7th

INTERNATIONAL CONGRESS ON DETERIORATION AND CONSERVATION OF STONE

PROCEEDINGS
VOLUME 3

--,

Lisbon Portugal, 15- 18 June 1992

Edited by

J. Oelgado Rodrigues fernando Henriques F. Telmo Jeremias

Organized by

_ boratorio Nacional de Engenharia Civil ~ _~='== ~-::::. . ~_ J

CONSERVAMON O FERRUGIN SANDSTMa WED H NORM-WIM DIM" amengat n d

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EDDY DE wi-7E Head f Department, Raayal institute for Cultural Heritage, Jubelpark 1, E-1040 Brussels, Beigi u m KAREL BOS Architect, Royal lnstitute for Culture! Heritage, Jubelpark 1, -1040 russe s, Belgium

SUWMARY The effectiveness of freatments of ferruginous sandstone with c nsolidants based n ethyl silicate and oligomeric methyl siloxanes water repelients w s investigated. Consoiidation is possible by a two or three foid application. Abrasion resistance increases in en import nt way without any negetive influence on the drying r te. Hydraaphobizatien protects ffectively against acid rein and 1ichen growth, but in a minor way against acid atrnosphere. Artificial ageing prove that the treatrnents wilt resist for at least one or twaa decades, but that care should be taken not to apply the hydrophobic agents on stne contai ing saaluble salts.

RSUM On a recherch l'efficacit des traitements du gres ferrugineux par consolidatie n vec des produits base de silicate d'thyle et d'hydrofugation avec des oilgomeres de siloxane de mthyle. La consolidation en deux aau trois traiterrerits successifs donne de bons rsultats. La rsistance l'abrasion augmente d'une maniere importante sans effet ngatif sur !a uitesse de schage, Les hydraafuges protgent efficacement contra pluies acides et les lichens, mais la protection contra ure atm.sphre acide est faible. Des vieillissements artificiels prouvent que les traitements rsisteront au mois me au deux dcennies, mais qu'il ne faudra jamais appliquer des hydrofuges sur d s pi rres qui contiennent des sets solubles.

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1. INTRODUCTION

In a previous paper [1] the quarrying, use and degradation of ferruginous sandstone as historical building material in central and north-east Belgium was discussed. Fresh and aged samples of two formations (Brussels and Diest) have been analyzed and the physical and hygric proporties measured. From the obtained data conclusions could be drawn concerning the resistance to air pollution and frost resistance. In this part the effectiveness of consolidation and hydrophobization of naturally weathered samples is investigated. For the identification of the samples investigated in this work, the same code as published in [1] was used : B : Fresh ferruginous sandstone from the Brussels Formation, originating from the sandpits of Chaumont-Gistoux DF: Fresh ferruginous sandstone from the Diest Formation, originating from the Area of Averbode DO : Recuperated ferruginous sandstone from the Diest Formation. If DF or DO is followed by an index, this refers to a quarry or particular monuments the samples were taken from.
2.CONSERVATION 2.1. Consolidation

