MATERIALS PROPERTIES, USE AND CONSERVATION: Construction

Materials and Binders

Karmela Crnović
Applied Science to Cultural Heritage, Materials, and

Sites

2022/2023
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1. INTRODUCTION.................................................................................................................................................................. 4
1.1. Construction materials and binders ................................................................................................................... 5
1.1.1. Energy balances...................................................................................................................................................... 7
1.1.2. Some general terms.............................................................................................................................................10
2. CALCIC BINDERS...............................................................................................................................................................17
2.1. Historical Survey.....................................................................................................................................................19
2.1.1. And then fire came …...........................................................................................................................................20
2.2. Lime-based binders, technology, and development ....................................................................................23
3. MAGNESIAN AND GYPSUM BINDERS ........................................................................................................................37
3.1. Magnesian binders ................................................................................................................................................38
3.1.1. Magnesian reactions............................................................................................................................................39
3.2. Gypsum binders ......................................................................................................................................................42
3.2.1. Gypsum cycle........................................................................................................................................................45
4. POZZOLANIC BINDERS ...................................................................................................................................................48
4.1. Pozzolanic reactions..............................................................................................................................................55
4.1.1. Reaction paths ......................................................................................................................................................57
5. HYDRAULIC BINDERS ......................................................................................................................................................59
5.1. General information..............................................................................................................................................64
5.1.1. Cement microstructure .......................................................................................................................................66
5.1.2. Hydratation of hydraulic binders ........................................................................................................................69
5.1.3. Supplementary cementitious materials.............................................................................................................70
6. EARTHEN ARCHITECTURE .............................................................................................................................................72
6.1. Clay minerals ...........................................................................................................................................................76
6.2. Earthen architecture .............................................................................................................................................79
7. STRUCTURAL COMPOSITES ..........................................................................................................................................82
7.1. Masonry....................................................................................................................................................................83
7.1.1. Mortar ...................................................................................................................................................................83
7.1.2. Masonry units .......................................................................................................................................................86
7.2. Concrete ...................................................................................................................................................................90
7.2.1. Different types ......................................................................................................................................................92
7.2.2. Degradation ..........................................................................................................................................................97
8. ANALYSIS OF BINDING COMPOSITES...................................................................................................................... 108

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 8.1. Petrographic analysis of binding composites ............................................................................................. 110
9. MORTARS AND PLASTERS: THE INFORMATION FROM ARCHAEOLOGY ...................................................... 114
9.1. Literary sources ................................................................................................................................................... 115
9.2. The use of mortars in ancient building contexts: foundations, walls, vaults .................................... 123

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 1. INTRODUCTION

, also called , the techniques and industry involved in the assembly

and erection of structures, primarily those used to provide shelter.
Construction is an ancient human activity. It began with the purely functional need for a controlled
environment to moderate the effects of climate. Constructed shelters were one means by which human being
were able to adapt themselves to a wide variety of climates and become a global species.
Human shelters were at first very simple, and perhaps lasted only a few days or months. Over time, however, even
temporary structures evolved into such highly refined forms as the igloo. Gradually, more durable structures began to
appear, particularly after the advent of agriculture, when people began to stay in one place for long periods. The first
shelters were dwellings, but later other functions, such as food storage and ceremony, were housed in separate
buildings. Some structures began to have symbolic as well as functional value, marking the beginning of the distinction
between architecture and building.
The history of building is marked by a number of trends.

Increasing durability of the materials used. Early building materials

were perishable, such as leaves, branches, and animal hides. Later,
more durable natural materials – such as clay, stone, and timber –
and, finally, synthetic materials – such as bricks, concrete, metals,
and plastics – were used.
Quest for building of ever greater height and span; this was made
possible by the development of stronger materials and by
knowledge of how materials behave and how to exploit them to
greater advantage.
The degree of control exercised over the interior environment of
buildings: increasingly precise regulation of air temperature, light and
sound levels, humidity, odors, air speed, and other factors that affect
human comfort has been possible.
The change in energy available to the construction process, starting
with human muscle power and developing toward the powerful
machinery used today.

Construction today is a significant part of industrial culture, a manifestation of its diversity and complexity and a
measure of its mastery of natural forces, which can produce a widely varied built environment to serve the diverse needs
of society.

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 1.1. Construction materials and binders

What is ARCHITECTURAL HERITAGE?

The architectural heritage includes buildings
and structures, their contents and settings
and designed landscapes and demesnes
which are of artistic, technical, social scientific
and cultural interest. The architectural
heritage also includes street furniture,
statuary, paving, and structures associated
with the industrial heritage and vernacular
heritage.
Architectural heritage generally applies to
structures, buildings, streetscapes or
landscapes which postdate Anno Domini (AD)
1700 but can include structures of
archaeological interest and structures which
predate AD 1700. Article 1 of the Convention for the Protection of the Architectural Heritage of Europe (also
known as the Grenada Convention, Council of Europe 1985) defines architectural heritage as:

Monuments: all buildings and structures of conspicuous historical, archaeological, artistic, scientific, social
or technical interest, including their fixtures and fittings.
Groups of buildings: homogeneous groups of urban or rural buildings conspicuous for their historical,
archaeological, artistic, scientific, social, or technical interest which are sufficiently coherent to form
topographically definable units.
Sites: the combined works of man and nature, being areas, which are partially built upon and sufficiently
distinctive and homogeneous to be topographically definable and are of conspicuous historical,
archaeological, artistic, scientific, social, or technical interest.

Architectural heritage assets are a finite resource which individually display a high level of architectural, artistic or
technical craftsmanship and collectively contribute to the character and sense of place of our towns, villages and the
cities.
Nationally, sites of architectural heritage interest are subject to statutory protection. Section 10 (2) (f) and Section
(51) of the Planning and Development Act 2000, places a statutory obligation on local authorities to include sites of
architectural heritage in their development plans and objectives for the protection of structures, or parts of structures,
which are of special architectural heritage interest. The principal mechanism for the protection of these structures is
trough their inclusion on the Record of Protected structures ( ) in the relevant city or county development plan.
Protected structures are defined under Part I Section 2 (i) of the Planning and Development Act as:

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 A structure, or a specified part of a
structure, which is included in a record of
protected structures, and, where that
record so indicates, includes any specified
feature which is within the attendant
grounds of the structure and which would
not otherwise be included in this
definition.

A structure is defined in Section 2 of the

Planning and Development Act as:

Any building, structure, excavation, or their thing constructed or made on, in or under any land, or any
part of a structure so defined, and in relation to a protected structure or proposed protected structure,
includes: (i) the interior of the structure, (ii) the land lying within the curtilage of the structure, (iii) any
other structures lying within the curtilage and their interiors, (iv) all fixtures and features which form part
of the interior or exterior of any structure or structures referred to in subparagraph (i) or (iii).

Section 51 of the Planning and Development Act defines protected structures as:

Structures, or part of structures, which form part of the architectural heritage, and which are of special
architectural, historical, archaeological, artistic, cultural, scientific, social or technical interest.

The Planning and Development Act also

introduced Architectural Conservation
Areas ( ). An is a place, area, group of
structures or townscape that is of special
architectural, historical, archaeological,
technical, social, cultural, or scientific interest, or
that contributes to the appreciation of a
protected structure or group of protected
structures. A list of and objectives for
are also contained in the relevant city or
county development plans.
Architectural heritage may also be afforded
protection under other county or city
development plan objectives including
Conservation Area ( ).
Architectural heritage assets may also be included in other official inventories. These inventories include the
National Inventory of Architectural Heritage ( ) etc. In considering additions to the , local authorities have
recourse to the which provides a source of guidance on the significance of buildings in their respective areas. While
these inventories do not afford statutory protection in themselves, they do recognize the heritage value of individual
heritage assets or landscapes and are used to identify heritage assets for protection.

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 All the processes of looking after a place so as to retain its cultural significance… based on a
Conservation respect for the existing fabric, use, associations and meanings. It requires a cautious
approach of changing as much as necessary but as little as possible.
Preservation Maintaining a place in its existing state and retarding deterioration.
Returning a place to a known earlier state by removing accretions or by reassembling existing
Restoration
elements without the introduction of new material.
Repair involving Returning dislodged or relocated fabric to its original location, e.g., loose roof gutters on a
restoration building or displaced rocks in a stone bora ring.
Returning a place to a known earlier state and is distinguished from restoration by the
Reconstruction
introduction of new material.
Repair involving
Replacing decayed fabric with new fabric.
reconstruction
Changing a place to suit the existing use or a proposed use. The definitions and activates
described above provide a framework, but decision-making and reasoning in favor of one or
another method is still required when considering change that may cause damage or harm,
whether proposed or previously carried out. Therefore, the need assess ‘significance’ arises.
In the UK, this term defines an inclusive approach towards a shared history – asking who
finds, interest, importance or value in a place or a building. Historic England identify a range
Adaptation of values that may be affected by change:
Which captures the intangible aspect of place, collective experience
Communal Value
and associated memory.
Historic Value Which is said to illustrate a past way of life.
Aesthetic Value Which describes sensory and intellectual stimulation.
Which describes the archaeological and longer term view of human
Evidential Value
activity in a place.

1.1.1. Energy balances

The study of the transformations of energy from one into another is called . The first law of
thermodynamics is concerned with keeping track of energy change. The second law of thermodynamics explains
why some chemical reactions take place, but others do not. Both laws are summaries of experience with bulk matter
and are independent of any model that we might have of its microscopic structure—you could do thermodynamics even
if you had never heard of atoms! However, we can use the models of atoms and molecules we have been developing to
elucidate these laws and enrich our understanding of them. The link between the properties of atoms and those of bulk
matter is statistical thermodynamics, the interpretation of the laws of thermodynamics in terms of the average
behavior of the large numbers of atoms and molecules that make up a typical sample.
Two of the fundamental concepts of thermodynamics are heat and work. People once thought that heat was a
material fluid called caloric, which flowed from a hot substance to a cooler one. The French engineer Said Carnot, who
helped to lay the foundations of thermodynamics, believed that work resulted from the flow of caloric, just as the flow

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of water does work by turning a water wheel. Some of Carnot’s conclusions survive, but we now know that there is no
such substance as caloric. About 25 years after Carnot proposed his ideas in the early 19th century, the English physicist
James Joule showed that heat and work are simply two ways in which energy can be transferred.

states that the

internal energy of an isolated system is
constant. A state function depends
only on the current state of a system.
The change in a state function
between two states is independent of
the path between them. Internal
energy is a state function, but work
and heat are not.
is the key to
understanding why one chemical
reaction has a natural tendency to
occur but another one does not. We
apply the second law by using the very
important concepts of entropy and
Gibbs free energy.
is the basis of the
numerical values of these two
quantities. The second and third laws
jointly provide a way to predict the
effects of changes in temperature and
pressure on physical and chemical
processes. They also lay the
thermodynamic foundations for discussing chemical equilibrium, which the following chapters explore in detail.

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 Enthalpy is the state function that allows us to keep track of energy changes at constant pressure. It is important
to realize that the enthalpy is not a measure of the energy that a system possesses in the same fundamental sense as
the internal energy. It is really an accounting device that accounts for the effects of allowing the volume to change
during heat transactions at constant pressure. When we transfer energy to a constant-pressure system as heat, the
enthalpy of the system increases by that amount. When energy leaves a constant-pressure system as heat, the enthalpy
of the system decreases by that amount. Entropy is a measure of disorder; according to the second law of
thermodynamics, the entropy of an isolated system increases in any spontaneous process. Entropy is a state function.
Gibbs free energy allows us to assess whether a reaction is spontaneous, and it also tells us how much non-expansion
work we can get from the system. The change in Gibbs free energy for a process is a measure of the change in the total
entropy of a system and its surroundings at constant temperature and pressure. Spontaneous processes at constant
temperature and pressure are accompanied by a decrease in Gibbs free energy.

is condition in the course of a reversible chemical reaction in which no net change in the amounts of
reactants and products occurs. A reversible chemical reaction is one in which the products, as soon as they are formed,
react to produce the original reactants. At equilibrium, the two opposing reaction go on at equal rates, or velocities, and
hence there is no net change in the amounts of substances involved. At this point the reaction may be considered to be
completed, i.e., for some specified reaction condition, the maximum conversion of reactants to products has been
attained. In physics, equilibrium is the condition of a system when neither its state of motion nor its internal energy state
tends to change with time.

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 1.1.2. Some general terms

The term geological

resource refers to all the solid, gas, and liquid
elements originating from the earth’s crust both
on the surface and below the surface with
optimal concentrations to be extracted. Based
on the potential usage, geological resources can
be classified into three main groups, namely:
♡ Material resources: that are
utilized in their physical form.
These include rocks, metallic and
non-metallic minerals, gemstones,
and others.
♡ Energy resources: that are
utilized to produce energy and or
further needs. Those include coal, oil, and gas, geothermal, groundwater, waterfalls, and others.
♡ Spatial resources: that are in the form of space or living space, for example land area, geomorphology,
and environment.

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 Based on this definition, geological resources can be defined as the accumulation of rock, metal and non-metal
mineral resources, coal, peat, solid bitumen, oil, natural gas, geothermal, and the environment (water and soil) existing
in the earth’s crust, both on the surface and below the surface, and are able to be extracted sustainably to meet human
needs.
Aside form the classification based on its potential usage, in general, geological resources are also classified as
renewable and non-renewable geological resources. What are they and what are included in these two groups?

Can be produced through natural regeneration. The timespan and place for the regeneration
Renewable geological

process are varied depending on the resource types. The examples of renewable resources are
water and soil. Soil regeneration is influenced by chemical, geological, hydrological, and biological
resources

processes. While water regeneration is controlled by the hydrological cycle that are influenced by
solar energy, climate, and topography. Although water and soil can be regenerated, excessive
extraction of renewable geological resources exceeding their capacity can cause depletion of the
resources and even worse the extinction. Sustainable use of renewable geological resources
requires extraction rate less than the regeneration of these resources or innovation of reusing the
resources (recycling).
The example of non-renewable geological resources are coal, petroleum, natural gas, rock
renewable
geological
resources

containing metals (iron, gold, copper, silver, lead, manganese, zinc) and non-metallic rocks. Non-
Non-

renewable geological resources will be depleted when they are continuously extracted due to the
long geological formation of these resources (millions of years). The use of non-renewable
geological resources today will surely reduce their reserves and availability.

Defined as the deliberate processes utilizing the control and manipulation of fire, or more
simply, the use of fire as a tool. The rems is frequently used in respect to high-temperature processes involved in the

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production of inorganic materials, but can also be used in respect of earlier habitual and controlled used of fire for
cooking, hearing, light and other activities. The uses and impacts of fire upon human evolution are ongoing debates.
There has long been a traditional
disciplinary emphasis on the where and when
of the earliest high-temperature
pyrotechnologies. These two questions have
provided a major focus for fieldwork,
laboratory analysis and occasionally
experimental replication by several
generations of material scientist, chemist, and
geologists. The societal revolutions
underpinned by the introduction of new pyrotechnologies as proposed by earlier, yet sill highly influential, archaeologists
such as V. Gordon Childe have been exposed as largely speculative. However, the contribution of these pioneer
archaeological scientists beyond this traditional emphasis to investigate how and why early pyrotechnologies were
created was, with notable exceptions such as Cyril Stanley Smith and hist students, frequently limited to explanations
grounded in technical constructions (e.g., kilns and furnaces), technical thresholds (e.g., temperature and atmosphere),
resource exploitation (e.g., fuel and taw materials), and rational economic behavior (e.g., least cost benefit and labor
mobilization). These traditional explanations were critiques extensively by theoretically orientated archaeologists for
treating the technologies and materials in isolation and are far to disengaged from the social context in which they were
produced, used and understood. Yet, as more recent scholarship has demonstrated convincingly, pyrotechnologies can
provide the detailed data required to evaluate how and why technological changes occurred within human
history. The choice underlying the observed sequences of transformative actions on materials performed by individuals
and communities can be reconstructed and subsequently compared across space and time as well as withing their
environmental, physical and social contexts.
However, the archaeometric data and discussion, are
usually published primarily in journals such as Journal of
Archaeological Science or Archaeometry. The technical
presentation of archaeometric findings is either not
understood or simply not engaging the majority of
mainstream archaeologists. The consequence is that the
major advances in understanding pyrotechnological
inventions and innovations in early societies have simply not
reached a broader archaeological audience. Though the
relationship between archaeology and archeomaterials research remains the subject of intense debate, the aim to
analyze materials and technologies and investigate how were they shaped by past societies is no longer in doubt.

