CONSTRUCTION USES
STONE, CONSERVATION
ERHARD M. WINKLER
The rapid decay and disfiguring of stone monuments in urban
and desert rural areas has challenged conservators to protect stone
surfaces from premature decay. They attempt to halt the natural
process of stone decay and possibly to restore the original strength
lost mostly by chemical weathering and the loss of binding cement.
Ageneral solution is not possible because the physical and chemical
characteristics must be considered for different stone types. The
failures of stone preservation and restoration are greater in number
than the cures. The need for repair of stone decay goes back to
evidence of Roman replacement of decaying stone.
The presence of excess water in buildings has long been rec-
ognized. Moisture tends to enter masonry from air in humid cli-
mates, a most important but often underrated factor (Fig. 1) sug-
gesting that sealing should be the answer. Undesirable staining and
efflorescence result in accelerated scaling. Today, the great variety
of chemicals available to the modem conservator for sealing. con-
solidating, or hardening stone fall into two very different categories:
surface sealers and penetrating stone consolidants, or a combination
of both.
SEALERS
Sealers develop a tight, impervious skin which prevents access
of moisture. Surface sealing has saved monuments from decay by
eliminating the access of atmospheric humidity. Pressure tends to
develop behind the stone surface by moisture escape. Efflorescence,
crystal growth action, and freezing can cause considerable spalling
(Anderegg, 1949). Flaking results when moisture is trapped behind
the sealed surface. Yellowing and blotchiness are also frequently
observed.
The following sealants are in common use today: linseed oil,
paraffin, silicone, urethane, acrylate, and animal blood on stone and
adobe. Extensive cracking and yellowing has resulted soon after
application. In the past many such treatments have created more
problems than cures:
1. Linseed oil and paraffin have been in use for centuries. Em-
brittlement and yellowing occur rapidly because these are
readily attacked by solar ultraviolet radiation.
2. Animal blood as paint has temporarily waterproofed adobe
mud and stone masonry. The origin of blood paint has a reli-
gious background rooted in the Phoenician and Hebrew cul-
tures. Instant water soluble dried blood can substitute for fresh
blood. Winkler (1956) described the history and technique of
the use of blood.
3. Silicones have proven very effective and are long lasting. In
contrast, acrylates, urethane, and styrene are generally rapidly
attacked by UV radiation (Clark et al., 1975).
Sealing of Different Rock Types
Granitic rocks have a natural porosity traced to 4.5% contrac-
tion of quartz, during cooling of the parent magma, compared with
only 2% contraction of all other minerals; protection against the
hygric forces may require waterproofing of granite in some in-
stances. The Egyptian granite obelisk in London is an example.
Soon after its relocation from Egypt to London, Cleopatra's Needle
was treated, in 1879, with a mixture of Damar resin and wax
dissolved in clear petroleum spirit; surface scaling became evident
after half a year of exposure to the humid London atmosphere. The
treatment of the ancient granite monument from Egypt has denied
access of high relative humidity (RH) in London to the trapped salts
inherited from the Egyptian desert and has protected the monument
from decay (Burgess and Schaffer, 1952). The sister obelisk set up
in Central Park, New York City, has fared less favorably because
similar treatment was done too late, only after the salts hydrated and
hundreds of kilograms of scalings disfigured the obelisk surface
(Winkler, 1980). Surface coating of other common stones may be
needed.
Crystalline marble absorbs moisture from high RH atmo-
s~heres:dilation mav ensue when curtain ~ a n e l sbow as the mois-
&re s t k s to expani during daily heating:cooling cycles. A good
sealer may prevent the moisture influx provided that no moisture
can enter from the inside of the building.
Limestones, dolomites and all carbonate rocks are subject
to dissolution attack by rainwater, especially in areas where acid
rain prevails (Fig. 2). The interaction of sulfates in the atmo-
sphere with the stone can be halted by waterproofing to avoid the
formation of soft and more soluble gypsum. The stone surface
attack can be diminished if nearly insoluble Ca-sulfite crusts can
form, instead of Ca-sulfate. Replacement of fluorite or barium
compounds at the stone surface acts as a hardener, rather than a
sealant.
Sandstones have generally high porosity and rapid water travel
can occur along unexpected routes and from any direction. Any
surface sealing may do more damage by scaling and bursting than
if the stone is left without treatment. Sealing of sandstones is
therefore not advised at any time.
Testing the efficiency of sealants: Several authors discuss
waterproofing materials, silicones, urethanes, acrylates and stear-
ates, as to their water absorption, spreading rates of water on the
treated surface, water vapor transmission, resistance to efflores-
cence, and general appearance (Clark et al., 1975). De Castro (1983)
measured the angle of contact of a microdrop (0.004 cm3) on a stone
surface as characteristic of the wettability. Laboratory tests and
limited field performance are described by Heiman (1981). The
crest of a Gothic sandstone arch, which was sealed with silicone,
360 INDUSTRIAL MINERALS AND ROCKS
Masonry Wall CONSOLIDANTS
Time of Wetness (%)
A

0
-
0
T
0
U O
0
P
0
V
0
I O
0
)
0
- J
0
O
0
~
0
W O Stone Consolidation (Table I), a method to replace natural
grain cement lost by weathering from the stone, has been practiced
since Roman times. Treatment with waxes, linseed oil, and lime-
I - water were in use for many centuries, but lasting cures were not
obtained. The chemical industry has developed a large variety of a
I - few inorganic and many organic chemical compounds to strengthen
stone with little or no visual disturbance and high effectiveness. It
I - should be clearly distinguished between a mere filler of stone pores
and filler-strengtheners. Inorganic and organic strengtheners are
summarized by Clifton (1980), Snethlage (1984) and Koblischek
(1985). Wihr (1980) compiled practical methods of treatment with
chemicals in his field handbook for conservators and stone masons.