The consolidation of the decayed surface of building materials with products based on ethyl silicate is common practice nowadays. It is, however, also known that the chemical composition of the consolidant, the nature of the building material and the application technique play an important role in the final effectiveness. The evaluation in situ of the effectiveness is stilt problematic as most techniques are destructive or difficult to achieve after the restoration of the monument. Therefore, preliminary laboratory investigations can give useful information. 2.1.1. Consolidation of powders. The ultimate state of degradation of a building material is the decomposition into a powder. So whenever the effectiveness of a consolidant or the feasibility of a consolidation has to be investigated, it is common practice in our laboratory to execute tests on powders with a granulometry which is similar to the one obtained by natural ageing. Therefore the granulometric curve of a series of powders, collected on surfaces of monuments, was determined. As can be seen in figure I the degradation material from Brusseliaan and Diestiaan between 53 and 1180 p.m is very similar, except for the region between 125 and 500 p.m, where the fraction for Brusseliaan is considerably higher. For the consolidation tests, naturally aged stone from both formations was crushed and powders with an identical granulometric curve were composed. Plastic molds of 2.5 cm diameter and 5 cm high were then filled with the powder mixture and the bottom was brought in contact with the consolidants, which can then be absorbed by capillary action. The time needed by the consolidant to reach the surface of the powder was measured. After impregnation, all samples were stored in a controlled environment (25 C, 50 % R.H.}. After 24
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h 50 % of samples were treated a second time. This was repeated twice. In this way a series of samples was obtained with 2, 3 and 4 consecutive consolidation treatments. For each application the time necessary to obtain a complete impregnation was noted. The test were executed with two commercial products : STONE CONSOLIDANT OH from Wacker (SOH) and TEGOVAKON V (TEGV) from Goldschmidt. Both are 75 % solutions of a prepolymerized ethylsilicate in either methylethylketon or white spirit and both are catalyzed by an organotin compound. The impregnation time for SOH was 4 minutes for the first impregnation and 15 minutes for each following impregnation. For TEGV the first impregnation took 9 minutes, the following ones 15 minutes. After 4 weeks of hardening the samples were removed from the moulds and if a consolidated block was obtained, the weight increase was measured. As can be seen from table I, successive treatments resulted in weight gain. During the lst treatment, this was of the order of 25 % . A second and a third impregnation resulted each time in an increase of about 10 %, a 4th treatment seemed to have been less effective as only 2 - 4 % material was absorbed. All samples were well consolidated and could be removed as solid blocks. In this way it is proved that solutions of ethylsilicate are potential ferruginous sandstone consolidators. 2.1.2. Consolidation of unaged blocks. The treatment with ethylsilicate changes the capillary structure of a building material as a result of the precipitation of siliciumdioxide gel. The purpose of the treatment is of course to decrease the capillarity of the altered zone in order to obtain a structure which resembles as closely as possible the original material while at the same time leaving the sound stone untouched. In practice this is not always possible and moreover the underlying, sound layer could absorb ethylsilicate. This can result in a harder layer and if this layer slows down the evaporation rate of absorbed water, frost damage could occur. It is difficult to evaluate the influence of such a phenomenon as the determination of physical and/or hygric properties is carried out on inhomogeneous samples. Indeed, in a treated sample one can have following zones : aged and treated; non-aged and treated; non-aged and non-treated. In order to evaluate the influence of a treatment on an unaged sample, some sound samples were completely impregnated with both consolidants and after hardening some physical properties have been measured and compared with blanc samples. As can be seen in table II the porosity accessible to water and the saturation coefficient of all samples decreased after treatment, but the drying rate increased. This enables us to conclude that a treatment with ethylsilicate does increase the resistance of the material against frost damage and that deep impregnations do not have a harmful effect.