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 Cement, mortars, and binders are
materials with adhesive and cohesive properties
primarily used for construction purposes. They form
an important class of building materials and have been
employed to create, protect, or decorate building and
engineering works for at least 10 000 years. Over the
last decades, as interest in ancient building materials
and practices has grown, a substantial number of
investigations have been devoted to the analysis of
samples taken from old masonry structures, finishing
coatings, and ornamental elements. Typically, the
materials samples have been analyzed for:
♡ Determining their composition and properties
♡ Deriving information about their production and its organization
♡ Assessing their age
♡ Understanding the causes of their degradation and evaluating repair and conservation strategies
A variety of analytical techniques have been used, and several standard protocols have been proposed to guide
mortar characterization.
Ancient mortars have attracted the attention of many specialists from different fields, not only from archaeology,
history, and conservation science, but also from architecture, civil engineering, and materials science. Many terms have
been used to describe them; and the lack of a common vocabulary across disciplines has led to inconsistency and
confusion in terminology. Different materials have been designated by the same term and different terms have been
applied to the same material. The terms cement, mortar and binder are no exception in this regard and have been
adopted as both generic and specific names for various materials.
Mortars may be defined as composite materials obtained by adding water to a mixture made up of two basic
components, a binder and a filler. The binder is the substance that gives consistency and adhesiveness to the mortar. It
forms a continuous matrix and plays an essential role in the setting process. While it is not impossible to use a binding
substance alone, in practice it is often necessary to add a filler, that is, a material that gives it bulk, strength, and stiffness.
Usually, this material consists of finely divided mineral matter, or of aggregates. Additional components eventually
incorporated into the mix to further enhance its performance or to achieve special properties are usually regarded as
additives. Water is used to make the mixture plastic and workable long enough for it to be properly placed and shaped.
Once in place, the paste progressively hardens into a solid and relatively permanent material as the binder sets.
It is to be noted that the terms binder and cement are frequently used interchangeably. However, in its more
restricted sense, cement only refers to a specific type of binder, produced with modern equipment and technologies.
Moreover, it should be also specified that mortar and concrete are similar in composition. Concrete is also composed
of water, a binder, and a filler. It may, however, be regarded as a distinct material, since it contains both fine and coarse
aggregates. The use of sand, gravel, or crushed stone as aggregates significantly affects the physical and mechanical
properties of the final product. Unlike mortar, concrete has no binding force, but can be used alone and is strong enough
to bear heavy loads.
Many different kinds of building constructed with mortar still survive in different parts of the world. They attest not
only to the widespread use of mortar, from prehistory up to the present day, but also to the great variety of mortar types.
Archaeological and historical evidence suggest that the selection of particular mortar was determined by several factors,
including the availability and cost of raw materials, local building practices, and mortar applications. As it is extremely
versatile and easy to produce in various forms, mortar has fulfilled a wide range of functions. Briefly, it may have served
as:

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 ♡ A bonding material (for bedding, jointing, and pointing stones and bricks, or for infilling masonry structures)
♡ A finishing material (for internal plastering, external rendering, flooring, waterproofing, and sealing)
♡ A decorative material (for casting, modeling, and fixing or supporting architectural ornaments)

A composite material (shortened to composite) is a material which is produced from two or more constituent
materials.
These constituent materials have notably dissimilar chemical or physical properties and are merged to create a
material with properties unlike the individual elements.
Within the finishing structure, the individual elements remain separate and distinct.
A binder or binding agent is any material or substance that holds or draws other materials together to form a
cohesive whole mechanically, chemically, by adhesion or cohesion. In a more narrow sense, binders are liquid or
dough-like substances that harden by a chemical or physical process and bind fibers, filler powder and other particles
added into it.
Cement based on Portland-type clinkers, mortars (pastes and plasters prepared with fine aggregates), and other
binders form an important class of construction materials:
♢ They are all supplied as powders
♢ When mixed with water they form a fluid mass (paste) that can b e shaped, molded, added to other
components, or attached to the surface of other materials
♢ The paste then hardens spontaneously at normal environmental conditions

Binding materials are used in building to the aim of:

♢ Making structural elements for constructions
♢ Increasing the resistance of the construction by linking the structural and architectural elements
♢ Increasing waterproof and protecting masonry surfaces from environmental degradation
♢ Preparing substrates for artwork and decorative purposes

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Excluding last century’s binders and adhesives based on polymeric compounds, the binders used in antiquity are
based on:
♢ Carbonates (calcite, dolomite)
♢ Sulphates (gypsum)
♢ Alumino-silicates (cements)

Masonry is the building of structures from individual units, which are often laid in and bound together by mortar;
the term masonry can also refer to the units themselves. The common materials of masonry construction are brick,
building stone, cast stone, concrete block, glass block, and adobe.

Mortar is a workable paste constituted by a mixture of sand, a binder, and a water, which hardens to bind masonry
units, to fill and seal the irregular gaps between them,
spread the weight of them evenly, and sometimes to add
decorative colors or patterns to masonry walls.

Concrete is a composite material composed of fine and

coarse aggregate bounded together with a fluid cement
(cement paste) that hardens (cures) over time. The mixture
forms a fluid slurry that is easily poured and molded into
shape.

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 2. CALCIC BINDERS

Mineral phases in
Starting reactive
Production process Material-water mixture Final product the hardened aged
material
material
Slaked lime (lime putty) Lime plater Calcite
Lime-plaster (quicklime) Calcinations of limestone
Slaked lime + fine aggregate Lime mortar Calcite + aggregate

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 2.1. Historical Survey

Living in a sheltered place, permanently or temporarily, is a

fundamental need of humans. Nevertheless, the use of natural
materials to build shelter is not exclusive to humans: termite
mounds, birds nests, beaver dams, and beehives are perfect
examples of efficient architectural skills on the part of animals.
According to Mike Ashby:

The difference lies in the competence demonstrated by man

in his extraordinary ability to expand and adapt that
competence and development.

After dwelling in natural caves and an extensive period of

preparation of temporary structures made of organic materials
(skin, wood, leaf, etc.), the development of long-lasting architecture
in human prehistory was based necessarily on the clever use of
natural rocks and/or man-made binders.
The use to plaster huts and floors is the
most direct use of natural minerals to solidify surfaces and make
them impermeable. This follows from the physical properties of clay minerals which exhibit a small particle size and a
marked flat morphology derived from the layered crystal structure. Clays in excess water form colloidal suspension, and
the settled fractions posses ideal plastic properties, so that readily formable materials can be obtained easily by soaking
dry clay minerals.
Clays (and loess in China) have been used since
Neolithic times to plaster walls (inside and outside),
to consolidate and smooth rough floors and
eventually reshape them repeatedly after use, to
waterproof roofs made of organic material, and
eventually as a mortar between stones and, finally,
mudbricks. There is ample evidence of this
architectural use of clays in the Middle East starting
from the 10th millennium BC. In its simplest form,
with no use of pyrotechnology, a masonry wall can
be composed of sun-dried bricks (adobe) bound by a
moist layer of mud that, on drying, makes the wall a
solid mass of dry clay. In other cases, earth-based
structures are formed by direct application and shaping of the constructions, and these techniques are variously referred
to as:
♡ Cob, if they have a load-bearing role
♡ Wattle and daub if the earth has an infilling role
In some cases, the clay slabs or blocks can be cut directly out of clay or muddy soil if they are naturally consolidated
by organic material (turf, sod) or other pedogenetic processes. The man-made clay bricks and the clay mortars regularly

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contain a substantial organic (straw, dung) or inorganic component (gravel, pebbles) in order to avoid cracking upon
drying – a technology developed before or in parallel with pottery making. The past use of unfired or sunbaked clay
products is often difficult to assess in the archaeological record because they are subject to rapid degradation mainly
by wind erosion, water and salts. Only in rather arid climates are ancient occurrences still recognizable, in most cases as
structures embedded in mounds (tells) formed by layers of sequential human activity.
The earliest evidence of the use of sun-dried bricks is reported from
the Pre-Pottery neolithic layers in Jericho, Israel ( ),
in Nemrik, Iraq and in Ganj Darreh, Iran at least from the
. Evidence of the use of mudbricks in the Indus Valley
(Harrapa, Mohenjo-Daro) started at about the same time (
). Jericho stands as a special site combining the early
systematic evidence of the use of mud-brick buildings alongside the
earliest example of a Cyclopean structure, a massive round tower ~10
m in diameter and standing to almost the same height; though the
significance of such massive construction is still debated. There is ample
use of mud-brick structures in the site of Çatalhöyük (
) and a number of other Anatolian sites, together with painted mud
plaster covering internal and external structures, for both practical and
symbolic purposes. Interestingly, although there is evidence that
Çatalhöyük people could have used pyrotechnologically produced lime
plaster, there is no firm evidence of it being employed. The wall surfaces
as well as the interior floors of the structures at Çatalhöyük were
carefully plastered and frequently re-plastered in time, but were coated
in earthen plaster, which were supplemented by a thinner coat of local
white marly clay. The first Mesopotamian building in brick on a monumental scare occurred in the Tell Halaf period (
). Rectangular mould-based bricks were introduced in Mesopotamia at least from the 4th or 3rd
millennium BC, rapidly becoming decorated or inscribed.
The tradition of using earthen architecture based on a mixture of clay, water and straw is still largely present in many
rural areas of the world, the splendid multi-story Al Mihdar Mosque of Tarim, Yemen, and the Mosque of Djenne,
Mali being two amazing examples of earthen architectural achievements. The technological basis of modern earth
constructions is very similar to that inferred from the prehistoric record. It is worth mentioning that several trends of
contemporary architecture (earth architecture, sustainable architecture, bioarchitecture, etc.) actively propose the
modern use of clays or consolidated clays as natural materials in building. Furthermore, in the field of modern and
ancient earthen architecture there are many unresolved issues concerning earthen conservation interventions on
historic building, settlements and archaeological sites composed of earthen materials. The Getty Conservation
Institute ( ) through its Earthen Architecture Initiative, a long-term legacy of the past Terra project, is at the
forefront of active research and education on the theme.

2.1.1. And then fire came …

The Sumerian, Babylonian, Assyrian, and Hittite civilizations used sun-dried clay tablets widely for cuneiform
inscriptions, which was the written system for most of the language of the Mesopotamian region. Large archives of

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tablets are available starting from about the 4th millennium BC and they
present a number of conservation problems because they are fragile
and salt-loaded. Only a very small number of them were originally fired,
often accidentally during destructive conflagrations, and these are the
most stable ones. Paradoxically, high temperature helps their
preservation, so that modern electrical heating up to 740°C seems to be
one of the best conservation treatments to stabilize these materials. By
firing clay tablets at high temperature, conservators are now applying
the long-known pyrotechnological process which has been the basis of
production of clay figurines since Upper Paleolithic times (Venus of
Dolní Veštonice), the making of early fired ceramics in Eastern Asia
since at least ~15000 BC, and the shift from sun-dried to fired bricks in
Mesopotamia around the 3rd millennium BC. It is the very same firing
process transforming plastic clays into stable structural products:
♡ During firing the clay minerals are dehydroxylated
progressively and reactive oxides are formed
♡ Yielding glass and a variety of high-temperature crystal phases
♡ Depending on the starting clay composition and the time temperature path
High temperatures and long firing times imply more complete reactions, better crystallization and highly
sintered micro-structures. Technically, fired bricks are ~15% denser than corresponding mudbrick of the same size,
and about five times more resistant to compression. They are also lighter than natural limestone but possess almost
doubled values of the compressive strength of many common carbonate stones.
.
Fired bricks bearing inscriptions have been found in most Middle Eastern excavations, including Babylonia, Nimrud
and Nippur. The buildings in many of the Mesopotamian tells are made of mixed construction materials:
♡ Mainly mudbricks
♡ Fired bricks
♡ Stones
In fact:

Once bricks had been developed, it became general practice to build the mass of a building in sun-dried
bricks, whilst facing the lower courses and paving the floors with kiln-fired bricks. In a country short of
wood for fuel, backed bricks were a luxury, commonly used only where necessary to protect the unfired
from erosion by wind or water.

The large prevalence of mudbricks may prove that:

Burnt bricks were not as fundamental to Mesopotamian civilization as was fine stone dressing to
Pharaonic civilization.

The culmination of burnt brick construction is Mesopotamia was during Neo-Babylonian times. A Mesopotamian-
type evolution of building techniques is present also in the Indus Valley, where the transition from mudbricks to fired
bricks appears in the Kot-Dijan period (2800 – 2600 BC) and burnt bricks become common in the mature Harappan stage
(2600 – 2450 BC), used mostly with simple clay mortar. There are no other known examples of structural use of fired

21
 bricks elsewhere in the world until the first half of the 1st
millennium BC, whereas already in the 2nd millennium BC there is
ample evidence of the use of terra-cottas for roofing tiles and
temple decorations in Greece and later in Etruria. Roofing tiles
were also introduced in China during the Shang Dynasty (1700 –
1027 BC).
It is puzzling to note that everywhere in the world the process
of mudbrick firing for architectural purposes occurred several
thousand years later than the use of pyrotechnology to fire lime
and ceramics in the same regions. The production of fired bricks of
course required large fuel resources and substantial manpower. In
any case the bricks were used to produce more flexible architecture and more stable masonry, even it the bricks units
were not strengthened with binder. In Mesopotamia a mixture of gypsum and clay was mostly used as mortar,
apparently following an interesting regional pattern, although the lack of scientific analyses and the use of ambiguous
terminology for materials makes many of the early archaeological reports rather unreliable. Note that some of the
Mesopotamian buildings encompass the early known water-treatment structures. In several of them some degree of
waterproofing was obtained by use of fired bricks and tar plastering. In Mesopotamia the first use of bitumen (a mixture
of gypsum and bitumen) as mortar in masonry is recorded, as also reported by historical sources.

Further, I must relate where the earth was used as it was dug from the moat and how the wall was
constructed. As they dug the moat, they made bricks of the earth, which was carried out of the place they
dug, and when they had molded bricks enough, they baked them in oven s; then using hot bitumen for
cement and interposing layers of wattled reeds at every thirtieth course of bricks, they built first the border
of the moat and then the wall itself in the same fashion… There is another city, called Is, eight days’
journey from Babylon, where there is a little river, also named Is, a tributary of the Euphrates river; from
the source of this river Is, many lumps of bitumen rise with the water; and from there the bitumen was
brought for the wall of Babylon.

The latter phrase of Herodotus indicates how common the tar material was in the area.