Inorganic Consolidants

The introduction of inorganic solutions into crumbling stone,

I - mostly sandstones and limestones, to replace substances lost by
weathering is a natural and logical method. The following chem-
I -
icals are in use today, often with limited success: water of lime,
w,
pozzolan-cements, silica as waterglasses, fluates, and baryte water.
I -
0 Lime: The limewater technique is the oldest and most natural
method to restore calcitic stone. Caroe (1987) describes the history
of limewater treatment on the sculptures of 13th century Wells
VI
A
0
A
VI
Cathedral carved on porous Doulting limestone. The soft stone soon
required renovation on which the burnt lime technique was applied,
Approx. Water Content (~01.%) and which has been improved through the centuries. Price (1984)
in experimented with limewater by applying freshly burnt lime as
Porous Masonry Wall paste held firmly against the stone surface with sacking, a technique
commonly used during the Middle Ages. The decaying statues
~ i1. ~ ~~~~~~i~~~~
. water content by moisture absorbed as above the main church entrance of Wells Cathedral in England were
a function of the relative humidity and a similar curve of the the focus of this method. Price found an increase in strength despite
tirne of wetnessin a porous masonry wall. D~~~adapted from the repetition of the process while the surface remained moist during
Voss and Tammes (1968). the time of treatment. The failure of the limewater method, explains
Gutschick (1988) is the slow rate of calcification. For instance, lime
mortars applied during the Roman period have not all reverted to
calcite. The limited solubility of burnt lime in water (18 mgh
Ca(OH),) is another inefficiency. Calcite has a similar solubility
which can be increased by a factor of 10 by the introduction of CO,
in the presence of 15% CO, (Fig. 2). A concentration of 100 to
200 mgn of CaCO, makes calcite precipitation possible, when CO,
is lost from the solution and the pH is controlled (Fig. 2), and is
similar to natural diagenetic processes.
Fluates: The replacement of the carbonates, such as limestone,
dolostone, and crystalline marble, by colorless fluorite (CaF,), is
reviewed by Kessler (1983). The process was developed about 90
years ago. The newly formed mineral fluorite is virtually insoluble
in rainwater through the entire pH range, in contrast to the limited
water solubility of calcite. Volume by volume replacement of cal-
cite by fluorite, a well documented natural geological process, may
take thousands of years or longer and may form a gray surface.
Barytization: Replacement of soluble carbonates with nearly
100 insoluble BaCO, in the presence of urea as a catalyst, has been
developed and field tested by Bear and Lewin (1970). It yields
Fig. 2. Saturation diagram for Calcite in water of different C 0 2 decreased solubility increased surface and near-surface hard-
Content and temperature. Saturation equilibria are drawn for ,,ing of the exchanged mineral material. The slow reaction rate and
rural, urban, urban industrial and soil atmospheres. Adapted change of color make this process impractical.
from Winkler (1987). Silica as Waterglass: The dissolution of silica in pure water
depends on the pH, the temperature of the solvent, and on the degree
of crystallinity (Fig. 3). Yet, pure SiO, introduction has not been
successful although silica can be readily introduced as waterglasses
illustrates spalling due to trapped salts. Sealing should be only (Table 2).
advised in special cases where no moisture can enter from anywhere The introduction of silica into crumbling quartz sandstones to
behind the treated surface or surfaces. replace the grain cement was first attempted 150 years ago with
 STONE, CONSERVATION 361
Table 1. Summary of Consolidants
Chemical Binds to Penetration Solvent Discoloring Crusts
A) Inorganic:
1) fluoric acid fluates limited water graying -
fluorite
CaCO,+ MgSiF, 4 6 CaF, + MgF,+SiO,
2) barytization baryte limited water graying -
+urea (catalyst) CaCO, to BaCO,
3) limewater calcite limited water graying -
Ca(OH), + CO, + CaCO,
5) waterglass silica gel limited water Na-crust
Na,SiO,
K,SiO, initial wetness
8) Organic:
1. oil, waxes organics surface org. solvents strong yellowing crusts
2. acrylic resins polymers limited org. solvents some seals gloss
3. epoxy resins polymers limited org. solvents yellowing seals
4. ethyl silicates silicone deep alcohol, ketone none
5. silanes=siloxenes 2 w. SiO, silanol(Si0H-J deep alcohols none reacts with quartz
ester
6. silicic acid
Si(OC,H,) + 4H,O = SiO, + alcohol
Source: Snethlage (1984), Koblischek (1985), Weber and Zinsmeister (1991).

