differences between untreated and treated samples are strong and visible. Sample A became less red and less yellow after treatment, this means a significant decrease in chroma (C*) and a strong variation in hue (h). Sample B became redder and yellower after treatment, this corresponding to a small increase in chroma and a strong variation in hue. For sample C, only a decrease in b* (less yellow) value can be observed that corresponds to a decrease in chroma and a small variation of hue.
Table 2. Colour values of untreated and treated wood samples

sample L* A B C
39.21 60.81 54.55

a*
4.47 7.47 12.70

untreated b* C*
13.71 21.77 31.01 14.42 23.02 33.51

h
71.95 71.06 67.72

L*
23.81 44.69 42.29

a*
3.51 13.21 12.14

treated b*
6.19 22.71 26.14

C*
7.11 26.27 28.82

h
60.48 59.81 65.10

dE*
17.16 17.14 13.20

Mechanical tests have been carried out in order to prove the mechanical properties improvements brought by impregnation. After applying Charpy test it can be said that no improvement has been noticed because of consolidation treatment. More of this, only consolidated sample A kept its impact resistance, samples B and C lost some of their impact resistance. This means that the wood fiber impregnated with styrene resin is equal or lees resistant at impact.
1000

800

Consolidated A samples 10 times more resistant

600 Stress in N 400 200

Non-consolidated A samples
0 0,0 0,2 0,4 0,6 Compression in mm 0,8 1,0

2000

Consolidated B samples 4 times more resistant
1500 Stress in N 1000 500

Non-consolidated B samples
0 0,0 0,2 0,4 0,6 Compression in mm 0,8 1,0

2500

Consolidated C samples 8 times more resistant

2000

Stress in N

1500

1000

500

Non-consolidated C samples
0 0,0 0,2 0,4 0,6 Compression in mm 0,8 1,0

Figure 3. Diagrams for application of penetration test

In Figure 3 there are shown the diagrams for penetration test applied at sets of consolidated and nonconsolidated samples. From all above diagrams it can be noticed that the consolidated samples have higher resistance to penetration in comparison with the non-consolidated samples. This means that the wood fiber impregnated with styrene resin is more resistant at penetration.

20

Consolidated A samples
15 Stress in MPa

10

5

Non-consolidated A samples

0 0,0 0,5 1,0 Strain in mm 1,5 2,0

14

12

Consolidated B samples

10

Stress in MPa

8

6

4

2

Non-consolidated B samples
0,0 0,5 1,0 1,5 Nominal strain in mm 2,0

0

150

Consolidated C samples
100

Stress in MPa

Non-consolidated C samples
50

0 0,0 0,5 1,0 Strain in mm 1,5 2,0

Figure 4. Diagrams for application of bending test

In Figure 4 there are shown the diagrams for bending test applied at sets of consolidated and nonconsolidated samples. From all above diagrams it can be noticed that the consolidated samples have higher resistance (about 2-3 times) to bending in comparison with the non-consolidated samples. It can be also noticed that consolidated samples crush faster than non-consolidated samples after the appearance of first small crushes in their structure. This means that the wood fiber impregnated with styrene resin is more resistant at bending and after the appearance of first small crushes in structure the flow to total crush is short. The presence of any free radical in an object gives a potential risk of its damage. Objects containing cellulose have natural free radicals. Irradiation treatment induces in any object free radicals and their persistence could constitute a damage risk. Considering these facts, the intensity of ESR signal of cellulose free radicals it has been used in order to evaluate the potential risk of damage for consolidated and non-consolidated samples. In order to be able to compare them, the intensities were brought at same gain. As can be seen in Table 3, the treated samples have shown three months after treatment about half intensity per mass unit of the untreated sample. Five months after treatment the intensity per mass unit for treated samples was higher than that after three months but lied between half and one third of the untreated samples. This shows that in addition to consolidation effect, the impregnation with the styrene resin has also a protective effect against natural cellulose free radicals.

Table 3. Semnal RES

Sample

A untreated A treated B untreated B treated C untreated C treated

Three months after treatment Intensity (a.u.) Mass normated intesity 54738 1766 78894 974 85968 1719 58059 907 39149 1223 97551 938

Five months after treatment Intensity (a.u.) Mass normated intesity 104859 3383 133497 1648 198648 3973 92979 1453 112194 3506 126054 1212

4. CONCLUSIONS
The delivered dose of 24 kGy was more than enough to disinfect the studied samples from insects and moulds. In addition, this dose is very close to the usual dose used for sterilization. So, after treatment the samples were almost sterile. Using this irradiation dose for disinfection, proper packaging of samples and post-irradiation handling procedures of them, after the disinfection treatment the conservator can seal first a totally clean object of biodeterioration factors, and after that proceed to its restoration. Irradiation doses up to 10 kGy can be used for prevention from the action of different biodeterioration factors or for first step of remediation treatment. In case of consolidation by impregnation with styrene resin, the wooden object becomes heavier and more resistant at penetration and bending. The treated object contains less free radicals than the untreated one. Also, the object changes its colour, generally getting darker, and does not get better impact resistance. When a conservator considers that disadvantages such application of a nonreversible consolidation treatment, darker colour and less impact resistance are not of crucial importance for a certain cultural heritage object then this treatment method can be a very good choice. As a general conclusion, the irradiation treatment is considered proper to be applied to different wooden cultural heritage objects only for their disinfection (as prevention treatment or as first step of remediation treatment aiming at conservation) or both for their disinfection and consolidation (as remediation treatment aiming at conservation).

5. ACKNOWLEDGEMENTS
The authors would like to thank COST Action IE0601 for the opportunity for collaboration given to them through the STSM of Dr. Mihalis Cutrubinis at ARC-Nucléart Grenoble, France and Romanian National Authority for Scientific Research for the economic support of scientific work.

6. REFERENCES
1. IAEA, 2003. Report from a technical meeting; emerging applications of radiation processing for st 21 century. Vienna, Austria. 2. Tiano P., 2002. Biodegradation of Cultural Heritage: Decay Mechanisms and Control Methods. Proceedings of ARIADNE Workshop 9 – Historic materials and their diagnostics, February 4-10. 3. Diehl J. F., 1996. Biological efects of ionizing radiation in Safety of irradiated food. Ed. Marcel Dekker Inc., New York, USA. 4. Ramiere R. and Tran K. Q., 1989. Nucleart: Nuclear Techniques Applied to Art. Nuclear Europe, 7:50.

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