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2.1.3. Consolidation of naturally aged samples Samples of naturally aged ferruginous sandstone were collected from different monuments and treated with SOH and TEGV. Both consolidants were applied by spraying the naturally aged surface for 30 seconds. By weighing the samples before and after treatment the consumption was calculated (table III). Depending on the original porosity and the state of degradation the average absorption of ethylsilicate varies between 1100 and 1800 g/m 2 . Extreme values of 650 and 2700 g/m 2 however were measured according to the porosity of the material. When consecutive impregnations were executed, roughly the same amount of product was absorbed each time, but each impregnation took considerably more time than the former. it is also notewortyh that in general the consumption of TEGV is lower than this of SOH. The difference between both products is however less important than the differences noticed between different samples. After 4 weeks of hardening the abrasion resistance was measured and compared with the results before treatment. The same drilt technique as described earlier was used [2]. As can be seen in figure II, a distinct improvement in abrasion resistance was obtained. In untreated samples, the drilt penetrated up to 2 3 cm in the sample after 2000 revolutions. After treatment the penetration was reduced to 2 7 mm. The increase from 2.5 to 7.5 mm between 600 and 700 revolutions for sample DO 4 is due to an extremely soft sandy part at the location where the test was executed. It was established that this method only works well on samples which were not too inhomogeneous to start with. If the stone contains thin layers of limonite alternated with softer sandy parts, it is very difficult to evaluate the effectiveness of a treatment. Each drilltest has to be checked by a visual inspection of the sample. In this case evaluations in situ will be extremely difficult. 2.2. Hydrophobization The treatment of a building material with a water repellent provides a protection against biological and chemical aggression for many years. Two commercial water repellents were applied : Wacker 090 and Tegosivin HL100 (Goldschmidt). Both are methylsiloxanes and have been used in a 7 % concentration in white spirit. The products were applied by spray. By using longer or shorter application times, the impregnation depth was monitored between 2 and 10 mm. The consumption measured during the treatments is listed in table IV. Here as well the consumption of TEGV is slightly lower than that of SOH. One week after the application of the water repellents, the water absorption coefficient (WAC) and drying rate (DR) were measured. The same techniques as described earlier were used. None of the samples absorbed any water during the 15 minutes of measurement. The DR however dramatically decreased in all cases, as shown in table V. 3. ARTIFICIAL AGEING In order to evaluate the long term effectiveness and eventually negative effects of the treatments, a series of
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artificial ageing tests was carried out. 3.1. Lichen It is known that lichen growth can damage building materials. As, however, lichen grow very slowly and only in well defined climatic conditions, specific for each species, artificial ageing testing becomes extremely difficult. Therefore stone samples were treated with a number of products secreted by lichen and commercially available. A small amount (0.03-0.09 g) of following products were applied on non-treated and on hydrophobized samples of 50 x 50 x 6 mm : B-sitosterol, adonitol, vulpinic acid, D-manitol, usnic acid, lichenan and oxalic acid. After application of the products, they were covered with a few drops of distilled water and then the samples were placed in closed containers in which the R.H. was kept constant at 95 % . After 60 days following effects were registered : - B-sisterol and adonitol did not cause any visible damage. The untreated samples, however, were completely covered by a white fungus, the treated ones were intact. This phenomenon was exclusively linked to these products. - Lichenan caused minute brown chips to detach from both the treated and untreated samples. - D-mannitol recrystallized into very large crystals on the surface of both samples without causing any damage. As this product is secreted in nature underneath the surface of the substratum, the formation of large crystals could cause damage to the rock. - Usnic acid and vulpinic acid did not show any visible damage. An SEM investigation, however, showed the etching of the grains by usnic acid and the formation of small crystals in the pores of the samples treated with usnic acid. - Oxalic acid caused a dramatic deterioration of the samples (fig. III). Especially the treated Brusseliaan samples showed a distinct discoloration, which also occurred in the other samples, although less marked. 3.2. Acid rain Hydrophobized and untreated samples with an average surface area of 0.00663 m 2 were soaked in a sulfuric acid solution of pH 2. After 7 hours the samples were rinsed with distilled water, dried for 17 hours at 60 C and weighed. The cycle was repeated 28 times. During the first hours of the test all samples show a remarkable weight loss, which decreases drastically after 7 hours. From the graph weight loss versus time the protection of water repellents against liquid acids can be calculated. The results are represented in figures IV and V. In the first phase, the weight loss of the treated samples was 30-50 % of the untreated samples. Later, the difference became even more pronounced : the weight loss of the treated samples was only 10 % in comparison with the treated ones. This means that although there is an important difference between the treated and untreated samples, the use of a water repellent does not completely stop the action of acid.
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3.3. Acid atmosphere Samples were exposed to an atmosphere with a R.H. of 95 % and loaded with 0.6 % of SO 2 gas. A cycle of 7 hours of exposure followed by 17 hours of non exposure was repeated 28 times. After this period samples B showed a marked color-change with noticeable corrosion and obvious crumbling of the surface. Samples DF showed some decay as well, although less dramatic. The untreated samples DO hardly showed any damage at all. Striking but in concordante with [3] is the fact that the treated samples showed more damage than the untreated ones. The reason for this can be that, unlike acid rain, the SO 2 gas as well as the water vapor penetrates the stone. During the drying period of the cycle, water as well as dissolved gas can evaporate from the untreated samples, while both are tapped in the treated ones. As a consequence, contact of the stone matrix with acidity is much langer for treated than for untreated samples. 3.4. Salt crystallization test In order to establish the resistance of ferruginous sandstone to salt crystallization and to control the effect of consolidants and water repellents on the crystallization resistance, tests were carried out with sodium sulphate, sodium chloride and potassium nitrate solutions. Cubic samples of 5 cm edge were placed with one side in a 0.345 mole/1 solution of the three salts. For the treated samples, care was taken that the treated surface was faced upwards. All space between the samples and the side of the box was thcroughly closed off with polystyrene in such a way that the evaporation of the water could only occur through the upper surface of the samples. The boxes were placed in an oven at 40 C for a period of 28 days. Every 7 days the samples were removed from the test boxes, the efflorescence washed off and the damage recorded. In the case of Na 2 SO4 the untreated samples withstood the test quite well, although some etching of the surface occurred. Exception has to be made for some soft samples of DO, which were further eroded. The samples treated with consolidants did not suffer any appreciable damage, except for a reddish discoloration probably due to a reaction of the salts with the consolidants. The samples treated with water repellents all showed important damage. In most cases the hydrophobic layer was completely exfoliated. Samples of type B seemed to resist slightly better than DO samples, although it is obvious that the occurrence of damage is rather a question of time than of chemical/physical properties. In the case of NaCl none of the untreated samples suffered any damage. On samples of type B the hydrophobic layer was never exfoliated, but the surface showed a distinct etching comparable to the damage noticed on untreated samples exposed to the sulphate test. All surfaces of samples DF and DO were badly damaged and several partially exfoliated. On all consolidated surfaces only minimal dusting could be observed. With KNO 3 the control as well as the consolidated samples did not show any damage. The hydrophobic layers were slightly altered, although no exfoliation was visible.
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3.5. Freeze-thaw test To assess the durability of treated and untreated ferruginous sandstone samples were submitted to a freeze-thaw test. The specimens were placed in a box, lined with 4 cm of polystyrene and filled with wet sand. The samples were placed in such a way that evaporation of water and frost attack could only occur through the one exposed surface. The boxer were placed in a climatic chamber and exposed to a cycle of 15 hours 10 C followed by 9 hours of 15 C and 95 % R.H. After 42 cycles half of the samples as well as a series of new ones were soaked for 8 hours in a 6.17 % solution of sodium sulfate. Then the frost-thaw test was continued for another 42 cycles. A visual inspection of the samples lead to the following conclusions : - After the first 42 cycles, no important damage could be recorded for any of the samples, although some softer parts of type DF and DO showed some erosion. This confirms our earlier findings that the ferruginous sandstone is frost resistant. - After 84 cycles, the untreated samples not saturated with sulfates as well as the samples of type B saturated with sulfates resisted well. The softer parts of samples of type DF and DO saturated with salts deteriorated somewhat more. In some cases samples treated with water repellents suffered extensively. This was mainly the case for samples DF as well as those samples where a deep impregnation (up to 20 mm) was achieved. In some cases the stone under the hydrophobized layer was completely destroyed. Samples treated with consolidant suffered more from the freeze-thaw test when sulfates were present. In contrast to the hydrophobized samples however there seemed to have beeen no major influence of the impregnation depth and the consolidated layer never split off. Damage always occurred in the lower part of the stone where no consolidant was present. 3.6. Weather-OMeter ageing Treated and untreated samples were exposed to an accelerated weathering cycle in an Atlas Weather-OMeter XR35 for 813 hours. The cycle consisted of : - 6 hours of exposure to - Xe-light (0.25W/m 2 /Nm at 340Nm) - 45 C and 20 % R.H. - 6 hours of exposure to - Xe-light (0.25W/m 2 /Nm at 340Nm) - 20 C and rain (spray of deionized water) The WAC was measured every 168 hours after drying the samples till constant weight at 60 C. Except for 2 samples on which only a small amount of water repellent was applied (less than 120 g/m 2 ), none of the samples showed any water absorption during or after the test. Earlier tests [41 had proven that under these ageing conditions a lifetime of 15 - 20 years can be expected.
4. REPLACEMENT

