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Technology and behavior of rubble masonry mortars

Article  in  Construction and Building Materials · March 1997

DOI: 10.1016/S0950-0618(97)07023-2

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 Consh-zcction andBuikfingMateri& Vol. 11, No. 2, pp. 119-129, 1997
0 1997 Elsevier Science Ltd
Printed in Great Britain. All rights reserved
0950-0618/97 $17.00 + 0.00
ELSEVIER PII:SO950-0618(97MOO23-2

Technology and behavior of rubble masonry

mortars

A. Moropoulou*f-, G. Biscontin$, A. BakolasS and K. Bisbikou*

* Section of Material Science and Engineering, Department of Chemical Engineering,

National Technical University of Athens, Athens, Greece
*Department of Environmental Sciences, Chemistry of Restoration,
University of Venice, Venice, Italy

Received 22 September 1996; revised 19 October 1996; accepted 2 1 October 1996

Rubble masonry mortars are distinct to the masonry mortar joints due to the different construction
techniques used and the prerequisites concerning their behavior in the structure. In the present work,
physico-chemical and mineralogical examination of rubble masonry mortars is performed on the
development of cohesion and adhesion bonds. A working hypothesis on production technology is
deduced consequently. Recent collapses of the rubble masonry at several bastions of the knights’
period in the Medieval fortifications of Rhodes allow for sampling. Investigations by optical microscopy,
scanning electron microscopy, fiber optics microscopy, X-ray diffraction analysis, differential thermo-
gravimetric analysis, porosimetry as well as total soluble salts measurements were performed. Various
types of rubble masonry mortars are evidenced and all of them present a very coherent matrix, either
‘cementitious’ or very finely crystallised and compact. From the top to the bottom of the masonry,
different microstructural characteristics are observed in the mortar nucleus, indicating different
lime-to-aggregates ratios. The microstructural stratification of the cementing material points out
different carbonation and drying levels and implies successive supply of water to slake the lime in situ.
The evidence of hydraulic components all around the bulk, but not on the outer top of the walls, is of
particular interest and proves the in situ slaking of lime as the energy source to activate either
hydraulic reactions among lime and clay minerals or the crystallization of portlandite. The high levels
of soluble salts measured indicate the mortars’ susceptibility to salt decay, specifically when pore size
distribution is in favor, as in the case of the modern cement or the pure calcitic mortar, in comparison
with the more resistant hydraulic mortars. 0 1997 Elsevier Science Ltd.

Keywords: rubble masonry; cohesion and adhesion of mortar joints; in situ slaked lime

Introduction different limestones; dolomite limestone, etc., at vari-

The historical mortars are composite materials formed
by a binder (or mixture of binding materials), a variety
of inert materials (mostly a mixture of inorganic com-
pounds not always of crystalline nature) and some
additives (sometimes of organic nature), added in small
quantities for the improvement of the mechanical
strength of the mortar. It is not rare that a component
could derive either from the binder or the inert ma-
terials ‘.
Usually binding materials include: hydraulic lime
arising from the different types of argillaceous lime-
stones and clay mixtures, or aerial lime arising from
tCorrespondence to A. Moropoulou
ous burning temperatures, slaked by different water
proportions and for various period of time (fat or thin
lime).
Aggregates include: inert aggregates, practically
non-porous and presumably passive materials like sili-
cate, carbonate or dolomite sand, or porous aggregates,
physico-chemically active, like crushed brick, etc.
Usually crushed brick and pozzolanic additives (terra
theraica, pozzolana, etc.) are added in order to ame-
liorate mortars’ performance towards better adhesion,
workability or compatibility 2.
Hence, the technological variations concern the raw
materials used, the technology of lime (burning tem-
perature, slaking time, water proportion, etcJ3s4, as well
as the production technology (mixture ratio and granu-
lometry of binder to aggregate)’ and construction tech-