22
 2.2. Lime-based binders, technology, and development

The first artificial binders used by mankind are the limestone- and gypsum-based plasters used widely in the Near
and Middle East in the 7th and 8th millennia BC. The technological basis of plaster material is very simple:
♡ The reactive compound (quicklime in the case of lime plaster) is obtained by burning limestone at the
appropriate temperature.
♡ Heated block is ground to a fine powder and slaked with water to form a slurry (at high water/solid ratio)
or a paste (at low water/solid ratio) composed of portlandite (calcium hydroxide, Ca(OH)2).
In Roman times long aging of the slaked slurry in excess water was priority with respect to the modern attitude of
using the ground powder and mixing it with water into a paste at the time of application. The effects of aging on the
properties of the lime putty has been investigated thoroughly, as the issue is relevant for the preparation of restoration
lime mortars.

The reactions involved in the production and use of lime are:

CaCO3 (calcite) + heat → CaO (lime) + CO2 (carbon dioxide)

CaO (lime) + H2O (water) → Ca(OH)2 (Portlandite) + heat
Ca(OH)2 + CO2 → CaCO3 + H2O

The temperature needed to produce CaO should be ~850°C, though the decomposition reaction of the carbonate
can also proceed at slightly lower temperatures (780 – 800°C) in reducing conditions. Operational temperatures of lime-

23
kilns are in the range 920 – 1000°C in order to speed up the decarbonation reaction. Excessive temperatures are avoided
because they produce unreactive dead-burned lime. The production of lime therefore is a very energy-intensive
process, and it requires a substantial amount of biomass fuel. It has been estimated that the ratio of fuel
biomass/quicklime is in the range 2 – 5, so that about 4 – 8 tons of wood would be required to produce the quicklime
necessary for one house. Considering the diffusion of lime had a serious impact on the environment. Similar claims were
raised for the Mayan Lowlands.
Traditionally, the burning of carbonates (limestones, dolomites, travertine, marbles, but also shells and corals) is
performed in , which are massive furnaces sometimes several meters high, charged from above with
decimeter- to meter-sized blocks of limestone, and then fired for days by adding wood or charcoal to the combustion
chamber at the base. Several ancient lime-kilns have been excavated from Roman, to Late Classic Maya, to more recent
times. A detailed description of lime burning operations in Roman times was supplied by Marcus Porcius Cato.

The fired blocks are then ground to obtain the fine powdered quicklime that is, however, rather unstable in
normal humidity conditions and tends to hydrate quickly to portlandite. If the CaO powder is mixed with an exact (i.e.,
stoichiometric) amount of water (lime/water = 75.7/24.3 = 3.12 by weight) the product is a fine dry powder and the
process is called because there is exactly the right amount of water required to produce portlandite. If
the CaO powder is mixed with excess water then a smooth paste is obtained in slurry form, and the process is referred
to as . The portlandite paste (slaked lime or lime putty) can then be used as a binder and an architectural
component (filler, adhesive, cracks sealer, floor consolidant, surface smoother, etc.) or as a raw material for modelling
objects, vessels and even artwork. After the application the paste dehydrates slowly and reacts with atmospheric CO2
producing a hard material composed of microcrystalline calcite. The kinetics of carbonation are slow so that in recent
samples the reaction is not complete and residual crystals of portlandite may be observed.
The quality of the binder depends on a variety of parameters, including the composition, porosity and impurity
content of the fired limestone, the maximum temperature and the time temperature path of the firing, and
the conditions of slaking. The starting limestone should have a non-carbonate mineral content (usually silicates and
clays) of < 0.1) or dolomite (CaMg(CO3)2), then the material is a magnesian- or dolomitic-lime. The periclase (MgO)
produced together with lime during firing has much slower rehydration kinetics with respect to CaO, so that in the
magnesian putty both periclase and brucite (Mg(OH)2) are present together with portlandite.

24
 During carbonation and hardening the microstructure of the slaked lime paste changes significantly. The
identification of lime-derived calcite from an unconsolidated archaeological layer of ground calcite therefore is essentially
based on the carbonate particles’ dimensions (in the range 0.12.0 mm), its texture, and its mechanical properties. Optical
microscopy is therefore a very useful tool to investigate the nature and texture of ancient lime mortars, although it may
prove difficult to discriminate between fine-grained calcite of geological origin (chemically precipitated) and that derived
from portlandite.

The presence and role of calcite nodules in the mortar (the so-called ‘lime lumps’) have been the subject of ample
discussion, because of their importance in identifying ancient mortars, in the quantitative determination of the original
binder/aggregate proportions, and in the protocols sometimes employed for radiocarbon dating. In general, we may
summarize that calcite nodules in the binder may have originated in one of three ways:
♡ As residues of unburned geological carbonate
♡ As in-homogeneously slaked lime putty forming portlandite lumps that underwent late carbonation
♡ As reprecipitated late calcite
Failure to identify the proper nature of the lumps may lead to serious errors in the interpretation of the material and
eventually in radiocarbon dating of the inappropriate fraction of the binder.
Very careful Fourier transform infrared spectroscopy ( ) work, based on the ratios of specific absorption
peaks of calcite (specifically the ratio between in-plane and out-of-plane bending modes of the carbonate group), has
been proposed as a technique to discriminate lime derived-calcite from natural calcite. This discrimination may also be
done using the luminescence properties of calcium carbonate. Both methods rely on the different density and
distribution of atomic defects in the calcite crystal structure. In principle the fractionation of carbon and oxygen stable
isotopes during portlandite carbonation could also be used to test the nature of the carbonate phase. Once more, the
issue is especially important when characterizing the carbonate fraction for radiocarbon dating of the mortar. In many
cases the presence of anthropogenic (i.e., man-made) carbonate is identified through micromorphological features,
or by textural elements such as clear smooth surfaces representing the floor used, sometimes with a finishing coating.
The earliest well characterized example of quicklime production is the Hayonim Cave in Israel, dated to the
Natufian period at ~10410 BC. Numerous other reports of lime-plaster in the Pre-Pottery Neolithic sites of the Levant
(8770 ky BC) were reviewed and characterized carefully by Kingery and co-workers (1988). They demonstrated beyond
any doubt that there was a widespread use of pyrotechnologically produced lime-based plaster in the Near East coastal

25
area from Palestine to Anatolia. Especially striking are the plastered faces from Ain Ghazal in Jordan, originally
modelled on human skulls, and the exceptional sculptured head found in Jericho and Yiftahel.

There are numerous interesting issues concerning the prehistoric development of lime-based binders in the Pre-
Pottery Neolithic of the Levant. In the first place, it is curious that limestone firing and production of reactive quicklime
pre-dates ceramic pyrotechnology, although this gap is now being partially revisited. Further, the plasters in this early
phase do not comprise the rendering of the floor, they are the floor itself, i.e., they are made as durable surfaces
supporting loads and meant to be cleaned. They also rapidly extended to walls for protection and decoration . It is
evident, however, that at least several thousand years separate this early burst in the use of lime binders from any
structural use connected with fired bricks in the region. Actually, there seems to be a puzzling discontinuity between this
widespread use of lime plaster in the 8th and 7th millennia BC in the Levant (especially in skull-plastering, figurine modelling
and floor plastering), and the subsequent evidence of use of lime in architecture in the 2nd millennium BC.
The case of Lepenski Vir, a small Neolithic village on the banks of the Danube, stands as an isolated example
apparently unconnected with the previous Levantine experience and the subsequent reprise of lime plaster in the
Minoan world. In Lepenski Vir a large number of peculiar trapezoidal huts have been excavated, each with a thick floor
of red-colored limestone plaster. The settlement has been radiocarbon dated to the Early Neolithic (6200 – 5400 BC),
though there are claims of early Mesolithic occupation. Despite the uncertainty in the early life-span of the village and
nearby settlements (Vlasac, Padina and Hajdutka Vodenica), the question of interest to us is whether the lime
pyrotechnology on the Danube has anything to do to the previous Levant experience, or rather is a stand-
alone development of lime production. Carefully contextualized investigations are needed to clarify the problem.
The report of the use of lime at Makri, Thrace and at the Drakaina Cave, Kefallonia, Ionian Islands in the 6th
millennium BC may prove to be an interesting link between the Levant and the Serbian lime experiences.
After the Lepenski Vir case, there were some four thousand years of technological discontinuity, or maybe lack of
archaeological information. Chronologically, the successive occurrences of lime mortars and lime plasters are in the
Minoan world (2nd millennium BC), where lime-based materials were used extensively in Crete, Cyprus and elsewhere
for wall decorations and cistern waterproofing. Without dwelling on the details too much, extensive lime plastering in
the walls has been found, mainly to cover rough wall surfaces and floors, leaving the smooth ashlar un-plastered. Plasters

26
covering wall surfaces have a fine lime finish or wash as they serve as support for the famous Palatial paintings (i.e.,
Knossos) and decorations. They are always lime-based, even when the wall-building stones are rock gypsum. We stress
that no hard evidence is observed in this period of the use of lime mortar as a structural component (i.e., to strengthen
the masonry or ashlar blocks): all the Minoan, Mycenean and the later Classical Greek ashlar is dry.

A key development occurring in the Greek world is the consistent and systematic use of
(volcanic ash, i.e., , or crushed ceramics, i.e., ) replacing inert aggregate in the mortar used
for waterproofing cisterns and waterways in Bronze Age Crete and Cyprus. The tradition continued in pre-Roman
Rhodes. The later use in Laurion, Greece (4th century BC) of a very peculiar waterproofing layer obtained by mixing Pb-
rich oxides (litharge) and Fe,Mn-rich ores with lime is also reported. This special occurrence is related to the mining and
treatment of Pb-rich ores in the nearby mines, though it is difficult to define whether the layer investigated is a deposit
developed as a byproduct of the ore processing or the conscious recycling of litharge slags during plaster manufacture.
As well discuss, the reported occurrences bear two important consequences:
♡ There is evidence of the appropriate use of hydraulic mortars and pozzolanic reactions in the
Mediterranean area well before the Roman world.
♡ There is no firm evidence of the structural use of lime mortars in constructions (i.e., as a binder among
masonry units) before the second half of the 1st millennium BC, except maybe the very early use of hot
bitumen within the Mesopotamian context.
Outside the Mediterranean world, there is hardly any evidence for the use of lime plaster prior to the late 2nd
millennium BC.
No evidence is reported on the early use of plaster or mortar in the pueblo cultures of the US southwest or in the
South American Andean world, where the Inca’s massive constructions of polygonal stones were assembled by
smoothing the edges to make close contacts. Limited use of lime mortar, sometimes mixed with bitumen, has been

27
reported at Machu Picchu (1450 – 1550 AD), though direct accounts and analyses are scarce. In Central America the
use of lime plaster is reported in Preclassical and Classical Central Mexico, and from the Classical Maya period. Some of
the earlier examples are the plastered platforms at Cuello, Belize (1100–600 BC) and Nakbé, Guatemala (900–600
BC). In Mayan monuments the use of lime is structural, although spectacular use was made of lime as substrate to
paintings and frieze decoration. Magnesian lime plasters were also extensively used. An early use of pumices as
lightweight aggregate in poured lime mortar is reported for the roof slab of Building Y in the El Tajin site, the sacred city
of the Totonac people (850–1100 BC).
Interestingly, there is
ample evidence that in
Mesoamerica the lime plaster
was prepared by mixing
different kinds of organic
materials such as honey or
juice extracted from a
number of local plants such as
cactus (nopal juice, Opuntia
ficus indica). The type and
extent of the effect of the
organic molecules on the
putty is still debated. On one
hand there are claims that the
organics destabilize
portlandite chemically and
release Ca ions, thus
promoting pozzolanic
reactions with impurity
phases. On the other hand, the physical effect of packing is emphasized, with the claim that the organics help the
development of a more homogeneous microstructure, with smaller portlandite crystals, and ultimately a greater
mechanical strength. The debate is open.
In China, there are accounts of the early use of lime during the Shang (1700–1027 BC) and the Zhou (1046–771 BC)
Dynasties, the lime being mixed with sand and loess for wall facing and flooring. The palace site of Xianyang, Shaanxi
province (350 BC) had the floors prepared with a mixture of lime, stone, and pig’s blood to give a dark red color. The
mortar formulation comprised lime, loess, and sand; it became known as ‘tabia’ and became the regular material in use
during the Eastern Tsin Dynasty (317–420 AD). Lime-based mortars were used extensively in ancient architecture, with
examples reported in the Qiantan River dam, Dutifulness Monument, Sticky Rice Bridge, and others, completed mainly
before the Ming (AD 13681644) and the Qing dynasties (AD 1644 – 1911). According to written sources lime-plaster
production followed a traditional standard formula mixing lime and sticky rice solution up to 1520 wt.%, and today the
plaster is reported to be still in very good condition. Sticky rice is a type of rice grown in southeast and east Asia and it is
composed mainly of amylopectin. Again, it seems that the organics influence the calcite dimensions and growth kinetics
during carbonation. A variety of organic substances has been reported to have been used in traditional Chinese mortar
recipes, used both in masonry and in wooden buildings.
The greater Indian region had a very early start with the use of mud and bitumen mortars (referred to as vajralepa
mortar) related to the Indus valley civilizations, much as in Mesopotamia. The vajralepa bitumen was made of wood-tar
and was used to waterproof walls and structures in bath houses. There is evidence of the early use of lime plaster in the
ovens and pits of the houses in Kalibangan, Rajasthan, dated to the proto-Harappan period (3500 – 2500BC), although
it came into more common use since the last centuries of the 1st millennium BC. The pure lime binder was often obtained

28
from kankar (lime
nodules) found
abundantly among
river gravel. Kankar
contains ~70% calcite,
30% clay and a fraction
of sand with other
impurities, so that
appropriate calcination
of kankar may confer
some hydraulic
property to the mortar.
Impure mortars with a
variable sand/lime ratio
are found in Buddhist
settlements
(Nagarjuna-Konda,
225–325 AD) and in the
city of Kausambi,
Uttar Pradesh (35 –
350 AD). A number of
more recent buildings offer evidence of the widespread use of fired bricks and mortars, especially in mosques, temples,
monuments, and tombs. The Great Stupa at Sanchi, Madhya Pradesh is the oldest stone building in India (3rd
century BC) and one of the largest fired-brick domes in the world.
The Charminar in Hyderabad (1591 – 1593 AD) was built with granite stones and mortar. Lime plasters were also
used extensively for decorations on temples and other monuments. The investigation of the decorations applied on rock
at the carved Ellora caves (6 – 11 century AD) surprisingly showed that many of the plasters contained a substantial
amount of kemp hurd (Cannabis sativa), so that the decorations provide one of the first examples of kemp-reinforced
plaster. Furthermore, India offers a long tradition of organics mixed with lime allegedly to increase carbonation and
durability:
♢ Curd
♢ Jaggery
♢ Bel pulp (the fruit Aegel mermelos)
♢ Black gram
♢ Oil of margosa
The change in the paste properties resulting from the addition of organic compounds has long been known, e.g., for
traditional recipes for lime plasters in ancient Mesoamerica, China and India. Egyptians, Minoans and romans modified
the lime mortars with Arabic gum, animal glue, fig’s milk, egg yolk and many other organic substances in an attempt to
improve the mechanical or working properties. In the De Architectura Vitruvius described explicitly the mixing of lime
with oil (calx ex oleo subacta) to improve waterproofing. The practice was passed down to the Middle Ages and
Renaissance, especially in the case of quality mortars for decoration and in applications exposed to weathering agents.
A large variety of organic and protein substances was apparently tested, with mixed results: cereal dough, animal blood,
fermented wine, beer, milk derivatives including cheese, bee’s wax, lard, and many others.

29
The kinetics and chemical mechanisms regarding calcination of carbonated had been widely discussed during the last
decades; especially calcination of CaCO3, because of its technological importance and its simplistic stoichiometry.
There are many aspects not well understood about the reaction. Several reactions have been presented since there
is no agreement upon the mechanism.