about 150 g/l in water; the potassium-carbonate dissolves almost 10

Temperature (Co)
Fig. 3. Solubility of silica (marked with dashed lines) as a
function of the degree of crystallinity,temperatureand the pH
of the solvent. Data from Kastner (1981); amorphous silica
precipitated from Wacker, OH, from Snethlage (1984).
water soluble sodium or potassium silicates. Today, commercial
aqueous solutions of silica as waterglasses of sodium or potassium
contain 10to 30% solids whereby the viscosity of the fluid increases
rapidly with the increase of the dissolved solids. Once the solution
contacts the mineral or matter of the stone, the waterglass solidifies
to Na,Si03 or K,Si03 and binding starts in less than 1 hr. The
subsequent interaction of the hardened waterglass with the CO, of
the atmosphere separates the remaining amorphous SiO, from
Na,C03, or K,CO,. Both compounds have a very different solu-
bility in rainwater. The solubility of sodium-carbonate is limited to
times more at 1 100 gmn. The carbonate of sodium tends to form
a white efflorescence in contrast, the carbonate of potassium, re-
mains in solution permanently above 40% RH, forming temporary
wet areas on the masonry until rain has washed away the dissolved
potassium-compound. Sodium, rejected by all plants, circulates
from the masonry into the ground and back into the masonry with
increasing concentration. In contrast, potassium is eagerly absorbed
as an important plant food and disappears from the environment.
The more expensive potassium-silicate is therefore preferred to
sodium-silicate. Waterglasses, however, have caused many prob-
lems in the past when applied to stone.
Laboratory experiments have recorded better strength and bind-
ing with quartz sandstones than with crystalline marble. Residual
sodium and potassium can form compounds with salts in solution
in the masonry which may combine to form insoluble efflorescent
compounds leading to spalling and flaking. The amorphous silica
residue cements the grains of quartz or calcite. Extensive experi-
ments with crumbling Carrara marble and quartzose sandstone from
Berea, OH, show a substantial increase of strength from the treat-
ment with potassium-waterglass, more for the sandstone than for
marble (Fig. 4). High ambient RH reduces the strength of the silica
residue, more at the beginning of the application than after half a
year of progressive recrystallization. The initial great difference
between oven dry and exposure to 100% RH atmospheres is as-
cribed to the great hygros~opicityof the potassiuin-s~licateabove
40% RH.Removal of the ~otassium-carbonateleaves behind a Dure
amorphous silica binder which appears to increase its strength,
probably by gradual crystallization from the metastable amorphous
silica on the way to the microcrystalline form. The present devel-
opment of new waterglass-type compounds without the presence of
alkali metals will eliminate the adverse effects of the carbonates of
sodium or potassium. The silica binder reduces the pore spaces by
about one-third of the original volume. Micro-cracking by shrinking
of silica gel could open up new pores for increased sensitivity to
frost action near the surface. There is no danger of color or other
alteration by ultraviolet (UV) radiation. Polluted urban rainwater is
not likely to attack stone reinforced with silica, but a sun heated
alkalic solution will dissolve silica gel. The complexity of the
process of curing is reflected in the time-strength graph (Fig. 4).
The geologic record shows evidence that a similar process
 INDUSTRIAL MINERALS AND ROCKS
Table 2. Waterglasses: Advantages and Disadvantages
Chemical Reactions
Na,Si03 Na,SiO, + H,O = Na,SiO, (liquid)
Na,Si03(solid)+C02 = SiO, . H,O (amorphous)+ Na,C03 (150gm/l)
K,Si03 + H,O = K,Si03 (liquid) =
K2Si03(solid)+CO, = SiO, H,O (amorphous) + K,CO, (1100 gm/l)
- Untreated Sandstone 100% RH
----------------- ---- ------
Untreated Marble 100% RH
I
0 been used successfully for many years with good durability and no
0 1 2 3 4 5 6 discoloring of the resulting inorganic amorphous silica. The chem-
Months from beginning of test
Fig. 4. Effectiveness and weatherability of potassium-wa-
terglass impregnated stone discs 35 mm in diameter, 2% mm
thick; samples of Hindostan siltstone, Bloomington, IN, and
deeply weathered Carrara marble. All discs were impreg-
nated 3 times and leached 1 hr in artificial "acid rain" of
pH=4.2 once a month and the modulus of rupture, R, tested
every other month (Winkler, 1986). Gradual change and re-
lease of K,CO, shows in the data.
involving natural waterglass has probably led to the formation of
feldspathic grain cement. The brownstone building fronts of the
northeastern United States have occasional microcrystalline feld-
spar cement (Hubert and Reed, 1978) which weathers rapidly to
clay while losing strength and durability. This Triassic-Jurassic
sandstone was formed in a desert valley near the present east coast
of the United States in the presence of alkalic waters. A pH of 9 or
greater could readily dissolve silica and alumina, the basis for the
formation of feldspars in the presence of additional potassium,
sodium, or calcium. Natural mineral materials and processes are the
most logical consolidant, although proper catalysts are still lacking.
Organic Consolidants
The use of epoxies and plastics has quickly become a very
profitable field in stone consolidation. The proliferation of propri-
Advantages Disadvantages
good; very hard strong white
efflorescence
hard hard white crusts
similar to Na compound occasional white
efflorescence;
temporary wet blotches
by hygroscopic attraction
etary new organic consolidants, often with minor variations from
one compound to another, makes a discussion of specitic consol-
idants impossible. Some organic compounds, such as the silicic
esters, cure to inorganic, hydrous, amorphous silica gel when ex-
posed to moisture in stone pores. Many stone conservators do not
consider a stone infiltrated with plastic a "stone" any longer.
The most important basic types of organic consolidants are:
ethyl silicates, organic resins, and silicones. Good summaries were
compiled by Snethlage (1984), Koblischek (1985), and Weber and
Zinsmeister (1991), and the chemistry of consolidants and consol-
idation was given by Amoroso and Fassina (1983). The variation
of chemicals is great and changes continuously with an ever in-
creasing number of patented products. Only the major groups of
organic consolidants are here discussed.