When the building material is so badly damaged that structural problems occur or that sculptured forms have lost all their meaning or even disfigure the monument, replacement has to be considered.
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It is obvious that as far as possible the same material as the original should be used. As, however, the economie growth of the Netherlands in the 16th century did not affect the region where ferruginous sandstone was traditionally used, a halt in construction activity occurred, resulting in a complete loss of the tradition to use this local building material. This was true to such an extend that, when restoration campaigns were launched again in the second half of the 19th century, sandstone from the Vosges was imported to replace the local ironstone. This pink colored sandstone does not match the original material and is still clearly distinguishable (fig. V). Even today the availability of ferruginous sandstone causes problems and most contractors have to resort to using salvageable stone from demolished buildings. Only one source of restoration material is available nowadays : the sandpits of Chaumont-Gistoux and Sart-Moulin. Larger quantities of Brusseliaan are available but the quality is very inhomogeneous and variable and because of the more even structure and purple hue, due to higher manganese content, it remains distinguishable from the original Dieststone. As the several quarries of this Diestiaan were closed in the 16th century not because of lack of stone but because of lack of demand, it is quite certain that considerable quantities of this building material are still hidden in the region of NE Brabant. A thorough exploration of the region and a feasibility study for the reopening of old quarries is advisable. 3. CONCLUSION Ethyl silicate based products prove to be very effective for the consolidation of ferruginous sandstone. Two to three consecutive applications result in a consumption of 3.5 to 5 1/m 2 , depending on the state of degradation of the stone and the product used. Such treatment results in an important increase in abrasion resistance, without negative effects on the drying speed. Hydrophobization can effectively be achieved with 7 % solutions in white spirit of oligomeric methylsiloxanes. Consumptions between 0.20 and 1.7 1/m 2 can be expected. Artificial ageing tests prove that the hydrophobization gives an excellent protection against degradation by lichen and acid rain, but not against acid atmosphere. Ferruginous sandstone containing soluble salts can be consolidated but should never be treated with a water repellent, as this will induce the splitting off of the impregnated layer or at least increase the surface degradation. For the replacement of structurally unstable stone it would be worthwhile to launch a exploration program for the reopening of old quarries.