119
 120 Technology and behavior of rubble masonry mortars: A. Moropoulou et al.
nique (width of the joint, outer or inner front, contact
and carbonation surface)5, in order to achieve a certain
cohesion and adhesion of the mortar to the building
stones.
The determination of mechanical characteristics of
mortars in existing monuments is usually assessed by
measuring the mechanical characteristics of new mor-
tars, composed by traditional materials, in the propor-
tions found by chemical analysis of the authentic ones6.
Schafer found experimentally the relationship
between binder content and open porosity and between
binder content and strength of lime mortars7. It is
obvious that the stress-strain curve of mortars with
hydraulic lime is similar to that of low strength con-
crete.
It is obvious that the relatively low strength of old
mortars does not explain their longevity. However some
traditional mortars, like the Hagia Sophia ones, present
considerable mechanical strength along with their
longevity and could be considered as early concrete
structures, due to adhesion phenomena among binding
material and brick fragments*. A false adhesion affects
negatively the durability of the masonry, especially
- SectiOn Of Englad
Bastion of England
Figure 1 Masonries of the medieval city of Rhodes.
when physico-chemical phenomena, like dissolution,
transport and recrystallisation of salts leading to salt
decay, occur9.
Among the very few studies on the topic, Binda
Mayer and Baronior’ concluded that the aerial lime to
brick adhesion should not always be attributed to phys-
ical mechanisms, as Palmer and Pasons in 1934 be-
lieved”, but to reactions of chemical character as well.
The adhesion mechanism among binding material and
brick fragments in crushed brick mortars has been
disclosed2 at the reaction rims of the interface identi-
fied as CSH’2,13.
Rubble masonry mortars are distinct to the mortars
of masonry joints due to the different construction
techniques used and the prerequisites, concerning their
behavior in the structure. In the joints, the mortar acts
as the adhesive agent by connecting two different build-
ing stones. In the rubble masonry, the mortar composes
the nucleus of a structural system built around (inter-
nal mortar), depending on the multivariable adhesion
bonds, built up among mortar-building stone and mor-
tar-aggregate fractals, which affect the strength proper-
ties of the system. In the case under study, particularly
_ ‘u Tower Nailacor
tower of Arabs
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_ _ _ _ _ _ - - Se
Intermediate tower IXaf 1. /
 Technology and behavior of rubble masonry mortars: A. Moropoulou et al.
coherent mortars are required for the development of
considerable adhesion among the structural units. Very
few studies give information on the physico-chemical
character of adhesion or, furthermore, on the produc-
tion technology assuring it. Doglioni et al. studied
rubble masonry mortars and concluded for particularly
interesting binder to inert material ratio, richer in
cementing material than the known traditional values,
and for a different production technology of lime char-
acterized by the use of very low water quantities14.
In the present work, physico-chemical and miner-
alogical examination of rubble masonry mortars is per-
formed, in reference to the development in the struc-
tural system of cohesion and adhesion bonds. A work-
ing hypothesis on production technology is deduced
consequently.
In siftr study and sampling
Recent collapses of the masonry at several bastions of
the knights’ period (14th-15th century AD) in the
121
medieval fortifications of Rhodes @‘@ue I) allow for in
siti study and sampling and, in particular,at the bas-
tions of Spain, of St. Athanasios and of St. John as
follows:
l horizontal to the ground, internal mortar nucleus is
revealed connecting a wide rubble stone masonry;
l on the back side of the masonry, there is a layer of
successive horizontal and uneven layers of raw
stones of equal size per layer. They are placed side
by side in right or left inclination. The course of this
inclination varies from one layer to the other, fol-
lowing the fish-bone shape. For this construction,
strong lime mortar was used as binding material to
form a solid nucleus, which could release the main
wall from the sideways thrusts.
Hence, a double (nibble) stone masonry Cmura a
sacco’) is concerned, joined by an artificial conglomer-
ate of gravel or broken stone and pebbles with sand
and lime or cement, consisting well adhered solid mor-
 Technology and behavior of rubble masonry mortars: A. Moropoulou et al.

Figure 2 Collapses of rubble stone masonry - sampling of the internal mortar.