Ethyl silicates: Silicic acid ester is the most used consolidant
for sandstones. The silicic acid ester reacts with moisture as follows:
Si(OC,H,), + 4 H 2 0 + SiO, + 4 C2H,0H
ethyl silicate + pore water silica gel + ethanol
The reaction takes several weeks to complete which permits good
penetration into the weathered stone surface. This technique has
ical cannot be used in air lacking sufficient relative humidity to
assure capillary moisture for polymerization through hydrolysis.
Residual moisture, on the other hand, may remain trapped behind
the solidified surface zone often leaving pockets of untreated stone.
Shrinkage of the silica gel by gradual dehydration can develop
undesirable cracks in the grain cement. The treated surface is
usually pervious enough to permit the escape of moisture before
flaking can take place. The pure residual silica gel derived from
Wacker, OH, is of similar solubility to silica deposited from wa-
terglasses (Fig. 5). Several commercial products of silicic esters are
presently produced. Zinsmeister et al. (1988) give an overview of
physical properties and testing of Ohio sandstone treated with silicic
esters.
Silanes, siloxenes, siliconates: Silanes, siloxenes, and sili-
conates are all characterized by hydrolysis forming silicon resins
with capillary moisture leading from silanes, possibly to siloxenes
by cross-linking with a silicon atom of the stone. It appears that this
group of silanes requires a quartz rock host to become effective.
Resins: Resins comprise a large variety of compounds and
processes. The most important are epoxy resins, methacrylic resins,
unsaturated polyester resins, and polyurethane resins. Snethlage
(1984) discusses the chemistry in more detail.
Epoxy resins harden by the addition of accelerators with active
hydrogen atoms in accurately prescribed proportion and tempera-
ture. Epoxies lack penetration, seal out moisture, and yellow readily
in exterior exposure to UV light.
Methacrylic resins are readily polymerizable to polymethyl
methacrylate (PMMA), generally known as plexiglass, which is
 STONE, CONSERVATION
-.. ..
e*
-' -
---
AM-=-
-Y
Sandstone
_________-_ ----
/
'
----
Unbeated Marble
0 I I I
0 1 2 3 4 5 6 42nd and 33rd parallel, but much higher at 2 300 m elevation.
Months from begiing of test
Fig. 5. Effectiveness and weatherability of ethyl silicate im-
pregnated stone discs as in Fig. 4, also reflects the gradual
conversion to amorphous silica. The change is also reflected
in the graph. Data show comparisonof untreated with treated
stone. Marble shows minor improvement when treated.
resistant to weathering, especially to UV radiation. Accurate dosing
of the ingredients is necessary to obtain favorable strength and
resistance to weathering. PMMA treated stone hardens and prevents
travel of moisture. The low viscosity of water permits deep pen-
etration and is therefore used for vacuum infiltration of small
crumbling art objects. Total impregnation should only be performed
on small objects in a vacuum vat if a statue cannot be saved in any
other way. A fully impregnated stone, however, should not be called
a natural stone any longer.
Polyester resins are neither resistant to alkalies nor to UV
radiation. Such resins should not be used any longer in the presence
of much better chemicals on the market.
Polyurethane resins tend to form elastic polymers which are not
practical as consolidants, but are favorable waterproofers.
UV Radiation Attack
Most organic compounds and plastics tend to react with the UV
part of the light spectrum. Fig. 6 shows the solar distribution of UV
radiation at summer and winter solstice for Cleveland, OH, on the
42nd parallel, for Phoenix, AZ, on the 33rd parallel, and for Kitt
Peak (west of Tucson, AZ), on the 32nd parallel and 2 300 m above
sea level with a considerable summer UV increase. The solar
irradiance maxima lie in the mid-latitudes. The UV ranges (adapted
from Brennen and Fedor, 1987) react differently:
UV A (400-3 15 nm): Damage to polymers, tanning of human skin,
formation of eye cataracts.
UV B (3 15-280 nm): Shortest wave length in nature; severe damage
to polymer, bactericide, strongly carcinogenic, and absorbed by
window glass.
UV-C (280-100 nm): Found only in outer space
-
'99.sw.$H -
- uv-c I uv-B I uv-A'
I
- I
I
I
I
- I
I
- I
I
Wavelength (nanometers)
Fig. 6. Seasonal variation and range of solar radiation in the
UV portion of the spectrum. Little difference between the
UV-A ( 4 0 M 1 5 nm): damage to polymers, tanning of human
skin. UV-B (315-280 nm): shortest wave length on the earth
surface; severe damage to polymers, bactericide, strongly
carcinogenic. Data adapted from Brennan and Fedor (1987).
Yellowing and cracking of most organic sealers and consol-
idants can lead to eventual crumbling after only a few years of
exposure. Consolidant fillings primarily in sandstones may become
quite sensitive to frost and other hygric actions; the degree of
damage varies with the compound. Inorganic silica, even if derived
from organic, silicic-acid esters, is not affected by UV. Some
polyurethane compounds are very vulnerable, but PMMA reacts
little and may be considered safe.
Effectiveness of Consolidation
The formation of crusts is the major concern in the use of most
chemicals. The critical problem is to achieve a uniform continuous
hardness profile from the surface inward to the unweathered stone
substrate. The penetration of a consolidant through a case hardened
surface can be a major problem in many sandstones and pervious
limestones. The data on duration of consolidation effectiveness are
still scarce.