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REFERENCES

1. BOS, K. and DE WITTE, E. - Use and deterioration of ferruginous sandstone in Northern Belgium. This edition. 2. NISHIURA, T and DE WITTE, E. - Drill-boring tests for the detection of the deterioration and consolidation effect. Scientific Papers on Japanese Antiquities and Art Craft, Vol. 30, 1985, pp. 11-14 3. SRAMEK, J. and PERINA, V. - Sensitive evaluation of the conservation efficiency of materials used for the treatment of stone. Vth Int. Congress on Deterioration and Conservation of Stone, Lausanne 25-27.9.85, pp. 553-560 4. PIEN, A. - Technique de controle du traitement des matriaux pierreux in situ. The Deterioration of Building Materials, Ed. F. Auger, La Rochelle, 1990, pp. 69-77

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Table I : Consolidation of powders Absorbed quantity of consolidant (weight %)

1

2x 7.5 8.4 5.6

3x 7.8 11.9 7.0

4x 2.6 2.5 4.3

Total 45.2 50.4 44.2

B DF DO

23.7 27.6 27.3

Weight increase after complete hartlening (weight %) 1x B DF DO 9.3 9.5 9.7 2x 12.7 12.4 10.9 3x 13.6 14.3 12.8 4x 15.7 15.6 13.8