tars (‘calcestruzzo da sacco murario’)‘5. Vitruvius de- Table 1 Sampling

scribes it as the ancient concrete’“. Sample Sample type Location
Sampling of internal mortar took place at the fol- no.
lowing collapsed parts of the walls: 6 Rubble masonry St. John’s bastion
old mortar (internal) (from the base of the wall - 5 m)
(1) The inner side of St. Ioannis bastion. There is a 7 Rubble masonry St. John’s bastion
old mortar (internal) (middle height of the wall - 2 m)
great gap opened at the concave part of the walls, 10 Rubble masonry St. John’s bastion
caused by the collapse of the sloping wall. In the old mortar (internal) (from the top - 4 m)
middle of the gap a drainage has remained almost 13 Rubble masonry St. Athanasios’ bastion
old mortar (internal) (from the base of the wall - 0.5 m)
intact, resting on the nucleus [Figures 2 (u-d)]. 15 Rubble masonry St. Athanasios’ bastion
The bastion of St. Ioannis was constructed in two old mortar (internal) (from the top - 4 m)
periods. The first and older part of it, that starts 19 Modem restoration Byzantine church
mortar Agisandrou St. (under
from the ground and continues up to 4 m, was restoration)
constructed around 1470 AD. The second part
that follows and goes up to 3 m, was constructed
around 1500 AD.
(2) At the bastion of Spain. Its part that faces the (Philips 515 Scanning Electron Microscope) and fiber
buttress of the fortress (contra scarpa) has col- optics microscopy allow for the evaluation of the ce-
lapsed and created a gap of 4 m (length). Its mentitious character of the mortar, its stratification,
nucleus is partially degrading round the rupture texture, microstructure, adhesion to aggregates and
[Figure 2 Ce)]. fragments.
A physical separation of granulometric fractions was
High humidity levels were evidenced in the collapsed achieved by sieving the mortar in sieves of diameter 63
walls and even higher inthe samples removed from pm, 125 pm, 250 pm, 500 ,um, 1000 pm, 2000 ,um,
their lower parts, close to the ground. Mortar samples 4000 pm, respectively, and weighing. It cannot be
were taken from the internal of the rubble masonry at assumed that the separation of binder from aggregates
various heights (Table I) and widths, wherever possible, is carried out by the separation of the fragments.
in order to be representative of the construction tech- However it is an acceptable working hypothesis that
niques and locations in the structure.
the fractions between 0 and 63 pm comprise the bind-
For comparative purposes a sample of modem con-
ing material, while mineralogical and chemical analyses
crete mortar was taken from the byzantine church in
give information on the nature and granulometry of the
Agisandrou street [Figure 2 (h)] under restoration.
aggregates. After the above-described physical separa-
tion the matrix of the mortar was examined as follows.
The mineralogical and chemical analysis involves
quantitative X-ray diffraction (Siemens D-500 X-Ray
Experimental procedures
Diffractometer) and differential thermo-gravimetric
Optical observations made by optical microscopy (Zeiss analysis (Perkin Elmer Thermogravimeter TG S-2 and
Polarised Microscope), scanning electron microscopy DTA 1700).
 Technology and behavior of rubble masonry mortars: A. Moropoulou et al. 123

Porosirnetry measures (Carlo Erba Mercury
Porosimetry 4000) the microstructural characteristics of
the mortar, which are critical for determining the
physico-chemical behavior of cementitious materials.
The total soluble salts are calculated by conductivity
measurements (HACH conductivity/TDS meter) on
dry wt.
Results and discussion
Calcite and quartz were proved to be the main compo-
nents of the examined samples, by X-ray diffraction
(XRD) analysis (Table 2). It is a common characteristic
between all samples that dolomite and other minerals
rich in Mg, like serpentine, chlorite and anthophilite
are present. Components like portlandite, montmoril-
lonite and tobermorite are also present almost in all
samples. A special characteristic of sample 19 (modem
cement mortar) is the presence of yoderite and
CaAlCl-hydrate.
The XRD results verify the presence of hydraulic
components (CSH, CAH, etc.), in almost all samples
except for sample 15; these results agree with previous
results 3.
Thin sections of samples 7, 10, 13, 15, 19 were
prepared and examined under optical microscopy with
crossed Nicols [Figures 3 (u-g)].
Sample 7: A significant quantity of serpentine, calcite
and a few small olivine grains were observed [Figure 3
(a)]. Plagioclase and quartz grains are shown in [Figure
3 (b)], while calcite was met more often in the binding
material than in fragments. Gxidised grains with fossils
were also observed [Figure 3 (c)l.
Sample 10: contains grains of quartz, plagioclase,
serpentine and pyroxene along with rounded grains of
calcite. Grains of pyroxene and oxidised calcitic micro-
veins were recognized. Many fossils were also present.
Sample 13: cementitious calcitic material with fossils
and a few quartz grains are presented in [Figure 3 (d)].
Cementitious calcitic material with serpentine grains
was also observed [Figure 3 (e)].
Sample 15: a cementitious calcitic binding material
with many fossils was observed, while primary rounded
calcite, angular quartz, plagioclase, serpentine and
probably amphibole and olivine grains were localised in
the matrix [Figure 3 cf-g)]. Moreover, many oxidised
calcitic grains were noticed.
Sample 19: angular fragments of primary calcite and
oxidised calcitic material were present.
The above results present mortars rich in lime, with
hydraulic components embedded by medium-grained
aggregates. These observations are in agreement with
previous works3 showing CO,, measured by calcimetry,
which fluctuates between 28 and 37% in the binding
material and indicates a rather high calcitic content
(63.56-83.99%), while the aggregates present consider-
able fragments of dimensions between 0.25 and 2 mm,
their major fractal ( m 20% by weight), observed around
0.5 mm. These are coarser than other mortars of the
medieval city of Rhodes’, but finer in comparison with
the crushed-brick/lime mortars and plasters’.
Microstructural characteristics of samples 6, 7, 10,
13, 15, 19 are given in Table 3.
Cumulative volume curves for all samples, except for
sample 19 (concrete mortar), are articulated by two
curvatures, as shown by the two maxima of the pore
size distribution histograms, which indicate different
phases of hydration and drying of the lime mortar
(Figure 4) and different levels of carbonation as we115.
These distinct phases are observed by the fiber optics
microscope [Figure 5 (c,e)] in the form of matrix strati-
fication in the samples 7 and 15. The successive supply
of the rubble stone masonry by lime is assumed, and