Clarke and Ashurst (1972) studied 24 different public buildings
after exposure for 20 years to natural weathering. The results of
these early organic treatments were not satisfactory, and the great
cost did not yield improved durability. More recently, Charola et al.
(1985) infiltrated three different porous, fossiliferous limestones
(Indiana limestone, Vicenza limestone, and Lecce limestone) with
Acryloid B 72 (supplied by Rohm and Haas). Depending on the
solvent exposure, rain has gradually restored the stones to their
original pretreated properties and porosity. The author believes that
the solvent in the consolidants is lost gradually as a function of the
exposure to the number of natural wetldry cycles.
Predictions of durability should be based on absolute terms per
1 000 mm of rain at a pH of 4.0. Durability tests for consolidants
should be kept simple and quantitative. Field exposures on rooftops
under urban or rural conditions can approximate the expected life.
Tucci et al. (1985) discuss the reduced effectiveness of acrylic and
silicone resins separately exposed to UV and acid rain in a chamber
for accelerated decay (CAD). The amount of decay of the organic
 INDUSTRIAL MINERALS AND ROCKS
filling and bonding was observed under the scanning electron mi-
croscope (SEM). The authors observed depolymerization of poly-
mers in 3 000 hr of exposure to UV while acid fog ate away the
calcite crystals in limestone leaving behind a residual acrylic skel-
etal network. Success with silicic acid ester was described by
Zinsmeister et al. (1988) for quartz sandstones which were carefully
solidified resulting in a pure inorganic silica gel residue and tested
for the apparent porosity (ASTM C20), density and water absorp-
tion (ASTM C97). modulus of rupture (ASTM C99), compressive
strength (ASTM C170), and abrasion resistance (ASTM C241).
- consolidants,
- and organic
DeWitte et al. (1984) tested 12 inorganic
ethyl silicate, siloxenes, silicic acid, potassium-silicate, fluosilicate,
polyurethane, epoxy, and PMMA for the following easily obtain-
able values for comparison: consumption of the consolidant, im-
pregnation depth after drying, decrease of capillary water absorp-
tion, scratch hardness, micro-sand blasting, and SEM photos. Pure
organic polymers discolor readily. The ethyl silicates are considered
most promising whereas the inorganic silicates showed poor per-
formawe. The literature for the evaluation of the efficiency of
consolidants and testing techniques is plentiful, yet there is no quick
and efficient evaluation method available.
Suggested Testing of Consolidants
A recent unpublished series of simple tests sheds some light on
the durability of consolidants. Thin discs, approximately 34 x 3 mm,
are cored from brick-sized stone blocks and sliced. They are sub-
sequently immersed for 3 sec into a consolidant three times. Testing
is at intervals of 2 months and at least six discs should be made for
each consolidant and test. The thin slices permit entry of consol-
idants from all sides. All specimens are dipped in artificial acid rain
at a pH of 4.2 for 1 hr every month before being tested dried at 60C
or after exposure to 100% RH for 3 days. Progressive weight loss
and the modulus of rupture are then determined.
Testing using simple techniques is summarized:
1. Water absorption: Specimens, submersed 48 hr in the
laboratory reflect the available total pore space. Water absorption
on a stone surface can be closely estimated with a small glass tube,
the Kersten permeameter. It is a reliable, consistent, easily read, and
a simple field instrument to measure permeability when attached to
a horizontal or vertical stone surface before and after treatment. The
degree of absorption per minute or second read in milliliters through
the stone substance at or near the stone surface measures the degree
of solidification, the effectiveness of a sealant, or the case hardening
of a surface of limited permeability. Gale (1989) describes the
Kersten tube and its operation, long used in Europe, for the Amer-
ican conservator. Large capillaries move the water downward by
gravity, capillaries narrowed by consolidant filling can change the
permeability, and the water from the tube often travels upward
leaving visible wet areas around the point of attachment to the stone
with putty (Winkler, 1988). Determine water absorption from the
atmosphere in stone slices after exposure to 3 days of 100% RH and
the strength after such exposure.
2. Modules of Rupture: Determine the modulus of rupture, R,
following each leaching, both oven dried and at 100% RH (Winkler,
1986).
3. Light Reflection: Determine light reflection with a light spot
meter, and the change of color shades compared using the US Soil
Color Chart.
4. Porosity: Prepare a porosity profile by grain size, for each
depth from the surface inward, as a three-dimensional presentation
for progressive change of critical pore sizes.
Tests 1, 2, and 3 reflect the progressive loss of the consolidant
during weathering experiments, especially expressed in the pore
size distribution. All figures should be cornpared with those from
the untreated original stone. The literature pays much attention to
comparative SEM tests which explain the kind and degree of filling
within the stone fabric; quantitative measurements, however, are
not possible with SEM pictures.
The great variation of the stone substance from bed to bed in
a natural outcrop should be considered when a testing program is
planned. Successful consolidants should be applied at dilutions in
which the strength and porosity does not exceed those of the un-
weathered stone thus avoiding the formation of hard crusts.