B : non aged samples from the Brussels formation DF : non aged samples from the Diest formation, DO : naturally aged samples from the Diest formation (collected from monuments)

Table II : Physical propertjes of untreated and completely impregnated samples 111111~1111111111111111111U.77 WP B B* DF 2 DF 2 * DF 3 DF 3 * 24.8 20.1 30.2 24.2 27.9 22.5 BD 2796 2717 2723 2607 1805 2695 RD 2120 2171 1900 1977 2021 2088 S 67 62 72 71 73 70 DR 506 585 492 653 300 578

* : treated samples WP(%) Porosity accessible to water (RILEM I.1) BD (kg/m 3 ) : Bulk density (RILEM I.2) RD (kg/m 3 ) : Real density (RILEM 1.2) S (%) : Saturation coefficient (RILEM II.1) DR : Drying Rate (1/m 2 .h)

112 2

Table III : Consumption of consolidants by naturally aged samples Absorbed quantity of consolidant/treatment (g/m 2 ) TEGV SOH lx DO x 1142 DO Y 1149 1354 DO x DO Y 1686 2x 1140 1392 1397 1689 3x 1116 1394 1395 1616 4x 1229 1105 1299 1781

Cumulative absorbed quantity of consolidant (g/m 2 ) TEGV DO x DO Y SOH DO DO y lx 1142 1149 1354 1686 2x 2282 2541 2751 3375 3x 3398 3940 4146 4991 4x 4917 5045 5445 6772

DO x Average value of a series of samples from 1 monument DO : Average value of a series of samples from 1 monument, other than Dx

Table IV : Consumption of water repellents in g/m 2 TEGOSIVIN HL100 ID : B DF DO 2 mm 188 103 316 132 242 23 5 mm 241 33 593 79 336 30 10 mm 849 182 1071 312 606 168

WACKER 090 ID : B DE DO 2 mm 316 97 444 163 256 30 5 mm 303 38 673 127 397 73 10 mm 716 137 1698 312 707 106

ID : impregnation depth

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Table V : Water absorption and drying rate before and after treatment WAC 1 BR DF 1 DF 2 DO x DO 1.5 ml (10') (4'10")

WAC 2 * * *
1

WAC 3 0 0 0
0

DR 1 DR 2 480 320 420 364 441 * * * 234 472

DR 3 66 45 82 60 191

ID 7-20 10-20 60-70 4-7 5-20

(3'50")

WAC 1 : Water absorption before treatment WAC2 : Water absorption after consolidation WAC 3 : Water absorption after consolidation and hydrophobization DR 1 : Drying rate (g/m 2 .h) before treatment DR 2 : Drying rate (g/m 2 .h) after consolidation DR3 : Drying rate (g/m 2 .h) after consolidation and hydrophobization ID : impregnation depth of water repellent : no measurement possible because of sandy surface : not measured, as samples were not consolidated

3.5

2-5 -

0.5 I- 0 ZCD <53 63 125 90 180 250 355 Siev4 500 600 710 1000
1180

400 600

800 12 '00 1600 2000 1400 1000 1800 Hurrher of revoluflore

53

2000

Figure I : Granulometry of powders collected on monuments (naturally decayed stone) BR : Brussels formation DST Diest formation

Figure II : Abrasion resistance of untreated and treated samples : A : D0 3 , untreated B : D0 3 , consolidated C : D04 , untreated D : DO4, consolidated

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90 80 70

2 e460
E 1,5c1

1.

40 30 20

Of

DC

oc

Figure III : Weight loss by acid solution (0 - 7 h) left : untreated middle : Wacker 090 right : Tegosivin HL700

Figure IV : Weight loss by acid sol. (7-200 h) left untreated middle : Wacker 090 right : HL100

Figure V : Diest, St. Sulpicius. The lighter parts are restorations with sandstone from the Vosges.

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