Table 2 X-ray diffraction analysis (XRD)

Sample no. Composition

6 (inside) Calcite, quartz, dolomite, plagioclase, gypsum, portlandite,

tohermorite, muscovite, illite, aragonite, montmorillonite
6 (outside) Calcite, quartz, dolomite, plagioclase, portlandite, aragonite,
montmorillonite
7 Calcite, dolomite, quartz, plagioclase, muscovite, portlandite,
anthophyllite, antigorite, serpentine
10 Calcite, quartz, dolomite, muscovite, plagioclase, chlorite,
portlandite, anthophyllite, serpentine
13 Calcite, quartz, dolomite, muscovite, serpentine, portlandite
15 Calcite, quartz, dolomite, aragonite, plagioclase, leucite
19 (white) Calcite, dolomite, quartz, anhydrite, yoderite, chlorite,
CaAlCl-hydrate, portlandite
19 (yellow) Calcite, dolomite, quartz, anhydrite, yoderite, tobermorite,
portlandite
Anthophyllite, (Mg,Fe),SisO,,(OH), (9-455); leucite, KAISiz06 (15-47); yoderite,
Mg,Ca0.2Fe0.5Al,~3Si,0,,~~(OH)z,., (12-625); tobermorite, Ca,Si,Al(OH)OI,.5Hz0 (19-52); serpen-
tine, Mg,Si,O,(OH)., (9-444); chlorite, MgFeAlOOH (16-362); MgFeAlOOH (16-351); aragonite,
C&O, (5-0453); plagioclase, NaAlSisO, (albite) (9-466); montmorillonite, @l,Mg)Si,O,a(OH)zNa
(13-259); tobermorite, CasSi,Or, + 5(HzO) (10-373); muscovite, KAl,Si,AIOu,(OH)z (7-32); port-
landite, Ca(OH), (4-733).
124 Technology and behavior of rubble masonry mortars: A. Moropoulou et al.

Table 3 Microstructural characteristics Very coherent mortars [Figure 5 (a)], with good ad-
RfTl AS
hesion both to the building stones [Figure 5 (b)] and the
Sample no. PU P% Y
aggregates [Figure 5 kf)l, more or less rich in lime are
6 17.32 35.12 204,415 1.52 2.03 observed.
7 25.66 43.07 6126 3.27 1.67
10 16.71 32.51 198,733 1.9 2.01 The large and medium pore radii (samples 6, 10, 13
13 23.22 42.16 204,088 1.92 1.81 and 15) give evidence to the use of water in abundance
15 11.69 24.86 202,858 4.66 2.12 for the in situ slaking of the lime.
19 9.253 19.47 2500 2.38 2.10
Figure 6 presents the scanning electron micrograph
Pv, total cumulative volume (cm3/g); P%, total porosity (%I; y. examination of the samples 7, 13 and 15.
apparent density (g/cm3);0As, actual specific surface area (m*/g);
Rm, medium pore radius (A>.
Sample 7: quite compact surface was observed, while
grains of magnesium-silicate minerals were localised in
the calcitic matrix [Figure 6 (a)]. Primary and secondary
interprets the stratifications of the more or less con- crystals of calcite are shown in [Figure 6 (b)].
densed zones, as the aggregates sediment in the lime Sample 13: porous cementitious matrix is observed,
putty create a white band of hardened lime mortar. two phases of hydration-carbonation, embedded by