Cleaning of Stone Masonry
Cleaning of buildings in polluted urban areas has become not
only a practice of building maintenance for esthetic reasons, but also
for the prolonged life of the buildings and monuments. A multitude
of techniques using numerous modem chemicals have entered the
market and have been generously applied, often without proper
understanding and testing of the possible interaction between the
chemical compound and the stone substance. The excessive use of
corrodents haifrequently caused much damage, such as accelerated
scaling and discoloring. Many special reports are available pub-
lished-by producers ofchemical;. unbiased reports on the evalu-
ation of cleaners were published by the National Bureau of Stan-
dards (Godette et d., 1975), Anderegg (1949), ASTM (Clifton,
1987), the Australian Mineral Development Laboratories (AM-
DEL) (Spry, 1982; Spry and West, 1985), and by many in short
articles devoted to special problems. Boyer (1984) and Jones (1984)
discuss the state of the art of modem masonry cleaning. The tech-
niques range from pure washing with water to high pressure steam
and water jet cleaning, to the use of chemicals, and to abrasive
methods, often with adverse results. Carbonate rocks respond dif-
ferently to cleaning chemicals than quartz sandstones or granitic
rocks. Grimmer's (1988) practical field handbook includes the
problem of graffiti removal and a summary chart that is the best
guide for masonry cleaning to date, starting with the most gentle
methods and avoiding the harshest whenever possible. Such labor
intensive and time consuming techniques are practiced by the cau-
tious US National Park Service and are now accepted by most
conservators. The basic methods are described in the following:
Water Washing: Washing starts with gentle irrigation with
enough water running down the wall to keep it wet while it softens
the crusts of soot, often intermixed with gypsum and dust, followed
by a mild water spray. Three hours are often sufficient to remove
most of the deposits from the stone surface when aided by gentle
hand operation with soft nylon brushes.
Washing with elevated pressure and water volume can range
from mild to high pressure jets, with operating pressures ranging
from near 13.78 x lo5 Pa to a still safe 68.9 x lo5 Pa. Boyer (1984),
as well as Jones (1984), give nozzle pressures and water consump-
tion at different pressures. Pressure washing can cause dissolution
of carbonate rocks in areas with soft washing water. Forcing water
under pressure into the capillary system may cause undesirable
travel routes. High pressure jets may also cause mechanical erosion
of delicate features. Hot water is occasionally helpful in removing
grease and paint.
Steam cleaning with nozzle pressures of 0.69 x lo5 to 5.51 x
lo5 Pa has been successful for many years when cooler water jets
cannot remove the crusts.
Abrasive Cleaning, Dry or Wet: A great number of abrasives
and equipment have been developed to remove crusts and stains.
Quartz sand blown through a nozzle at high pressure against a stone
surface has become restricted by laws against both flying fragments
and dust in the atmosphere which can cause silicosis. Upon elim-
ination of silica sand, milder and safer abrasives were introduced,
 STONE, COF
r BLACK CRUST
Fig. 7. Cleaning of marble surface by laser beam; black crust
of soot (and gypsum). Laser gasifies the organic matter until
the marblesurface is reached; beam reflectsoff white marble
then. Adapted from Asmus, Murphy, and Munk (1973).
like soft glass beads, which do not cause silicosis. Com husk grit
and other mild abrasives are often included in a water jet. Me-
chanical abrasion tends to model the stone surface, often smooths
edges of fossil shells, but accentuates relief between the shells and
generally softer matrix in fossiliferous limestones. Relief can be
readily measured across the surface, to an accuracy of 0.2 mm, with
macro stereophotogrammetry (Winkler, 1983). Such relief tends to
trap soot and dust where it may adhere to the stone substance more
strongly than before the treatment.
The removal of secondary lime crusts has become a serious
problem. Structural concrete or lime mortar leak from joints and
tend to dissolve readily and redeposit as gray crusts of lime and
occasionally as dripstone formations. The strong adherence of such
crusts to any natural stone surface makes their removal very dif-
ficult. Matero (1984) describes field tests with a variety of com-
mercial wet abrasives on the Commodore Perry Memorial column
on Bass Island, OH, with granite facing a concrete structure. Mul-
tiple roof leaks supplied the water for leaching and deposition of the
lime crusts. Mechanical removal appears to be the only solution.
Laser Cleaning: Asmus et al. (1973) evaporated thin layers of
black soot on marble statues, where no other means of cleaning
could have reached, using long pulse ruby laser beams to bum away
the black crusts in several short bursts while the white marble
substrate remains unaffected. The soot bums off at 4 000 to
5 000" C, but very little heat is conducted into the marble substrate.
Fig. 7 shows a section across an encrusted marble. The laser tech-
nique has recently evolved to be a useful, but limited and expensive
tool.
Chemical Cleaning: The chemicals fall into three categories:
acidic cleaners, alkaline cleaners, and organic solvents.
Acidic cleaners range from harsh hydrofluoric acid (HF) to
other acid precleaning solutions. Hydrofluoric acid is generally only
used on silicate rocks. HF attacks silicate minerals, etching and
corroding them and often leaving non-shiny, non-reflecting feldspar
surfaces regardless of the strength of the acid. Eisenberg and Milton
(1972) report dulling of originally sparkling feldspars-on a granite
facade of the Old Cleveland Trust Buildine. Cleveland. OH. Porous
u.
sandstones and limestones readily retain acid in the pore systems
where it remains active. Carbonate rocks appear to be endangered
most by acidic cleaners.
Sodium hydroxide (NaOH) or ammonium hydroxide (NH,OH)
are the most common alkaline cleaning agents for use in removing
surface stains. Careful application and subsequent rinsing are very
important. Iron or silica are known to mobilize, during alkaline
treatment, from inside the stone to its surface forming rusty blotches
or gray coatings.