CaCO3 (s) → CaO (s) + CO2 (g), ∆HR = +168 kJ/mol

CaCO3 (s) → CaO* (s) + CO2 (g) ↔ CaO (s) + CO2 (g)
CaCO3 (s) ↔ CaO (g) + CO2 (g) ↔ CaO (s) + CO2 (g)

Hyatt et al, propose the existence of metastable structure of CaO. It is supposed that the active CaO, denoted as CaO*,
acts as a bridge between the freshly made CaO crystal and the unreacted CaCO3. Another approach, proposed by
L’vov is that CaCO3 decompose into gaseous species CaO and CO2 and simultaneous condensation of low volatility
CaO.
Regardless of mechanisms involved in calcination, the reaction is summarized in three steps:
♢ Heating the particle surface and heat transfer from the surface to the reaction front
♢ Chemical reaction occurs at the reaction front
♢ CO2 transfer from the reaction front to the surrounding atmosphere
The reaction depends on several parameters, e.g., chemical composition of the limestone, limestone grain size,
surrounding gas composition, and ambient temperature. This contributes to uncertainty in the kinetic field.

30
The chemical composition and structure of limestone varies even within the same quarry, as there are different layers
that may separates structures and composition of the limestones. Thus, the thermal behavior varies, since thermos-
physical properties, e.g., specific heat capacity, thermal conductivity and reaction enthalpy varies with temperature.
Thermal conductivity varies with material and temperature. During phase changes, the thermal conductivity of the
material may dramatically change. The thermal conductivity usually falls within 3-0.6 [W/(mk)] for limestone at 0 –
700°C, and for lime 1.7-0.3 [W/(mk)] at 100 – 1100°C.
The specific heat capacity varies with material and phase. Reported values for limestone ranges from 0.6-1.7 [J/(gK)]
and for lime 0.7-1 [J/(gK)]. For lime, it was found that the average heat capacity is independent of temperature,
however, the heat capacity of lime differs individual due to different morphology within each lime.
The reaction enthalpy is independent of origin and is published as 178 kJ/mol at atmospheric conditions. However,
at calcination temperature, the reaction enthalpy varies between 160-172 kJ/mol, since the calcination temperature
has been reported to vary between 850-925°C when comparing limestone samples from all over the world.

♢ The temperature to produce CaO must be above 898°C, though the decomposition reaction of the
carbonate can proceed also at slightly lower temperatures (780-800°C) in reducing conditions.
♢ Operational temperatures of lime-kilns are in the range 920-1000°C in order to speed up the decarbonation
reaction.
♢ Excessive temperatures are avoided because they produce unreactive dead-burned lime.

In ancient times production was carried out on batch basis with each cycle averaging 15 days. The cycle is as follows:
i) 3 days for loading (14 person required)
ii) 3 days for calcining
iii) 4 days for cooling
iv) 3 days for discharging
v) 1 day for cleaning the kiln

31
 ♢ The quality of the binder depends on a variety of parameters,
including the composition, porosity and impurity content of
the fired limestone, the maximum temperature and the
time-temperature path of the firing, and the conditions of
slaking.
♢ The starting limestone should have a non-carbonate mineral
content (usually silicates and clays) lower that 5-10 wt%, and
the carbonate should be pure calcium.

The aim of the slaking reaction is to produce a slurry containing

calcium hydroxide particles with high surface areas. Because particles
with higher surface areas are more highly reactive, such slurries are
more efficient in the end-use process, creating the required result
from the minimum input of lime.
There are six main factors that impact the slaking process and,
therefore the quality of the lime slurry:
- Slaking temperature
- Slaking water temperature
- Slaking water chemistry
- Slaking residence time
- Slaking agitation
- Steam control
Slaking temperature: perhaps the most important, as it directly influences the particle size of the hydrated lime –
and, therefore, the reactivity of the slurry. The closer the slaking temperature is to the boiling point of water 100°C,
the finer the particles size, the greater the surface area, and the most reactive the slurry. Ideally, it should also not
exceed this temperature so as to avoid boiling over the slaker.
Slaking water temperature: the second fundamental factor of lime slaking. Particular challenges arise when using
cold water (< 21.1°C) in the slaker, as it makes it difficult to reach the required slaking temperature. This results in a
less reactive slurry (due to coarser hydrated lime particles), as well as producing significantly more waste product
(known as a grit or residue). To avoid these issues, we typically recommend a slaking water temperature of between
21.1°C and 32.2°C, and the use of a water preheater when the water falls below that.
Chemistry of the slaking water: water with high concentration of sulfates and sulfites (> 1000 ppm) can cause
delays in the slaking rate, as well as issues around the slaking temperature and wasted quicklime. High levels of
phosphates can similarly impact the slaking process, although are generally less detrimental to the process. When
possible, it is recommended to use portable water, which typically contains low levels of the problematic
chemistries.
Slaking residence time: factor to consider when using a continuous slaker (detention, ball mill and paste). As
quicklime constantly moves through these types of slaker, it is important to ensure the quicklime spends enough time
in the slaker to complete the slaking reaction.
Slaking agitation: a poorly mixed slurry will not react well, reducing slaking speed and delaying the slaking reaction.
To avoid this, regular, proactive maintenance is required on the agitation device, whether that be mixing paddles or
agitators in the case of detention, paste and batch slakers, or the ball mill media in a ball mill slaker. In the case of paste

32
slakers, proper mixing is also needed to mitigate against the risk that localized hotspots (i.e., above boiling point) will
develop in the slurry.
Steam control: the slaking reaction will generate significant amounts of steam, which needs to be removed from
the slaker in a controlled fashion. If not controlled effectively, steam will naturally migrate through the path of least
resistance – which tends to be up the dry quicklime feed systems and into the silos. Here it will quickly degrade and
quality of the quicklime, may cause handling issues – including blockages – and may result in significant scale build-up
inside the silo. Steam that escapes into the surrounding work environment also poses a safety risk to personnel, as
well as creating issues around cleanliness and housekeeping.

♢ The fired blocks are ground to obtain the fine powdered

quicklime, which, however, is rather unstable in normal
humidity conditions and tends to hydrate to portlandite
( ).
♢ The CaO powder is mixed with and exact (i.e., stoichiometric)
amount of water (lime/water = 75.7/24.3 = 3.12 by weight) the
product is fine dry powder and the process is called dry
hydration, because there is the right amount of water to
produce portlandite.
♢ If the CaO powder is mixed with excess water than a smooth
paste is obtained in a slurry form, and the process is referred to
as lime slaking.
♢ The portlandite paste (slaked lime or lime putty) can then be
used as a binder and an architectural component (filler, adhesive,
cracks sealer, floor consolidant, surface smoother, etc.) or as a
raw material for modelling objects, vessels, and even artwork.

33
 ♢ In early Roman times there was the widespread belief that aging of the slaked lime was crucial to the quality
of the plaster.
♢ Vitruvius (De architectura, Book VII) had realized the importance of properly mixing the lime with a hoe to
ensure good homogeneity and above all slaking for a sufficient time in pits.
♢ Similarly, Plinius (Naturalis Historia, Book V) claimed that lime putty needed to mature for at least three
years to produce a good binder. Long homogeneous mixing and aging definitely helped in producing a slaked
compound with a very fine grain size and little porosity, and this is one of the ‘’secrets’’ of the excellent quality
of Roman mortars, which are still astonishingly solid and hard.

Setting time plays a big role in hydration behavior. The influence of the setting on the building process in the Roman
period is not well known. Vitruvies only stated that sea-sand slow down the drying process as well as the construction
process. Therefore sea-sand can not be used for mortar to erect vaults.
On the other hand, Alberti (De re aedificatoria) is more precise and writes that the building process had to be
stopped from time to time to allow mortar to dry properly. Alberti describes how the centering of vaults and arches
have to be lowered down to guarantee a proportional and smooth setting of the masonry due to the plastic
deformation of the mortar. This plastic deformation influences the stress distribution in the arch and in the vaults.
Setting can take some years and requires a little bit of humidity, mortar may not dry out as this slows down the
hardening. The progress of the construction has to take into account the time needed for the setting of the mortar.
The understanding of the mechanisms responsible for the production, the hardening and the setting of lime for
different applications, has changed together with the evolution of scientific understanding and human’s perception
of the earth.

34
35
36
 3. MAGNESIAN AND GYPSUM BINDERS
Starting reactive Production Material-water Mineral phases in the hardened
Final products
material process mixture aged material
Calcination of Dolomitic or
Lime-plaster (quicklime) Slaked magnesia-lime Calcite, brucite, periclase
dolomite magnesian plaster
Bassanite (± anhydrite) Gypsum plaster Gypsum
Gypsum-plaster (plaster Calcination of
of Paris) gypsum Bassanite + fine
Gypsum mortar Gypsum + aggregate
aggregate

37
 3.1. Magnesian binders

If the carbonate contains magnesium, deriving from the presence of magnesian calcite (Ca1-xMgxCO3 with x < 0.1)
or dolomite (CaMg(CO3)2), then the material is a or . The periclase (MgO) produced
together with lime during the firing has a much slower rehydration kinetics with respect to CaO, so that in the magnesian
putty both periclase and brucite (Mg(OH)2) are present with portlandite.

38
 3.1.1. Magnesian reactions

% CaMg(CO3)2 in carbonate rocks:

- 10% = magnesian limestone
- 50% = dolomitic limestone
- 90% = calcareous dolostone
- 100% = dolostone

Dolomite calcination is an important step in the processing of dolomites into other materials of higher value.
Dolomite begins to decompose into its oxide in one step in an inert atmosphere, as in the following reaction:

CaMg(CO3)2(s) → CaOxMgO(s) + 2CO2(g)

The mechanism is different when dolomite decomposes in atmosphere containing CO2, as it decomposes with two
step reactions as in the following:

CaMg(CO3)2(s) → CaCO3(s) + MgO(s)+CO2(g)

CaCO3(s) → CaO(s) + CO2(g)

The study on dolomite decomposition using nitrogen as the inert atmosphere, showed that decomposition of
dolomite is a one step process that began at 700°C and finished at 850 °C with activation energy of 149,5 kJ/mol. This

39
study also showed that the maximum conversion of dolomite calcination in a laboratory scale tubular furnace is 100% at
900 C. Meanwhile, study on dolomite decomposition in tubular furnace using atmosphere consisting of air and CO2, as
an atmospheric replication in rotary kiln, shows that decomposition of dolomite occurs in two steps, starting at 650°C
until 820°C with 162 kJ/mol of activation energy. In addition, the maximum conversion of 80 – 90% in this atmosphere
was achieved at 900 °C.

Differences with respect to CALCIC LIMES:

♢ Lower heat development (contribution of MgO)
♢ Slower hydrogen rate (MgO less soluble than CaO)
♢ Reduced volume increase (MgO crystals absorb less water)
♢ Brucite (Mg(OH)2), fibrous-acicular crystalline habitus, less plastic behavior than portlandite (Ca(OH)2),
lamellar habitus

Degree of carbonation → 60% magnesian putty / 95% calcic putty

Mechanical strength → magnesian putty, good even before carbonation / calcic putty, null before carbonation

40
41
 3.2. Gypsum binders

Gypsum rock and gypsum plaster have exactly the same chemical composition and cannot be distinguished by
chemical tests. , however, has a distinctive microstructure consisting of a forest of well-formed
microscopic interlocking, needle-like crystals that cause the rehydrated reaction product material to cohere. This
material is easy to form and use (it forms the core of modern wallboard and is widely used for sculptural purposes), but
has limited application as a structural architectural material. The mix tends to set quickly, and the resulting product is
relatively soft and susceptible to chipping. It absorbs water and can only be used for exterior purposes in dry climates.
Gypsum plaster has a solubility in water of about 0.2% weight at room temperature; the solubility of lime plaster
depends on the water acidity but is about 0.0015% weight. As a result, lime plaster is much more resistant to moisture;
gypsum plaster, because of its solubility, is not well suited for exterior architectural use except in quite dry climates. Thus,
even though lime plaster is more difficult and expensive to manufacture and to use, its properties make it the material
of choice. Because of solubility, gypsum can undergo metamorphic changes when exposed to moisture for long period,
more so as the ambient temperature is raised. Initial material consists of fine particles that, over time, are changed by
process well known to scientists as grain coarsening by Ostwald ripening and as densification and strengthening by
liquid-phase sintering. As a result, we should expect plasters exposed to wet conditions from time to time over several
millennia to have a coarse grain size and perhaps become harder and stronger. Metamorphic changes can be
accelerated by autoclave treatment (a more powerful pressure cooker) and we have tested this conjecture in the
laboratory by preparing a gypsum plaster from Colorado gypsum heated at 150°C and a lime plaster made from natural
New England limestone heated at 900°C.

42
Gypsum = CaSO4 x 2H2O

Properties:
- High setting speed
- High hardening speed
- Hygroscopic material (it absorbs H2O)
Uses:
- Binder for masonry (warm climates)
- Binder for interiors
- Stuccoes, decorations

♢ Gypsum-based mortars and plasters have been used

since ancient times, especially to cover masonry, as
decoration, or as a support for mural paintings.
♢ Due to their setting upon addition of water, gypsum-
based binders could be considered the first hydraulic binder used by mankind since ca. 9000 years BP.
♢ Gypsum was the most common binder in Ancient Egypt both for masonry and decorative purposes since
Pharaonic times.
♢ Gypsum plasters were commonly used in the Middle East and in countries around the Mediterranean basin,
especially during the Middle Ages (e.g., Islamic Architecture).
♢ In the area around Paris, gypsum mortars were thoroughly used in gothic buildings such as the Cathedrals
of Chartres and Bourgues, which may explain why gypsum-based binders are known as Plaster of Paris.
♢ Despite its low strength and poor durability in humid environments, examples of gypsum mortar application
in northern Europe are numerous.

43
♢ The technological bases of gypsum binders are very similar to those of lime plaster.
♢ Gypsum blocks are heated in the kiln to produce the reactive bassanite (calcium sulphate hemihydrate),
or a mixture of bassanite and anhydrite (anhydrous calcium sulphate) if the temperature is too high or
the firing time is too long. Anhydrite is commonly not desired because it is much less reactive than bassanite.
♢ An advantage over lime is that the dehydration of gypsum to bassanite takes place at relatively low
temperature (nominally at 128°C), generally in the range 100 – 160°C depending on the water pressure and
therefore the production of the plaster of Paris requires much less energy and biomass fuel then lime plaster.
♢ However, the gypsum-bassanite-anhydrite transitions are fairly complicated from the kinetic point of view.
♢ Depending on the pressure and on the thermodynamic path different forms (polymorphs) of bassanite
can be formed (α-, β-, -bassanite), which differ in the thermodynamic and kinetic properties because of
structural ordering, microstructural features such crystal size and morphology, and defect density.
▪ The α-form is produced by dehydration of gypsum in conditions of high PH2O, it is commonly fairly
crystalline, it requires less water to rehydrate, thus producing a dense plaster with good mechanical
properties.
▪ The β-form is produced by dehydration at low PH2O or in vacuum, it is nanocrystalline and has a
high surface area, thus requiring much more water to rehydrate into gypsum, and the plaster has
consequently more volume shrinkage.
▪ The -bassanite is generally produced by slow hydration of anhydrite.
♢ Anhydrite also has several forms depending on the temperature of bassanite dehydration (α-anhydrite: 160-
200 °C, β-anhydrite: 250-300 °C, -anhydrite: 300-600 °C): the solubility of anhydrite decreases with the
temperature of formation.
♢ Above 900 °C the sulphate starts decomposing into CaO and SO2.
♢ The powderized bassanite (plaster of Paris) is very hygroscopic and needs to be stored in dry places.
♢ The plaster is used by mixing bassanite and water, causing the dissolution of bassanite (and eventually the
associated anhydrite) and the precipitation of gypsum.
♢ The growth of the gypsum crystal creates the interlocked crystal grid that makes the hardened plaster.