Figure 3 Microphotographs - optical microscopy with crossed Nicols (25 X 1. Sample 7 a,b,c; Sample 13 d,e; Sample 15 f,g.
 Technology and behavior of rubble masonry mortars: A. Moropoulou et al. 125

P
7 ‘T
250 Cum. vol (mm3t3) 100 Rel. v
s. 6

250

Pore radius (A> Pore radius (A)

Figure 4 Total cumulative volume pore size distribution curves (samples 6.7, 10, 13, 15 and 19).

quartz and calcite grains is observed [Figure 6 (c)l. The
more humid and less calcitic matrix phases, darker in
colour, consists probably of hydraulic components like
tobermorite.
Sample 15: compact finely crystallised matrix with
many fossils is presented in [Figure 6 (d-f)]
DTGr and DTA results present considerable water
loss (6-7%) in the range of 300-700°C which gives
evidence to the presence of H,O bounded to hydraulic
compounds (CSH, CAH).
A considerable CO, weight loss is recorded in the
range of 690-935°C implying the presence of calcite,
dolomite and clay minerals (Table 4, Figure 7).
The DTGr peaks at approximately 500°C indicate
the deformation of crystalline hydraulic components.
Portlandite is identified in particular. The formation of
hydraulic components like CSH, CAH in a high alka-
line environment requires energy consumption, which
could be provided by the exothermic reactions, giving
rise to relatively high temperatures (over 300’0, by the
in siru slaking of lime4. For montmorillonite clays such
a possibility has been reported for low temperatures
around 300°C. This is a temperature level poss-
ibly achieved when the lime is slaked in situ (calce
calda). Relevant references are made concerning ma-
rine structures of great antiquity. The view that basic
silicates are formed in burning and are subsequently
hydrolysed by water, yielding lime and hydrated sili-
 126 Technology and behavior of rubble masonry mortars: A. Moropoulou et al.

Figure 5 Fiber optics microscope observations (X 50). Sample 6 (a-b): mortar surface - building stone mortar interface. Sample 7 cc): mortar
stratification. Sample 13 (d): mortar aggregates. Sample 15 (e): interface among mortar layers. Sample 19 (0: cement mortar.

cates, was pronounced by Winkler17 and has since fully
established itself. As it is well known and has already
been proved by the authors in the case of hot-lime
technology, raw clays consist essentially of a group of
hydrated aluminium silicates, though alumina may be
replaced to varying extent by ferric oxide and to a
lesser extent by bases such as MgO, Na,O and CaO.
The water content can also vary considerably4~‘8.
It is not by chance that the carbonation is higher at
the outer and top of the masonry (samples 10 and 15)
as shown by the sequence of the CO, loss (Table 4),
while the higher water content due to the successive
watering, and the higher temperatures evolved and
retained in the bulk, interpret the more cementitious
matrix in the masonry mortars close to the ground
(samples 7 and 13). A similar phenomenon of stratifi-
cation is reported regarding zeolitic materials as alter-
ation products by analogous hydrothermal reactions.
Santarelli” has cited the gradual diminution of poz-
zolanic activity from the base to the top of the Italian
quarries and the greater abundance of crystalline con-
stituents in the materials of more recent origin.
The noticeable presence of portlandite, as compared
to calcite (Table 2), especially in the samples closer to
the ground, proves that the energy offered by the
watering of the in situ slaked lime activates the produc-
 Technology and behavior of rubble masonry mortars: A. Moropoulou et al. 127

Figure 6 SEM micrographs: sample 7 (a-b); sample 13 (c); sample 15 (d-0.