Organic solvents, aromatic hydrocarbons, and chlorinated hy-
drocarbons are often used for the removal of oil, grease, and other
bituminous materials. Flammability and toxicity of many organic
solvents restrict their use.
Several authors have accumulated and summarized chemical
cleaning data in charts useful to the masonry cleaner (Spry, 1982,
Boyer, 1984). but the most complete and practical work is by
Grimmer (1988).
BIBLIOGRAPHY
Amoroso, G.G., and Fassina, V., 1983, "Stone Decay and Conservation,"
Materials Science Monographs, Vol. 11, Elsevier, New York, 453 pp.
Anderegg, F.O.. 1949, "Testing Surface Water Proofers," ASTM Bulletin,
TP33. pp. 71-77.
Asmus, J.F., Murphy, C.G., and Munk, W.H., 1973, "Studies on the In-
teraction of Laser Radiation with Art Artifacts, Development in Laser
Technology, 11," Proceedings, Sociery of Photo-Optical Instrurnenta-
tion Engineers, Vol. 41, pp. 19-27.
Bear, N.S., and Lewin, S.Z., 1970, "The Replacement of Calcite by Fluorite:
A Kinetic Study," The American Mineralogist, Vol. 55, Mar.-Apr., pp.
466-476,
Boyer. D.W., 1984, "Masonry Cleaning-the State of the Art," Cleaning
Stone and Masonry, J.R. Clifton, ed., ASTM Special Technical Pub-
lication 935, pp. 25-5 1.
Boyer, D.W., 1987, "A Field and Laboratory Program-Determining the
Suitability of Deteriorated Masonries for Chemical Consolidation,"
Association Preservation Technology Bulletin, Vol. 19, No. 4, pp.
45-52.
Brennan, P., and Fedor, C., 1987, "Sunlight, UV and Accelerated Weath-
ering," Plastics Compounding, Vol. 12, No. 1, pp. 44-49.
Burgess, G., and Schaffer,R.J., 1952, "Cleopatra's Needle," Chemistryand
Industry, pp. 1026-1029.
Caroe, M.. 1987, "Conservation of Figure Sculptures, Wells Cathedral
1975-86," Association Preservation Technology Bulletin, Vol. 19,No.
4, pp. 11-15.
Charola, A.E., Laurenzi Tabasso, M., and Santamaria,U., 1985, "The Effect
of Water on the Hydrophobic Properties of an Acrylic Resin," Pro-
ceedings, 5th International Congress on Deterioration and Conserva-
tion of Stone, Lausanne, pp. 739-747.
Clark, E.J., Campbell, P.G., and Frohnsdorff, G., 1975, "Wate~proofing
Materials for Masonry," US Department of Commerce, National Bu-
reau of Standards, NBS Technical Note 883, 76 pp.
Clarke, B.L., and Ashurst, J., 1972, "Stone Preservation Experiments,"
Building Research Establishment, Department of the Environment, 78
PP.
Clifton, J.R., 1980, "Stone ConsolidatingMaterials-A Status Report," US
Department of Commerce, National Bureau of Standards, NBS Tech-
nical Note 1118, 46 pp.
Clifton, J.R., 1987, "Preliminary Performance Criteria for Stone Treatments
 INDUSTRIAL MINERALS AND ROCKS
for the United States Capitol," US Department of Commerce, National
Bureau of Standards, NBS IR 87-3542, 12 pp.
De Castro, E., 1983, "Studies on Stone Treatments," Laboratorio Nacional
de Engenharia Civil, Memoria No. 584, Lisbon, 6 pp.
DeWitte, E., Charola, A.E., and Cherryl, R.P., 1984, "Preliminary Tests on
Commercial Stone Consolidants," Proceedings, 5th International Con-
gress on Deterioration and Conservation of Stone, Lausanne, pp. 709-
718
- -
Eisenberg, K.S., and Milton, C., 1972, "Case History of a Structural Granite
Cleaning Problem," Proceedings, 1st International Symposium on the
Deterioration of Building Stones, LaRochelle, France, pp. 129.
Gale, F., 1989, "Measurement of Water Absorption," Association Pres-
ervation Technology Bulletin, Vol. 21, No. 314, pp. 8-9.
Godette, M., Post, M., and Campbess, P.G., 1975, "Graffiti-resistant Coat-
ings: Methods of Test and Preliminary Selection Criteria," US De-
partment of Commerce, National Bureau of Standards, NBS IR 75-798,
35 PP.
Grimmer, A.E., 1984, "A Glossary of Historic Masonry Deterioration and
Preservation Treatments," US Department of the Interior, National
Park Service, Preservation Assistance Division, TH 532 1 .G56, 65 pp.
Grimmer, A.E., 1988, "Keeping It Clean," US Department of the Interior,
National Park Service, Preservation Assistance Division, 33 pp.
Gutschick, K.A., 1988, "Lime, Important Construction Material," ASTM
Standardization News, July, pp. 32-35.
Hawkins, W.L., 1973, "Environmental Deterioration of Polymers," Poly-
mer Stabilization, W.L. Hawkins, ed., Wiley, New York, pp. 1-28.
Heiman, J.L., 1981, "The Preservation of Sydney Sandstone by Chemical
Impregnation," Experimental Building Station, Technical Record 469,
Chatswood, New South Wales, 22 pp.