44
 ♢ The hardening process may be slowed down by adding salts that increase the solubility of gypsum, or it
may be accelerated using a mixture of gypsum seeds and potassium sulphate, favoring nucleation and
precipitation. The presence of additives, the relative proportions of bassanite and anhydrite forms in the
mixture, their crystal size and morphology, and the temperature of dehydration are the parameters affecting
the reactivity and the final type of plaster, i.e., its ability to hydrate fast or slow, its crystallinity and
appearance, its workability.

3.2.1. Gypsum cycle

Crushing the gypsum rock is advisable before processing further, especially if subsequent heating is to be done in a
pan rather than a shaft kiln. Crushing will ensure a product which is more uniform and requires less energy to heat.
Crushing should reduce the gypsum to grains of less than a few millimeters across. Gypsum sand does not need crushing.
Heating may be done in a number of ways involving a range of technology levels and costs. The simplest
method is to mix the gypsum stone and fuel in a mound or in a shallow pit in the ground and burn it. Medium-scale batch
production might be carried out in an excavated hillside kiln, a shaft kiln with alternate fuel and stone layers, or a
permanent walled kiln. An alternative method is to heat the gypsum in large pans or on a flat metal plate positioned
above a kiln.

Gypsum rock when heated to 100 – 190°C looses ¾ of its H2O.

45
 CaSO4 x 2H2O → CaSO4 x ½ H2O + 3/2 H2O Plaster of Paris

This low burning process is incomplete calcination. When calcination is carried out at temperatures above 190°C all
water is removed:

CaSO4 x 2H2O → CaSO4 + 2H2O Gypsum anhydrite

The high-burning process is complete calcination.

When gypsum is mixed with water, the resulting paste is plastic

(shapeable) which sets and subsequently hardens as time passes. Process of setting causes the loss of the initial plasticity

46
or the gaining of rigidity. Hardening is a process where gypsum gain in strength and the ability of the material to resist
indentation or abrasion.

CaSO4 x ½ H2O + 3/2 H2O → CaSO4 x 2H2O

CaSO4 + 2H2O → CaSO4 x 2H2O

If the amount of water used in the preparation of the paste is more than that required for the chemical reactions,
the extra water is lost eventually through evaporation.

47
 4. POZZOLANIC BINDERS

Starting reactive Production Material-water Mineral phases in the hardened

Final products
material process mixture aged material
Hydraulic mortar
Calcination of Slaked lime + fine
Lime-plaster (quicklime) (Roman opus Calcite, Zeolites, C-S-H + aggregate
limestone aggregate + pozzolan
caementitium)

Mixing of lime plaster with partially or totally reacting aggregate marks the development from lime-based aerial
mortar to hydraulic mortars. If the quartz aggregate of the mortar (formally inert) is replaced in part or fully with reactive
Si,Al-rich material (generally defined pozzolanic material) then the highly alkaline environment created in the lime-
saturated water induces the dissolution of the silicate or aluminosilicate phases and the subsequent precipitation of
insoluble Si-rich hydrous phases.
The reactive pozzolanic material may be natural or synthetic silica glass, volcanic ash, radiolarite or diatomaceous
earth, phytoliths, ceramics, clay, metallurgical slags, or any other reactive aluminosilicate compound. The materials
employed in the past as pozzolanic additions in hydraulic lime mortars are also used today as supplementary
cementitious materials ( ) in the formulation of modern binders. Such materials can be represented in the lime-
silica–alumina (CaO–SiO2–Al2O3) ternary diagram. The reaction of lime with aluminosilicate phases is referred to as a
pozzolanic reaction or a hydraulic reaction. When the presence of reactive aluminosilicate phases stimulates the
pozzolanic reaction in the binder, then it is called a ‘hydraulic’ or ‘pozzolanic’ binder (‘plaster’, ‘mortar’). If natural
volcanoclastic materials were not available, hydraulicity in the binder was often obtained by the use of crushed ceramics
(pottery, bricks, tiles) together with traditional inert aggregates. Fired ceramic is actually compositionally similar to
volcanic materials, so the pozzolanic character of thermally activated clays and fired clay-based materials has been
investigated thoroughly. The best ceramic-material yielding pozzolanic reaction is the very fine-grained kaolinite-rich
pottery in which meta-kaolinite-type phases were formed by firing in the temperature range 600–900°C. The use of clay
minerals in the production of the ceramics as well as firing at higher temperatures induces the formation of less reactive
phases, such as mullite, and thus reduced pozzolanic reactivity.
One of the earliest instances of pyrotechnologically produced lime mortar mixed with volcanic ash occurs at Asikli
Höyük, Turkey. The pozzolanic reaction observed in the Pre-Pottery Neolithic B Asikli Höyük plaster (8th millennium BC),
however, is probably accidental and there is no evidence of systematic use of hydraulic materials in this early period.
The possibility indeed exists that the silica phytoliths and other siliceous minerals derived from plant ashes could indeed
have induced pozzolanic-type reactions in other cases of primitive plaster technology.
Hydraulic binders based on pozzolanic reactions developed in the Greek and Aegean world in the 2nd millennium
BC. They became the technological basis for the highly successful binders used in later Roman architecture. Between the
Aegean tradition and the standardized adoption of the hydraulic mortar technology by Romans some thousand years
later there is a fuzzy period of use and diffusion of these materials, possibly linked to cultural diffusion from the Eastern
Mediterranean along the African coasts during the first Iron Age. Important clues to these pre-Roman developments are
the hydraulic plasters of Tell es-Safi/Gath, Israel and the carbon-containing mortars (ash mortars) used in Punic
cisterns of Tunisia. It is again important to note that the hydraulic mortars in all these examples are limited to flooring
and cistern plastering, mainly with a waterproofing function. Consistently, the analysis of the excavated structures and
the mortars from a residential quarter in the Punic-Roman area of Palermo, dated firmly to before the final conquest of

48
the city by the Romans during the First Punic War (254 BC), show only wall and floor plasters, with crushed pottery
present in two of the samples investigated.

The crucial evolution in the architectural use of hydraulic mortars occurred in a relatively short period in the first half
of the 2nd century BC: the mortar is finally employed to strengthen masonry structures in both public and military
buildings. It is the first fully recorded structural use of binders in
architecture, in which the binder intimately links the units of the masonry
and actively contributes to the mechanical strength of the composite
structure. Marcus Porcius Cato (De agricultura liber, dated approximately
to 160 BC following the Oxford Classical Dictionary) described the systematic
use of lime-based mortars as a binder in foundations, walls and complex
architectural components of buildings. Following the critical chronological
revision by Mogetta (2015), with which the present authors largely agree, the
oldest known remaining example of concrete (caementa) in Rome is the
Porticus Metelli, dated to ~130 BC. Most of the other concrete building
traditionally dated to the late 3rd century or the early 2nd century BC should be
postdated to the last two decades of the 2nd century BC. Furthermore, there
are recent indications that pozzolanic mortars were used to pour the
foundations of fortification walls in wet areas far from Rome at very early
periods. Apparently, Roman military engineers already knew that volcanic
pozzolan performs better than crushed pottery in marshy or salt-water
environments. If confirmed, such occurrences of pozzolanic reactions are

49
even older than the examples in Rome, suggesting an early and rapid diffusion of the technology involving hydraulic
reactions based on volcanoclastic material.
Three major innovations and/or technological optimization in the use of the binders were introduced rapidly and
systematically at the beginning of the 2nd century BC or shortly thereafter.

♡ The use of mortars to strengthen important architectural structures: for the first time binders are
not limited to plastering and waterproofing.
♡ The systematic use of crushed ceramics (pottery, bricks, tiles) in terrestrial structures that required
resistance to water. This technology, certainly derived from the Greek world, was carefully optimized in
the so called opus signinum, widely used in cisterns, aqueducts, fountains, and baths.
♡ The exclusive use of highly pozzolanic volcanoclastic material in hydraulic mortars used to build
structures in contact with sea water.

Not surprisingly, it was in late Republican times (2nd – 1st

centuries BC) that the architectural capabilities of Roman
engineers, previously limited by the robust but cumbersome
properties of ashlar (the Servian walls of the 6th century BC
were still built in opus quadratum), started to produce efficient,
solid and durable buildings rapidly complying with the formula
later encoded by Marcus Vitruvius Pollio. As the only
architectural book surviving from classical antiquity, the
Vitruvian statements and prescriptions are considered the
primary source of information concerning Roman and
Greek building techniques. Vitruvius’ De Architectura met
with immense favor and reputation from the Renaissance to
the end of the 19th century, becoming the conceptual
reference for most Western architecture of the period. In his
work, Vitruvius not only illustrated building techniques and
architectural theories, but described at great length the nature
and preparation of the materials, including mortars. As an
example, Vitruvius in his Book II indicates clearly that the
proportion of lime and sand must be increased if poor quality
or marine sand is used as aggregate. His descriptions find neat
experimental evidence in a number of recent investigations of Roman materials, where Vitruvius’ recipes for binder
formulation and preparation found precise confirmation.
During the last part of Republican times, Roman engineers crucially improved the Aegean-derived technology of
hydraulic binders by using slaked lime in a mixture with local high-alkali volcanic ash, first drawn from the banks of the
river Tevere, and then from the volcanic sands found near Naples, at Pozzuoli; hence the name pozzolan, still in use
today. Recent studies of the evolution of Roman mortars from Republican through Imperial times reveal specific changes
in the composition and use of the mortar components. The mineral components of the ash outcrops within and around
ancient Rome show that specific zeolite-rich tuffs with highly reactive properties were carefully selected from the
very beginning in order to produce exceptionally hard and durable mortars. These important studies not only confirm
the early chronology of Roman mortars identified by macroscopic observations, reparation of quality mortars (black and
red sands, or harenae fossiciae: De Architectura 2.4.1). Further, Vitruvius states that this pozzolanic material is the only
one that is able to harden under water (De Architectura 2.6, hence the name hydraulic mortar). The physicochemical
and engineering characteristics of mortars used for the construction of Roman harbors have been investigated

50
extensively in the frame of the project.
Not only are the outstanding properties and durability
confirmed, but the tuffs used in the mortars of the
harbor of King Herod in Caesarea seem to have been
transported all the way from the Bay of Naples. The
Roman harbor builders knew very well that proper
hardening of mortar at sea required good quality
pozzolans, even at the cost of long-distance
transportation.
The local occurrence of reactive volcanic sand (such
as in Central Italy, or in the German Eifel area, known as
Trass), and the availability of recycled crushed pottery
and bricks gave Roman engineers the appropriate
technology to build flexible, innovative and durable
architecture and ultimately set the basis for the efficient infrastructure of the Roman empire. In fact the Romans also
developed the concept of lightweight robust structures by the use of innovative building techniques, such as the
vaulting tubes, the use of appropriately shaped bricks, and the incorporation of lightweight pumiceous aggregates in the
binder. The arches of the Colosseum and the Pantheon dome are reported to have been made with such innovative
materials and techniques.
Note that the word cement (opus caementicium) in ancient Roman times referred to the concrete masonry of
monuments composed of cm-sized brick and tuff fragments (caementa) used as aggregates and which are bonded by
hydraulic mortars with alkali-rich, calcium-alumino-silicate volcanic ash sands. Only in recent times has the meaning
changed to refer to modern clinker-based materials.
The ability of producing and using
excellent mortars was lost slowly after the fall
of the Roman Empire. The dome of the
Hagia Sophia Basilica in Costantinople
(532-537 AD) is probably the last great Roman
building formed by the monolithic pouring of
Roman pozzolanic mortar based on crushed
ceramics. Lime-based mortars continued to
be used through the Middle Ages, though in
many cases the mortars were of rather low
quality, made of partially burned lime, sometimes mixed with charcoal and clays, and the lime putty was frequently
unaged and poorly slaked. The careless preparation made them mostly porous and degradable. Many of the Saxon,
Norman and Langobardic materials are of this kind. The standardized production during the Roman Empire was thus
followed by very local productions, mostly having only a small technological content, and it was only in specific and
prestigious construction sites that high-quality binders were produced, as in the case of the Byzantine mosaics in
Ravenna, or the Leaning Tower of Pisa. In the latter case, the absence of volcanoclastic material and the presence of
CSH products hints at the possible use of very reactive silica sources, such as diatomaceous earths. Most of the mortars
used through the Middle Ages until the Renaissance to build cathedrals, fortresses and palaces are lime-based. However,
some binders show a limited hydraulicity due to pozzolanic reactions. Although discontinuous, the tradition of making
hydraulic mortars by the use of crushed ceramics persisted in several regions of the Roman Empire and beyond: it is
called cocciopesto in Renaissance Italy, horasan in Turkey, homra in the Middle East, surkhi in India.
A peculiar kind of traditional material produced by clay activation is called sarooj. It was apparently used widely in
ancient Persia and other areas around the Persian gulf, especially for cisterns and waterproof structures. It is claimed

51
that a number of ancient temples and buildings, such as the Elamite zigurrat at Chogha Zanbil, Iran were built
partially using sarooj, although experimental evidence is scarce. The reported preparation of the material indicates that
a mix of clays, dung and water was sun-dried into decimeter-sized blocks, which were then fire-heated for activation.
The final product was ground and mixed with lime to produce the final binder. Sarooj seems to be the earliest example
in which thermal activation of clay was consciously and systematically employed to obtain hydraulic reactions.
The technology based on thermally activated clays is regarded as one of the future solutions for the replacement of
modern Portland-based clinker with more sustainable products. As a matter of fact, our understanding of the pozzolanic
reactions that occurred in ancient hydraulic binders allows modern interpretation of their mechanical durability, and has
fundamental implications for the development and technological control of modern cement alternatives to Portland
clinkers. On a technical note, the protocols of separation and characterization of the binder fractions for reliable
radiocarbon dating of ancient mortars require adequate understanding of the phases present and their reaction history.
The presence and extent of pozzolanic reactions in ancient mortars is commonly assessed by:
♡ Measurement of the mechanical resistance to compression tests, which is substantially greater
that those measured on traditional lime mortars.
♡ Calculation of empirical parameters derived from bulk-chemistry measurements (i.e.,
hydraulicity index, cementation index).
♡ Characterizing the nature and micro-textural features of the mineralogical phases present in the
binder fraction of the composite, which are the result of pozzolanic reactions.

Testing the mechanical resistance is an indirect bulk measurement and leaves space for ambiguities in the
interpretation of the mechanisms that lead to the development of the physical properties. The hydraulicity index:

HI = SiO2 + Al2O3/CaO

Or the cementation index:

CI = 2.8 SiO2 + 1.1 Al2O3 + 0.7 Fe2O3/CaO + 1.4 MgO

Are generally proportional to the amount of Si,Al-rich species in the mortar, though the presence of aluminosilicate
phases is not sufficient to indicate that the pozzolanic reaction did actually take place to a sufficient extent in the binder,
as they can be inert or very slowly reacting.
On the other hand, a thorough mineralogical characterization of the phases and of the textures resulting from the
lime–pozzolan interaction yields direct evidence of the pozzolanic reaction. Adequate characterization, therefore,
requires identification of reaction products (by X-ray powder diffraction (XRPD), FTIR, Raman spectroscopy, or other
micro-analytical techniques) and/or micro-imaging of the reaction textures, such as the reaction rims formed around the
pozzolanic particles through dissolution-recrystallization processes. The limiting factor of the pozzolanic reaction rate in
general is the dissolution kinetics of silicate phases. The issue is fundamental when assessing the reactivity of materials
to be used as supplementary cementitious materials (SCM) in modern binder formulations.
The hydrous phases formed by the pozzolanic reaction have a variable composition depending on the chemistry of
the system. They range from pure C-S-H phases in the lime-silica join (tobermoritic Ca,Si-hydrates) tin ire cinokucated C-
A-S-H phases as the Al activity increases. Zeolite-like phases are favoured in complex N-K-C-A-S-H environments, and
their formation is reported to be enhances by interaction with sea water. It is the interaction between sea water and the
volcanic tuff that yielded tobermorite and zeolitic phases and produced the extremely hard and durable binders of
Roman harbors.