tion of crystalline substances as well, in parallel with
hydraulic products.
As shown in Table 5, considerable amounts of total
soluble salts (TSS), in percentage of dry weight, have
been measured (2.5-4.2%) on all the samples, con-
sisted meanly of chloride salts. Samples 15 and 19
present a higher percentage of the total soluble salts.
The susceptibility of porous materials to salt decay
can be evaluated by the pore structure’8. Actually,
Hihen a large amount of small pores coexists with an
adequate amount of large pores, the material is more
susceptible to salt decay. In the case under study, the
samples 15 and 19 (i.e. the more calcitic lime mortar
and the modem cement) even though of lower porosity,
present pore structure in favor of salt decay. On the
contrary, the TSS amount in the mortar nucleus pre-

Table 4 Differential thermogravimetric analysis

Sample no. Weight % CO1 loss from From-to Weight % H,O loss (temperature
change mineral phases range 300-700°C)

7 19.2 Cc + D + clay min. 726-935 6.50

10 23.2 Cc + D + clay min. 701-910 6.09
13 27.46 Cc + D + clay min. 714-923 6.31
15 28.99 Cc + D + clay min. 689-873 6.77
128 Technology and behavior of rubble masonry mortars: A. Moropoulou et al.

Sample 7 WT: 40.7404 mg Rate: 20.00 deg/min Sample 13 WT: 21.4586 mg Rate: 20.00 deg/min
--- = derivative -.-.-- = derivative

From: 713.89
To: 923.12 \
WT % change: 28.46

I Id. I
10 210 310 410 510 610 710 810 910 1010 Ill 111D 210 310 410 510 610 710 810 910 1010 lll(
Temperature (“C) 870 Temperature (“C)

Sample 10 WT: 24.6590 mg Rate: 20.00 deglmin Sample 15 WT: 24.5438 mg Rate: 20.00 deg/min
----_- = derivative ------ = derivative
IO.-

‘r
I\
0 210 310 410 510 610 710 810 910 1010 1111 0 210 310 410 510 610 710 810 910 1010 11lf
Temperature (“C) Temperature (“C)
Figure 7 Differential thermogravimetric analysis for the samples 7, 10. 13 and 15.

ergy required to activate reactions for the production

sent a stable and relatively lower level (2.5%), indi-
cating considerable physico-chemical resistance to the
marine atmosphere of Rhodes.
Conclusions
Various types of rubble masonry mortars are evi-
denced, all of them of hydraulic lime, presenting a very
coherent, cementitious compact matrix, well adhered to
the medium grained aggregates.
From the bottom to the top of the masonry, different
textural and microstructural characteristics indicate
different lime/aggregates ratios and lime stratification,
which points out various carbonation and drying levels.
The successive supply of the rubble stone masonry by
lime, interprets the stratification of the more or less
condensed zones, as the aggregate sediment in the lime
putty creates a white band of hardened matrix.
either of hydraulic neoformations or of crystalline com-
pounds, like portlanditem.
This technology interprets the different carbonation
and drying levels, i.e. the higher carbonation at the
outer and top of the masonry and the more cemen-
titious matrix in the mortar nucleus nearby the ground,
due to successive watering and the higher temperatures
evolved and retained in the bulk.
Hence, crystalline hydraulic components render the
mortar nucleus to dense pore structures imparting high
strength and adhesion to the rubble masonry.
The high levels of soluble salts measured, in the case
of the calcitic mortar more exposed to the environment
at the top of St. Athanasios Bastion, and in the case of
the modern cement mortar, indicate their higher sus-
ceptibility to salt decay, due to the favorable pore size
Table 5 Total soluble salts (%)

The large and medium pore radii give evidence of Sample no. W C TSS (%)
the use of water in abundance for the in situ slaking of
6 103.9 40 2.65
the lime. Hence, reduced water portion used for lime 7 103.4 41 2.73
preparation is deduced. IO 100.6 37 2.53
In situ slaking of lime, as an exothermic reaction, 13 106.2 37 2.40
15 106.1 64 4.15
gives rise to relatively high temperatures (> 3OO”C), 19 101 55 3.15
which in the high alkaline environment offer the en-
 Technology and behavior of rubble masonry mortars: A. Moropoulou et al.
distribution, in comparison to the hydraulic mortar
nucleus.
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