Hubert, J.F., and Reed, A.A., 1978, "Red-bed Diagenesis in the East Berlin
Formation, Newark Group, Connecticut Valley," Journal of Sedimen-
tary Petrology, Vol. 48, pp. 175-184.
Jones, L.D., 1984, "Criteria for Selection of a Most Appropriate Cleaning
Method," Cleaning Stone and Masonry, J.R. Clifton, ed., ASTM
Special Technical Publication 935, pp. 52-70.
Kastner, M., 198 1, "Authigenic Silicates in Deep Sea Sediments, Formation
and Diagenesis," The Sea, The Oceanic Lithosphere, Vol. 7, C. Emi-
liani, ed., Wiley Interscience, New York, pp. 915-940.
Kessler, L., 1983, "Sur un ProcCdC de Durcissement des Pierres Calcaires
Tendre au Moyen des Fluosilicates ? Base
i d'loxydes Insolubles,
Comptes-Rendus," AcadJmie des Sciences. Institut de France, Vol. 96,
pp. 1317-1319.
Koblischek, P., 1985, "Polymers in the Renovation of Buildings Con-
structed of Natural Stone," Proceedings, 5th International Congress on
Deterioration and Conservation of Stone, Lausanne, pp. 749-758.
Lewin. S.Z., 1972, "Recent Experience with Chemical Techniques of Stone
Preservation," Proceedings, Meeting for the Conservation of Stone,
Bologna, ct. 1-3, 1971, pp. 139-144
Matero, F.G., 1984, "A Diagnostic Study and Treatment Evaluation for the
Cleaning of Perry's Victory and International Peace Memorial," As-
sociation Preservation Technology Bulletin, Vol. 16, No. 314, pp.
34-5 I .
Price, C.A., 1984, "The Consolidation of Limestone Using a Lime Poultice
and Limewater," Internatl. Coll. Natursteinkonservierung, Munich,
May 21-22, Arbeitsheft, pp. 31.
Riederer, J., 1989, Bibliography on the Cleaning of Stone, Rathgen-La-
borberichte, pp. 1-5.
Sleater, G.A., 1983, "Stone Preservatives: Methods of Laboratory Testing
and Preliminary Performance Criteria," US Department of Commerce,
National Bureau of Standards, NBS Technical Note 941, 72 pp.
Snethlage, R., 1984, "Steinkonservierung (Stone Conservation)," For-
schungs Programm des Zentrallabors f. Denkrnalpflege 1979-1983,
Bayer. Landesamtf: Denkmalpjege, Arbeitsheft 22, Munich, 203 pp.
Spry, A.H., 1982, "Principles of Masonry Cleaning Buildings." Australian
Council of National Trust, Technical Bulletin 3.1, 30 pp.
Spry, A.H., and West, D.G., 1985, "The Defense Against Graffiti," Aus-
tralian Mineral Development Laboratories, Report 1571, 196 pp.
Torraca, G., 1976, "Treatment of Stone in Monuments, A Review of
Principles and Processes," The Conservation of Stone, R. Rossi-Man-
aresi, ed., Bologna, June 19-21, 1973, pp. 297-315.
Torraca, G., 1978, "Solubility and Solvents for Conservation Problems,"
International Centre for the Study of the Preservation and the Resto-
ration of Cultural Property, 60 pp.
Tucci, A,, et al., 1985, "The Influence of Acid Rain and UV Radiation on
the Aging of Acrylic and Silicone Resins," Proceedings, 5th Interna-
tional Congress on Deterioration and Conservation of Stone, Vol. 2,
Lausanne, Sept. 25-27, pp. 891-898.
Voss, B.H., and Tammes, E., 1968, "Flow of Water in the Liquid Phase,"
Institute TNO for Building Materials and Building Structures, Report
No-B-1-68-38, Delft, Holland, 45 pp.
Weber, H., and Zinsmeister, K.J.H., 1991, Conservation of Natural Stone:
Guidelines to Consolidation. Restoration and Preservation, Expert
Verlag, Germany, 163 pp.
Wihr, R., 1980, Restauricrauz von Steindeukurolern, VerCamp Calliog
Munich, 230 pp.
Winkler, E.M.. 1956, "The Influence of Blood onclays," Soil Science, Vol.
82, NO. 3, pp. 193-200.
Winkler, E.M., 1980, "Historical Implications in the Complexity of De-
structive Salt Weathering-Cleopatra's Needle, New York," Associ-
ation Preservation Technology Bulletin, Vol. 12, No. 2, pp. 94-102.
Winkler, E.M., 1983, "A Macro Stereogrammetric Technique for Measur-
ing Surface Erosion Losses on Stone," Cleaning Stone Masonry, J.R.
Clifton, ed., ASTM Special Technical Publication 935, pp. 153-161.
Winkler, E.M., 1986, "A Durability Index for Stone," Bulletin Association
of Engineering Geologists, Vol. 23, pp. 3 6 3 4 7 .
Winkler, E.M., 1987, "Weathering and Weathering Rates of Natural
Stone," Environmental Geology and Water Science, Vol. 9, No. 2, pp.
85-92.
Winkler, E.M., 1988, "Response to a Field and Laboratory Program,"
Association Preservation Technology Bulletin, Vol. 20, No. 3, pp. 28.
Zinsmeister, K.J.H., Weiss, N.R., and Gale, F.R., 1988. "Laboratory Eval-
uation of Consolidation Treatment of Masillon (Ohio) Sandstone,"
Association Preservation Technology Bulletin, Vol. 20, No. 3, pp.
35-39.