52
53
54
 4.1. Pozzolanic reactions

Greek and Etruscans started to mix some volcanic ash or finely ground pottery (cocciopesto) to the mortar, resulting
in materials with higher strength and durability. The volcanic tuff of Santorini (the so-called Santorini earth) was a
reputed material for the preparation of water-resistant mortar. Silica-lime reactions were also activated, probably by
chance, in one of the early instances of pyrotechnology at Aşıklı Höyük, Turkey (8200 to 7400 BC), where lime and
volcanic ash particles were mixed in the plaster. The possibility exists that the silica phytoliths and other alkali minerals
derived from plant ashes indeed could have induced pozzolanic-type reactions in other cases of primitive plaster
technology. The Romans, during the period between 300 BC and 200 AD, crucially improved this technology by using
the slaked lime in a mixture with high alkali volcanic ash (pozzolana) first from the banks of the river Tevere, and then
from the volcanic sands found near Naples, at Pozzuoli; hence the name pozzolan.
Recent studies of the evolution of Roman mortars from Republican
through Imperial times reveal neat changes in the composition and use
of mortar components: detailed investigation of the ash outcrops within
and around ancient Rome show that specific zeolite-rich tuffs with highly
reactive properties were carefully selected especially in later Imperial age
to produce exceptionally hard and durable mortars. These important
studies not only confirm the early chronology of Roman mortars
identified on macroscopic observations, but also confirm the incredibly
detailed description of the materials that Vitruvius indicated as ideal for
the preparation of quality mortars (black and red sands, or harenae
fossiciae: De architectura 2.4.1).
The physic-chemical and engineering characteristics of mortars used for the construction of Roman harbors are
presently investigated in the frame of the project. Not only the outstanding properties and durability are
confirmed, but surprisingly the tuffs used in the mortars of the harbor of King Herod in Caesarea Maritima (Israel)
seem to have been transported all the way from the Bay of Naples.

55
 The Romans are known to have used all the known occurrences of zeolitic tuffs, including Santorini (Greece) and
the volcanic tuffs present in the German Eifel area known as Trass. When volcanic sand was not available, finely ground
pottery and ceramics was used to induce hydraulicity to the material, a technique that originated in Minoan Crete.

56
 4.1.1. Reaction paths

Ca(OH)2 dissolution produces an alkaline solution saturated in Ca and

hydroxyl ions, with a pH over 12. At high pH values silica solubility increases, causing the pozzolana products to dissolve
according to hydrolysis processes at the mineral-water interface. Dissolution occurs at first in far-from-equilibrium, highly
undersaturated condition, with a progressive slow-down of the reaction until reaching of Ca(OH)2 saturated conditions.
During this phase, a layer of C-S-H phases replaces the external dissolved layers of the pozzolan grains, covering the
unaltered grain core, while it is believed the C–A–H phases precipitate far from the pozzolana grains due to the greater
diffusivity of alumina due to the smaller electric charge and lesser oxygen content.

After the initial dissolution period, a dormant phase occurs, linked to the previously
described formation of a protective layer enclosing the reacting pozzolana particles. Such periods terminates after the
rupture of the passivating layer, related to its semi-permeable characteristics, which allows osmosis of water from the
outer to the inner, more concentrated solution, and rupture due to the osmotic pressure.

The rupture of the passivating layer causes a massive triggering of nucleation and
growth of reaction products. Such exponential reaction rate increase is short-lived due to the rapid transition toward a
diffusion-controlled regime. Other factors contributing to the slow-down of the reaction are the consumption of the
smaller, more reactive, particles and a lack of space or densification of the C–S–H rim that hinders the free growth of the
hydrate particles. From this moment on, the reaction process proceeds indefinitely until total drying of the system or
total consumption of the reactants.

57
♢ Inosilicates (chain silicates)
♢ SiO3, radical
♢ Orthorhombic-monoclinic-triclinic symmetry
♢ Ca/Si ratio: between 0.8 and 2.3
♢ Complete solid solution between tobermorite (Ca/Si: 0.8) and jennite (Ca/Si:
2.3)
♢ Variable amount of structural water (variable basal d-spacing)

♢ Layered double hydroxides ( )

♢ Hexagonal symmetry
♢ Brucite-like structures
♢ Layers of cations with octahedral coordination
♢ Substitution of divalent ions (Ca2+, Mg2+) with trivalent ions (Al3+, Fe3+)
♢ Most common LDH’s are hydrotalcite (Mg, Al), hydrocalumite (Ca, Al),
calcium monocarboaluminate
♢ Ample solid solution

♢ Tectosilicate scaffold (Si, Al) and Na+, K+ and H2O ions in varying amounts.
♢ The tetrahedra form a continuous network of channels and cavities with variable
dimensions.
♢ H2O is weakly bound through hydrogen bonds to the anions of the lattice. It can
leave the structure by heating through the channels, leaving the structure
without causing its collapse

58
 5. HYDRAULIC BINDERS

Starting reactive Production Material-water Mineral phases in the hardened

Final products
material process mixture aged material
Portland cement paste Portland cement Portlandite, C-S-H, calcite
Portland cement paste + Portland cement Portlandite, C-S-H, calcite +
fine aggregate mortar aggregate
Calcinations of
Portland-clinker Portland cement paste + Portlandite, C-S-H, calcite +
limestones + clay Concrete
fine and coarse aggregate aggregate
Cement paste + fine Pozzolanic Portland Portlandite, C-S-H, calcite, Ca-
aggregate + pozzolan cement mortar aluminosilicates

A particular type of hydraulic binder was developed in Europe in the 18th and 19th centuries by firing impure
limestones containing clays in lime kilns; they are called natural hydraulic limes ( ) or Roman cements. In these
natural hydraulic binders the reactive phases are not added as aggregate, but formed in the kiln through the reaction of
the clays and the quicklime. They can be considered the precursors of modern Portland clinker. NHL were very popular
for building construction and façade decoration in Central Europe in the 19th century. They were, and are still, used
extensively for restoration of historical buildings because of their good mechanical properties and compatibility with
ancient materials.
A very early instance of production and use of NHL in
the 14th century AD was identified during the
investigation of the mortars and slags of the Gothic
Obrâny Castle, Moravia: the interpretation is that the
lime binder incorporated high-temperature phases
derived from the kiln lining and local metallurgical
activities. Slags from ore processing were also observed in
the mortars of the medieval archaeological complex at
Montieri, Tuscany, Italy, which is located in an area of
intense exploitation of argentiferous ores.
Both pozzolan-added mortars and NHL were used in
the Czech Republic to build 14th century bridges, such as
Charles Bridge in Prague and the Gothic bridge in
Roudnice. The slightly hydraulic character of the Narni
bridge, in Central Italy (3rd century AD) is thought to be
derived from the accidental firing of impure limestones, containing cherts. In extreme cases, the burning in lime kilns of
chert-containing limestones in the presence of alkali lowering the melting point of silica yields the production of
amazingly colored silica glasses, which were found at the base of the furnace after firing.
Vitruvius recommended the use of very white and pure limestone for the production of lime in classical times. It
appears that whenever the Vitruvian recipes were abandoned or not followed closely, the accidental use of impure
limestones with various amounts of silica or aluminosilicate phases randomly produced binders with very variable
degrees of hydraulicity. Sometimes the fine-grained size of the original material and the heterogeneity of the
microtexture makes it very difficult to assess the degree of hydraulicity and/or deduce unambiguously the complex
dynamic of the production process. The emerging picture is one of unstandardized binders and largely uncontrolled

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production processes from late antiquity until approximately the 18th century AD, when systematic experiments were
carried out to produce optimized materials.
A significant change from traditional lime
mortars was made by John Smeaton in
England in 1756, when he was involved in the
reconstruction of the Eddystone
lighthouse. As the story goes, he was driven
by the need to develop a masonry
construction durable in a marine environment
and thus built using a binding lime mortar that
did not dissolve in seawater. Among several
attempts, he also departed from the Vitruvian
recommendations of using pure white
limestone. Using clay-rich carbonates of marly
composition he obtained better hydraulic
properties than lime. This class of materials
may be defined as natural hydraulic limes
and can be considered intermediate between
slaked lime and modern Portland cement. Eventually the material that Smeaton selected for the lighthouse was a mortar
prepared with equal proportions of local argillaceous limestones (blue Liassic limestones) and pozzolan from
Civitavecchia, Italy, the closest stuff he could access resembling the ancient Roman material. Slightly improved mixtures
of this kind were in use until the introduction of Portland cement. v
In the first half of the 19th century the search for optimal hydraulic binders was pursued actively in several countries.
In England Smeaton was testing alternative formulations of hydraulic mortars, and J. Parker introduced and patented
a so-called Roman cement, defined as a:

Cement or tarras to be used in aquatic and other building and stucco work.

It was made by calcination of nodules of argillaceous limestone (known as

septariae) and it produced a quick-setting cement. In France, Louis Vicat’s
experiments led to the preparation of hydraulic lime by calcination of a mixture of high-
grade quicklime (produced by the chalk of the Upper Cretaceous carbonatic formation
of the Paris Basin) and clay. His formulation, called the twice-kilned process, met with
considerable success, and led his son Joseph Vicat to establish the well-known Vicat
Cement company. This is considered by many to be the
.
A lot of patents were issued around the same time establishing plants in southern England, including the London
area. The most famous one is that related to the three stage process of Joseph Aspdin (patented in 1824), who
named his product , because, at that time, the Portland limestone had a reputation among builders
for quality and durability, and he wanted to capture the similitude between his cement and Britain’s favored quarried
stone. Portland cement was marketed as an improvement in the production of artificial stone. In one of the several plants
established by Aspdin or his son, the temperatures were running high enough to produce partial or complete vitrification
and crystallize alite, as shown by the retrospective analysis of the type of clinker material from Aspdin’s kiln. The clinker
is the reactive product formed by cooling from the high-temperature processing (1450°C) of the limestone and clay
mixture within the kiln. The temperature is such that partial fusion occurs and the reacted molten material forms nodules

60
that are partly crystalline and partly vitrified, the whole material being highly reactive with water. The four major phases
making up the clinker are reported, though the real situation is made more complicated by the existence of several
polymorphs for each phase, and by compositional deviation from stoichiometry. The basic chemical composition of
Portland cement is shown and it is evident that the composition of the two major phases (alite and belite) lies on the
CaOSiO2 join as a result of the lime-silica reaction. The hydration products, composed mainly of calcium silica hydrates
(C-S-H) and portlandite also lie in the same portion of the diagram.

Following Blezard (2003), the historical evolution of clinkers after the illustrated pioneering experiments moved
from proto-Portland materials (i.e. Aspdin’s original patent), which shows limited interaction between CaO and SiO2
because of the limited temperature in the kiln, to meso-Portland materials, which are very heterogeneous materials
showing some silica-lime interaction and containing mostly belite and some alite, and finally to normal-Portland
cements as we know them today. The main characteristics of modern Portland clinkers are derived mostly from the
use of rotary kilns in place of the traditional shaft kilns, a technical development that also allows continuous production
in place of the batch process. The carefully-controlled initial formulation of calcareous and argillaceous components,
together with the use of the rotary kiln that determines a long permanence at high temperature and continuous mixing,
helps to:
♡ Minimize the amount of unreacted lime
♡ Maximize the alite/belite ratio
♡ Obtain the appropriate crystal size of the mineral components, commonly in range 10 – 40 μm

Modern clinkers contain about 60-65 wt.% of C3S, and < 2 wt.% of unreacted free lime. The standard reaction
properties of modern Portland clinker are essentially due to a high alite/belite ratio and to a careful control of the grinding
of the clinker into a fine powder.
The very reactive Portland cement powder is mixed with water to produce a final hardened material through a
series of complex reactions, the so-called hydration process, involving dissolution of the crystal phases, surface
reactions, gel formation, precipitation of new phases and textural changes. The different crystal phases present in the
clinker have very different reactivities, having the highest and the lowest. In fact is so reactive exothermally
in water that it can cause unwanted rapid setting of the paste (flash set), with consequent loss of workability. Therefore
calcium sulfate (commonly gypsum) is usually added to the clinker in the amount of ~48 wt.% as a set-controlling agent,

61
because the sulfate ion retards the dissolution of the clinker phases, and promotes the formation of ettringite. The finely
powdered mixture of clinker and gypsum is marketed as standard Portland cement (also called = ordinary
Portland cement), which is then mixed with water in the ratio water/cement > 0.38, i.e., the least amount of water
necessary for complete hydration of the cement phases. As in ancient binders, when an aggregate material is added to
the paste we have mortar (fine aggregate, such as sand with grain size < 1mm) or concrete (fine and coarse aggregate,
such as coarse sands or gravel). They can both be considered to be cement composites, with the aggregate having the
role of reducing the formation of fractures during the shrinkage that accompanies the hydration and hardening; for the
same reason temper is added to pottery clays before firing. The aggregate may be composed of any type of loose or
ground rock, and it is assumed not to react with the cement paste (hence, it is referred to inappropriately as the inert
component), though this is not necessarily the case.
Upon mixing with water, the clinker phases react at different times to produce first a series of intermediate phases
(the so-called AFt and AFm phases) such as:

Ca6Al2(SO4)3(OH)1226H2O ettringite
Ca4Al2(SO4)O612H2O monosulfoaluminate

And then the reaction proceeds to the final hydrous phases: portlandite and amorphous calcium silicate hydrate
(CSH), which are the phases forming the interlocked gridwork of the material and producing high mechanical resistance.
Figure 15 shows environmental scanning electron microscope (ESEM) evidence of the growth of ettringite and CSH at
different times on the surface of the clinker grains. It is important to understand that it is the microstructure of the
material, that is the final assemblage of crystalline and amorphous phases that governs the macroscopic and engineering
properties of the material. With time, portlandite will eventually convert into calcite through a carbonation reaction with
atmospheric carbon dioxide, so that abundant calcite is found in old cements.
Reaction kinetics play a crucial role in determining the final microstructural properties. The completion of the
hydration process may take days, months, or even years, depending on crystal size, defectivity and polymorphism of the
phases, porosity of the paste, environmental conditions, etc. The system is so complex that reactions can be inhibited
for a long time. It is often observed in old concrete that highly reactive species such as aluminates are still present years
or decades after manufacturing. Many of the practical problems in the modern cement industry derive from the lack of
control of clinker composition, poor concrete design, or sloppy practice: even small changes may affect the hydration
kinetics and determine substantial degradation of the engineering properties. Incidentally, the same problems, mostly
due to human factors such as incompetence and fraud, were present and well recorded in Roman times.
Strength development is related to the degree of hydration and to the speed of the process. In general, the slower
the hydration kinetics, the higher the compressive strength developed. This is one of the differences observed
between modern clinker-sand those produced in the early part of the last century. Modern cement is required to
develop high resistance to compression (> 40 MPa) within a few days of emplacement, whereas early 1900s cements
developed high strengths (in the range of 20-30 MPa) over much longer periods, because of the greater belite content.
This has some consequences also in terms of durability. High-compression resistance combined with tensional resistance
are, of course, obtained by steel reinforced concrete ( ), which is a composite in which the concrete is poured and
solidified around a metal skeleton. The French-Swiss architect, Le Corbusier, was one of the first to understand and
exploit the properties of SRC in modern architecture. He had discovered the use of reinforced concrete very early in Paris

62
 from one of the pioneers of its use, architect
Auguste Perret, and then employed it to realize his
architectural vision. He later wrote:

Reinforced concrete provided me with

incredible resources, and variety, and a
passionate plasticity in which by themselves
my structures will be rhythm of a palace, and
a Pompeiian tranquility.

Nowadays only ~35% of the cements produced

industrially for the global market are OPC, and most
of the materials are special composite formulations,
where special components or SCM are added to
enhance specific physicochemical or mechanical
properties, such as resistance to alkali or sulfates,
thermal resistance, or low-heat emission. The main
added constituents are:
♡ Latent hydraulic components (granulated blast furnace slags, class C fly ash) that have self-cementing
properties that need to be activated by OPC.
♡ Pozzolanic aluminosilicate components (class F fly ash, silica fume, metakaolin, pozzolan) that have no
self-cementing properties and need to be activated by portlandite.
♡ Non-reactive or poorly reactive components that modify the grindability of the clinker or the rheology
of the paste.

Because of the low market cost of cement, the materials added to the clinker are large-volume but low-cost
byproducts of other industrial activities. Therefore on one hand the production of cement represents a virtuous route to
recycle large quantities of waste material (e.g., slags from the metallurgical industry, fly ash from coal plants); on the
other hand the market for special cements will need alternative materials should the global changes in metal and energy
production decrease the availability of SCM materials in the future.
One of the most important properties of modern cement pastes and concrete composites is fluidity: it ensures the
possibility of transportation, pumping, levelling concrete to fit modern architectural requirements, and also proper
consolidation by grouting. The rheological and working properties of the cement and concrete are so important that
they are now controlled invariably by the use of chemical admixtures (water-soluble organic polymers) that allow good
fluidity of the paste with a smaller water/cement ratio. The net result is also a lower porosity of the paste and a greater
mechanical strength: ultra-high performance concrete and high-strength concrete are made this way, they can reach
compression strengths in excess of 150 MPa. The modern generations of plasticizers, ensuring fluidity at low water
content are called water reducing admixtures. Besides rheology, organic and inorganic additives are also used to control
specific properties of the mortars and cements, such as air entrainment (for better resistance to freeze and thaw cycles),
acceleration or retardation of the setting (to control the time of progressive increase in mechanical resistance) and even
resistance to chemical attack. Virtually all modern concrete formulations include polymeric admixtures to optimize
performances.

63
 5.1. General information

Hydraulic binder constituted by a polyphasic mixture (clinker) of calcium silicates (C3S, C2S), calcium aluminate
(C3A) and calcium-aluminoferrite (C4AF) + calcium sulphates (to prevent flash set). Clinker is obtained after firing a
mixture of limestone and clays at temperatures around 1450°C. The obtained compound is finely ground after the firing
process.

64
 ♡ Fine grinding of the raw materials (Ø < 160 µm) and drying of the obtained flour.
♡ Progressive heating (100°C → 900°C) within a series of cyclone stages (4 – 5).
♡ Elicoidal movement of the flour in the cyclone stages, against a flow of hot gases.

♡ Pre-calcination stage (completion of limestone decarbonation around 900°C).

♡ Relevant fuel consumption (endothermic process)
♡ Firing in horizontal rotary kiln. Slow movement of the flour within the kiln and agglomeration of the mixture
around 1300°C after partial fusion. Permanence at the higher temperature (~1450°C) to favor the clinker
processes.

♡ Two cooling systems:

o Satellite cooler (cooling pipes parallel to the kiln)
o Grid cooler (better temper of the clinker, cold air flux toward horizontal grids over which the
clinker flows through oscillatory movement)
♡ Grinding in ball mills → transfer of the clinker material and mineral additions within chamber loaded with
griding elements of variable diameters.

Main reactions are

subdivided into three groups:
Reactions under 1300°C:
♡ Calcite decomposition
♡ Clay minerals decomposition
♡ CaO reaction with silica and clays decomposition products to form belite, aluminates, and ferrite

65
 The liquid phase is present in low
amounts.
Reactions between 1300°C and
1450°C (clinkering): formation of a
molten mass mainly derived from
aluminates and ferrite (liquid fraction 20-
30% of the total mixture), reaction of belite
with CaO to form alite.
Reaction during rapid cooling:
crystallization of the liquid phase to form
aluminates and ferrite, polymorphic
transformation of alite and belite.

5.1.1. Cement microstructure

The reactions during the firing process influence the clinker texture (dimensions, shape and distribution of the
phases). , , euhedral crystals formed at high temperature in presence of liquid phase. Crystallization of the liquid
phase during cooling without relevant crystal growth, formation of a fine interstitial matrix of and .

66
♢ Stable between 2070°C and 1250°C. Decomposition under 1250°C to form C2S + CaO.
♢ Slow transformation process → Room T permanence due to the rapid cooling.
♢ 7 polymorphs, 3 spatial groups (industrial products: M1, M3).

♢ 5 polymorphs.
♢ β polymorph is the only reactive.
♢ β polymorph formed during the cooling process. If it is not formed the α polymorphs are transformed into
the γ one (volume increase, detrimental after hardening).

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♢ Pure: no polymorphism.
♢ Na+ incorporation within the crystal structure → polymorphic solid solutions.

♢ Solid solution: Ca2(AlxFe1-x)2O5 (0 < x < 0.7) → 5 polymorphs, 2 spatial groups.

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 5.1.2. Hydratation of hydraulic binders

When hydraulic binder is mixed with water, we

get dissolution of the reactive anhydrous phases,
hydraulic reaction with H2O, formation of low
solubility phases, mainly hydrated microcrystalline
compounds. At the setting phase, reaction stage
implies loss of workability of the binder-water
mixture. At hardening phase we can see slow
process producing a progressive gain of mechanical
properties. It ends when all the reactions between
water and binder are completed. Differentiated
contribution of the hydraulic phases to the
hydration speed and strength gain.
Main process related to the setting
and hardening of the cement paste. C3S-C2S in
contact with water dissolute and release in solution
of Ca2+ silicates and OH- in solution. pH increases (>
12), and we have formation of amorphous calcium
silicate hydrates (CSH) and calcium hydroxide
portlandite (CH). Ca/Si ratio of CSH is between 0.8 and 2.3 (variable amount of structural water).

C3A hydration during the first minutes of reaction (flash set). This is poor crystalline phase,
metastable and varying in composition. Amorphous gel is progressively crystallizing to form hexagonal phases, named
AFm phases (Al-Fe-mono). Conversion to AFm to the stable cubic hydrogarnet phase.

69
 Presence of gypsum and other soluble sulphates creates atmosphere for reaction of C3A to form Aft phase
ettringite. Ettringite forms a barrier around C3A granules hindering water and ions diffusion, preventing the formation
of AFm phases and the consequent flash set. Ettringite is stable when sulphate ions are available in solution. Total SO42-
consumption means conversion to monosulphate (AFm), dissolution of the passivating layer and restart of C3A
hydration.

5.1.3. Supplementary cementitious materials

Natural pozzolans are pyroclastic

powders mainly composed of silicate matrices of low
crystalline order. Industrial pozzolans are clays that
underwent a thermal process transforming them into a
silicate glass.
Pozzolanic reaction: dissolution in alkaline
solution of glasses and silicate minerals due to the
rupture of Si-O chemical bonds, release in solution of
silicate ions, reaction with Ca ions released by portlandite
dissolution → formation of calcium silicate hydrates (C-S-H).
Foundry slags related to the
production process of metallic iron. Variable composition, generally
high in SiO2, CaO and Al2O3. Formation of a highly reactive silicic-calcic
glass due to rapid cooling.
Latent hydraulic reaction: CSH formation not related to
pozzolanic reaction processes, but after dissolution of slag in alkaline
solution and subsequent reaction between calcium and silicate ions
released in solution by the slag itself.
Fly ashes are glassy
microspheres (Ø 5 – 90 µm) obtained as byproducts of the coal power

70
plants; composition strictly related to the one of the original coal and to the combustion processes (high in SiO2, Al2O3 ,
variable in CaO). Silica fumes are glassy micro-nanospheres (mean Ø 0.1 µm) obtained as byproducts of the metallic Si
and Si-Fe alloys productive process; composed of 95 - 99.5% amorphous silica. Pozzolanic reaction with portlandite and
filtering effect (silica fumes).

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 6. EARTHEN ARCHITECTURE

Living in a sheltered place, permanently or temporarily, is a fundamental need of humans. Nevertheless, the use of
natural materials to build shelter is not exclusive to humans: termite mounds, birds nests, beaver dams, and beehives
are perfect examples of efficient architectural skills on the part of animals. According to Mike Ashby:

The difference lies in the competence demonstrated by man in his extraordinary ability to expand and
adapt that competence and development.

After dwelling in natural caves and an extensive period of preparation of temporary structures made of organic
materials (skin, wood, leaf, etc.), the development of long-lasting architecture in human prehistory was based necessarily
on the clever use of natural rocks and/or man-made binders.
The use to plaster huts and floors is the most direct use of natural minerals to solidify surfaces
and make them impermeable. This follows from the physical properties of clay minerals which exhibit a small particle
size and a marked flat morphology derived from the layered crystal structure. Clays in excess water form colloidal
suspension, and the settled fractions posses ideal plastic properties, so that readily formable materials can be obtained
easily by soaking dry clay minerals.
Clays (and loess in China) have been used since
Neolithic times to plaster walls (inside and outside),
to consolidate and smooth rough floors and
eventually reshape them repeatedly after use, to
waterproof roofs made of organic material, and
eventually as a mortar between stones and, finally,
mudbricks. There is ample evidence of this
architectural use of clays in the Middle East starting
from the 10th millennium BC. In its simplest form,
with no use of pyrotechnology, a masonry wall can
be composed of sun-dried bricks (adobe) bound by a
moist layer of mud that, on drying, makes the wall a
solid mass of dry clay. In other cases, earth-based
structures are formed by direct application and shaping of the constructions, and these techniques are variously referred
to as:
♡ Cob, if they have a load-bearing role
♡ Wattle and daub if the earth has an infilling role
In some cases, the clay slabs or blocks can be cut directly out of clay or muddy soil if they are naturally consolidated
by organic material (turf, sod) or other pedogenetic processes. The man-made clay bricks and the clay mortars regularly
contain a substantial organic (straw, dung) or inorganic component (gravel, pebbles) in order to avoid cracking upon
drying – a technology developed before or in parallel with pottery making. The past use of unfired or sunbaked clay
products is often difficult to assess in the archaeological record because they are subject to rapid degradation mainly
by wind erosion, water and salts. Only in rather arid climates are ancient occurrences still recognizable, in most cases as
structures embedded in mounds (tells) formed by layers of sequential human activity.

72
 The earliest evidence of the use of sun-dried bricks is reported from
the Pre-Pottery neolithic layers in Jericho, Israel ( ), in
Nemrik, Iraq and in Ganj Darreh, Iran at least from the
. Evidence of the use of mudbricks in the Indus Valley (Harrapa,
Mohenjo-Daro) started at about the same time (
). Jericho stands as a special site combining the early
systematic evidence of the use of mud-brick buildings alongside the
earliest example of a Cyclopean structure, a massive round tower ~10 m
in diameter and standing to almost the same height; though the
significance of such massive construction is still debated. There is ample
use of mud-brick structures in the site of Çatalhöyük ( )
and a number of other Anatolian sites, together with painted mud plaster
covering internal and external structures, for both practical and symbolic
purposes. Interestingly, although there is evidence that Çatalhöyük people
could have used pyrotechnologically produced lime plaster, there is no
firm evidence of it being employed. The wall surfaces as well as the interior
floors of the structures at Çatalhöyük were carefully plastered and
frequently re-plastered in time, but were coated in earthen plaster, which
were supplemented by a thinner coat of local white marly clay. The first Mesopotamian building in brick on a
monumental scare occurred in the Tell Halaf period ( ). Rectangular mould-based bricks were
introduced in Mesopotamia at least from the 4th or 3rd millennium BC, rapidly becoming decorated or inscribed.
The tradition of using
earthen architecture based on a
mixture of clay, water and straw is
still largely present in many rural
areas of the world, the splendid
multi-story Al Mihdar Mosque
of Tarim, Yemen, and the
Mosque of Djenne, Mali being
two amazing examples of earthen
architectural achievements. The
technological basis of modern
earth constructions is very similar
to that inferred from the
prehistoric record. It is worth
mentioning that several trends of
contemporary architecture (earth
architecture, sustainable
architecture, bioarchitecture, etc.) actively propose the modern use of clays or consolidated clays as natural materials in
building. Furthermore, in the field of modern and ancient earthen architecture there are many unresolved issues
concerning earthen conservation interventions on historic building, settlements and archaeological sites composed of
earthen materials. The Getty Conservation Institute ( ) through its Earthen Architecture Initiative, a long-term
legacy of the past Terra project, is at the forefront of active research and education on the theme.

73
 In Morocco, the four imperial cities – Fez, Marrakesh, Meknes and Rabat – are classified as World Heritage Sites
because of their traditional medinas built of adobe and rammed earth (pisé). In Europe, earthen constructions are not
restricted to rural environments. In Granada, the dazzling Alhambra palace (meaning “red” in Arabic, in reference to
the color of the earth), was largely built from rammed earth in the 13th century, in particular its ramparts. France is one
of the few countries featuring earthen heritage buildings using the 4 main traditional techniques – rammed earth (pisé),
adobe, torchis cob and bauge cob – and where the majority of the earthen buildings often date back more than a
century. Lyon is home to some remarkable examples of earthen architecture. In the Croix-Rousse neighborhood,
people have been living in 4 and 5-floor rammed earth buildings since the1800s. The tradition of using earthen
architecture based on a mixture of clay, water, and straw is still largely present in many rural areas of the world. The
technological basis of modern earth constructions is pretty much the same as the one that we infer from the prehistoric
record. It should just be mentioned that several trends
of contemporary architecture (earth architecture,
sustainable architecture, bioarchitecture, etc.) actively
propose the modern use of clays or consolidated clays
as natural materials in buildings.
The use of clay-rich mud to plaster huts and
floors is the most direct use of natural minerals to
solidify surfaces and make them impermeable. It
follow from the physical properties of clay minerals,
which exhibit a small particle size and a marked flat
morphology derived from the layered crystal

74
structure. Clays in excess water form colloidal suspensions, and the settled fractions possess ideal plastic properties, so
that easily formable materials can be easily obtained by soaking dry clay minerals. The man-made clay bricks and the clay
mortars regularly contain a substantial part of organic (straw, dung) or inorganic (gravel, pebbles) temper to avoid
cracking upon drying, a technology developed before or in parallel with pottery making.

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 6.1. Clay minerals

Phyllosilicates are sheet silicates, formed by

parallel sheets of silicate tetrahedra with 2:5
ratio for Si:O. The basic structure of the
phyllosilicates is based on interconnected six
member rings of SiO4 tetrahedra that
extend outward in infinite sheets. Three out
of the 4 oxygens from each tetrahedra are
shared with other tetrahedra. Tetrahedral
sheets have a negative charge. A cation
octahedral sheet (octahedral refers to coordination) can connect to the tetrahedral sheet. Apical not saturated oxygen
and hydroxyls are linked to divalent or trivalent cations of the octahedral sheets. As concerns the octahedral sheet, the
structure of phyllosilicates can be:
♡ Dioctahedral: Only two out of three octahedral sites are occupied by trivalent ions (divalent ions may also
occur).
♡ Trioctahedral: All three out of three octahedral sites are occupied by a divalent ions (trivalent ions may
also occur).
Crystalline habit is lamellar, consistently with the crystalline structure.

76
77
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 6.2. Earthen architecture

After extraction using rudimentary or more elaborate tools, the earth (consisting of clay, silt, sand and possibly gravel
and pebbles) is transformed into building material using traditional or more contemporary methods. The methods
can be grouped into four main categories.

♡ Compacted earth, not saturated with water: to make rammed earth walls and blocks of compressed
earth.
♡ Stacked or molded earth: to make bauge cob walls and adobes.
♡ Earth mixed when wet with plant fibers: to make torches cob (to fill a wooden framework), straw
earth, hemp earth, etc.
♡ Earth poured in a liquid state into framework, such as fluid or self-consolidating concrete.

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 There are a lot of advantages to using earth: it is a natural material, abundantly and locally available (transport
is often nil), with low embodied energy (energy consumed throughout the life cycle of a material) and infinitely
recyclable. It is raw and diversified, and offers a variety of granularities, natural colors, and lively textures, for a minimalist

80
aesthetic. Earth also provides hygrothermic natural comfort, optimal acoustics, and a healthy indoor atmosphere. It
provides hygrometric regulation and solid walls provide good thermal inertia and sound insulation. It emits no VOCs
(volatile organic compounds) and absorbs odors. These virtues have been empirically understood for thousands of years,
but have now been confirmed scientifically.
But earth also has its limits. The main problem is its sensitivity to water. To overcome this, mud walls are
traditionally protected, especially in rainy climates, with a base (made of stone for example) to prevent moisture soaking
up through capillary action, and a roof overhang to protect against erosion due to rain. A small amount of cement is
sometimes added to limit sensitivity to water and to increase, albeit modestly, mechanical properties. However, this
“stabilization” technique is open to criticism because it impacts the ecological advantages and penalizes the life cycle of
the material.

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 7. STRUCTURAL COMPOSITES

A structural composite is a multi-layered low-density composite used in applications requiring structural integrity,
ordinarily high tensile, compressive, and torsional strengths and stiffnesses. The properties of these composites depend
not only on the properties of the constituent materials, but also on the geometrical design of the structural elements.

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 7.1. Masonry

Masonry is the building of structures from individual units, which are often laid in and bound together by mortar;
the term masonry can also refer to the units themselves. The common materials of masonry construction are brick,
building stone, cast stone, concrete block, glass block, and adobe.

In this type of masonry, mortar is

not used in the joints. This type of construction is the
cheapest and requires more skill in construction. This may
be used for non-bearing walls (compound walls, etc.).

7.1.1. Mortar

Mortar is a workable paste constituted by a mixture of

sand, a binder, and water, which hardens to bind
masonry units, to fill and seal the irregular gaps between
them, spread the weight of them evenly, and sometimes to
add decorative colors or patterns to masonry walls.

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 Building mortars are mixtures used for the jointing of bricks, stones, blocks, etc. Mortar may be defined as a paste
(capable of setting and hardening) obtained by adding water to a mixture of fine aggregates such as sand and binding
material, e.g., clay, gypsum, lime or cement or their combinations. The pyramids of Egypt have been built with clay-
gypsum, gypsum-lime and lime mortars. Indians have used lime mortar for monumental structures such as Taj Mahal
and forts. In the years that followed, if was found that burning limestone with clayey substance produced hydraulic lime
of high water-resistant properties. Lime with a still higher content of clay led to the manufacture of Roman cement. In
1824 Portland cement appeared; today it is considered to be the strongest binding material for making mortar.

MORTAR = BINDER + AGGREGATE

Crushing origin: material with a sandy grain size

Natural origin: incoherent material of sedimentary
obtained by grinding rocks or minerals of sedimentary
origin
origin
- Fluvial sand
- Rocks
- Marine sand (washed)
- Minerals
- Quarry sand
- Reused materials (ceramic shards, mosaic
- Fine gravel from groundwater debris
tesserae, bricks, construction and demolition
- Pyroclastic deposits
wastes)

Aggregate is component of the mortar that limits shrinkage phenomena (cracks) following the loss of mixing water.
Diameter generally below 4 mm.

7.1.1.1. Different types and their properties

Cement mortar can be prepared by mixing cement, sand, and water in desired proportions.
Portland cement and blast furnace slag cement form excellent mortars for walls built with\ bricks, stones and large
blocks. Pozzolana Portland cement and sulphate-resisting cement form mortar which is used for constructions
exposed to aggressive and waste waters. Cement mortars are used for plastering, rendering smooth finishes and damp
proof courses.
Lime mortar is made by
mixing lime, sand and water. Lime used for mortar
may be fat lime (quick or hydrated lime) or
hydraulic lime. Fat lime has high calcium oxide
content. Its hardening depends on loss of water
and absorption of carbon dioxide from the
atmosphere and possible recrystallisation in due
course. Hydraulic lime contains silica, alumina
and iron oxide in small quantities. When mixed
with water it forms putty or mortar having the
property of setting and hardening under water. Slaked fat lime is used to prepare mortar for plastering, while hydraulic
lime is used for masonry construction and are most suitable for construction of chimneys and lightly loaded
superstructure of buildings. Lime mortars have plasticity and placability, good cohesion with other surfaces and little
shrinkage. They harden and develop strength very slowly continuously gaining strength over long period. Fat lime

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mortars do not set but stiffen only as water is lost by absorption (by masonry units) and evaporation. The gain in strength
is a very slow reaction of lime with carbon dioxide absorbed from air.
It is prepared in the same way
as lime mortar, with surkhi replacing sand. Surkhi should
be ground to pass through 4.75 mm sieve and about less
than 15 per cent through 150 micron sieve. Sand is also
mixed sometimes.
Also known as
guarded mortar or gauged mortar is made by mixing
cement and lime. The advantages of lime-cement
mortar are increased water retentivity, workability,
bonding properties and frost resistance. The mortar
gives good and smooth plaster finish and is used in
buildings.
They are the cheapest type of
mortar prepared with locally available ingredients and
are used for masonry works, surfacing floors and
plastering wall surfaces in low cost houses. To improve
resistance to rain water, the plastered surfaces are sometimes sprayed with bituminous material.
The most basic binder used to produce mortar is mud, or
earthen material. Earth is available almost everywhere and can
easily be made into a malleable paste through the addition of water.
Given the variability of soil types from place to place, the properties
of the material obtained can differ widely. Generally, however, the
most suitable soils are characterized by a homogeneous particle size
distribution and by a moderate proportion of clay minerals. The clay
content is especially important, since it determines the cohesive
strength and the plastic behavior of wetted earth, as well as its
drying shrinkage rate. If the proportion of clay minerals is too low,
the mud will lack binding force; if it is too high, the mud will tend to
crack on drying. Unlike gypsum and lime binders, mud simply sets
and solidifies by desiccation, without undergoing chemical change. Although some soils may produce relatively good
mortars without further modification, mud-based mixes are traditionally improved by adding mineral aggregates and
fibrous matter. The addition of copious quantities of chopped straw or other natural fibers helps increase strength,
control shrinkage, and reduce cracking. Mud may also be combined with lime or other additives in order to prevent the
formation of cracks and provide better water resistance and durability.
The resilience of mud and the tendency of earthen materials to promptly soften and crumble if unmaintained or
exposed to natural elements partly explain why ancient mud mortars have left rather scant and poorly recognizable
archaeological evidence by comparison to other bonding and plastering materials. Pieces of accidentally burned mortars
and plasters or exceptionally well-preserved remains show, nevertheless, that this type of mortar has been extensively
used, at least since Neolithic times and in nearly all preindustrial societies. Moreover, although its popularity has
progressively decreased in the recent past, it still continues to be a material of choice in various regions of the
world.

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 7.1.2. Masonry units

Stone masonry in which either undressed or roughly dressed stones are laid. In this masonry,
the joints of mortar are not of uniform thickness. The strength of rubble masonry depends on:
♡ The quality of mortar
♡ The use of long-through stones
♡ The proper filling of mortar between the spaces of stones
Coursed rubble masonry: the masonry work is carried out in courses such that the stones in a particular course
are of equal height.

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 Uncoursed rubble masonry: the courses are not maintained regularly. The larger stones are laid first and the
spaces between them are then filled.

Stone masonry in which finely dressed stones are laid in thin mortar beds. All the joints are
regular and of uniform thickness. This type of masonry is costly in construction, as involves heavy cost of dressing of
stones. This masonry is used for heavy structures, arches, architectural buildings, high piers, abutments of bridges, etc.
Ashlar fine masonry: each stone is cut to uniform size
and shape with all sides rectangular, so that the stone gives
perfectly horizontal and vertical joints with the adjoining stone.
This type of ashlar masonry is very costly.
Ashlar rough masonry: the beds and sides are finely
chiseled-dressed,
but the face is
made rough by means of tools. A strip made by means of chisel is provided
around the perimeter of the rough dressed face of each stone.
Ashlar chamfered masonry: the ashlars are chamfered with a chisel
at an angle of 45° for a depth of about 25 mm.

Stretching bond: the bond in which all the bricks are laid as stretchers.
Heading bond: the bond in which all the bricks are laid as headers.
English bond: this bond consists of headers and stretches laid in alternate courses. It is stronger than the previous
ones.

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 Flemish bond: the bond in which headers and stretchers are laid alternately in the same course. It is the strongest
of all bonds.

Stretching and heading bond

English and Flemish bond

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 7.2. Concrete

Concrete is a composite material composed of fine and coarse aggregate bonded together with a fluid cement
(cement paste) that hardens (cures) over time. The mixture forms a fluid slurry that is easily poured and molded into
shape.
It is to be remarked that the world cement (Opus caementicium) in ancient Roman times was referred to the
concrete masonry of the monuments composed of centimeter sized brick and tuff fragments (caementa), which are
bonded by hydraulic mortars with alkali-rich, calcium-alumino-silicate volcanic ash sands. Only in recent times the
significance changed to refer to modern clinker-based materials. The Romans also developed the concept of lightweight
concrete by casting jars into wall arches as well as using extensively pumice aggregates, which were obtained by crushing
porous volcanic rocks. The arches of the Colosseum and the Pantheon dome are reported to be made with such
materials.

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 Concrete a composite man-made material, is the most widely used building material in the construction industry. It
consists of a rationally chosen mixture of binding material such as lime or cement, well graded fine and coarse
aggregates, water and admixtures (to produce concrete with special properties). In a concrete mix, cement and water
form a paste or matrix which in addition to filling the voids of the fine aggregate, coats the surface of fine and coarse
aggregates and binds them together. The matrix is usually 22-34% of the total volume. Freshly mixed concrete before
set is known as wet or green concrete whereas after setting and hardening it is known as set or hardened concrete. The
molded concrete mix after sufficient curing becomes hard like stone due to chemical action between the water and
binding material.
Important properties of concrete are:
♡ It possesses a high compressive strength.
♡ It is a corrosion resistance material and atmospheric agent has not appreciable effect on it.
♡ It hardens with age the process of hardening continues for a long time after the concrete has attained
sufficient strength. It is this property of cement concrete which gives it a distinct place among building
materials.
♡ It is more economical than steel.
♡ It binds rapidly with steel and as it is weak in tension, the steel reinforcement is placed in cement
concrete at suitable places to take up the tensile stresses. This is termed as the reinforced cement concrete
or simply as R.C.C.
♡ Under the following two conditions, it has a tendency to shrink:
o There is initial shrinkage of cement concrete which is mainly due to the loss of water through
forms, absorption by surfaces of forms etc.
o The shrinkage of cement concrete occurs as it hardens. This tendency of cement concrete can be
minimized by proper curing of concrete.
♡ It has a tendency to be porous. This is due to the presence of voids which are formed during and after
its placing. The two precautions necessary to avoid this tendency are as follows:
o There should be proper grading and consolidating of the aggregates.

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 o The minimum water-cement ratio should be adopted.
♡ It forms a hard surface, capable of resisting abrasion.
♡ It should be remembered that apart from other materials, the concrete comes to the site in the form
of raw materials only. Its final strength and quality depend entirely on local conditions and persons
handling it. However the materials which concrete is composed may be subjected to rigid specifications.

7.2.1. Different types

Reinforced concrete
( ), also called reinforced cement concrete ( ), is a
composite material in which concrete's relatively low
tensile strength and ductility are compensated for by the
inclusion of reinforcement having higher tensile strength
or ductility. The reinforcement is usually, though not
necessarily, steel bars (rebars) and is usually embedded
passively in the concrete before the concrete sets.
1848, Lambot: boat consisting of a wire mesh
immersed in concrete conglomerate. Presented at the
1855 Paris World's Fair.
1854, Wilkinson: introduction of reinforced
concrete in construction. Patent for "improvement in the
construction of fireproof dwellings, warehouses, other
buildings and parts thereof". Construction of the first
building with reinforced concrete floors.
1861, Coignet: Publication of the first data on
experiments on beams, slabs and vaults with embedded
steel profiles.
1867, Monier: patented procedure for constructing
pots from cement mortar reinforced with iron wires.
System later extended to pipes and tanks (1868), slabs
(1869), bridges (1873), stairs and vaults (1875). Elements
and principles of reinforcement layout still based on
empirical concepts.
1871-1875, Ward: construction of the first complex reinforced concrete building in the U.S. (Port Chester, N.Y.).
1884-87, Wayss and Bauschinger: first systematic studies on reinforced concrete, theories on the steel-concrete
interface, design of the positioning of reinforcement in the tensile portion.
1886, Könen: first fundamentals of calculation.
1892: Hennebique system patent (reinforcements in tension zone, stirrups to counteract shear stress). First
reinforced concrete construction system to become widespread and successful worldwide, through a dense network of
national dealers (Italy: Porcheddu Company).

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 1903, Perret: construction of Rue Franklin palace, Paris. First building without load-bearing walls, replaced by a
load-bearing reinforced concrete frame.
1928, Freyssinet: first patent for the use of prefabricated and prestressed reinforced concrete (experiments
started as early as 1911 with the construction of the Le Veurdre bridge).

Concrete differs from cement by virtue of its large content of mineral aggregate; it is a composite. Mineral
aggregates- sand, crushed stone, gravel- are very cheap and do not significantly reduce strength until they
exceed about 80-85 volume %. The result is a composite material bound by cement. Mortar is a fine-aggregate
concrete. Aggregate sizes usually less than 4 mm.
Aggregate – especially for concrete – has to be graded: the sizing should fill space efficiently, so that the remaining
space, which has to be filled with cement, is kept to a minimum. Aggregate should be physically strong, inert towards
cement and have low permeability and water sorption. Many commercial aggregates do not fill all the above criteria.
Aggregate supply:
♡ Historic times: sands and gravels quarried from the riverbeds (rounded shapes, high mineralogical and
petrographic heterogeneity).
♡ Today: sands and gravels quarried from alluvial fans and/or from crushing of quarried stone (subangular
shapes, low mineralogical and petrographic heterogeneity).

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Aggregate further requirements (EN 12620):
- Adequate compressive strength
- Fragmentation resistance of the coarse aggregate
- Wear and abrasion resistance of the coarse aggregate
- Freeze/thaw resistance
- Volume stability
- Low alkali/silica reaction

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 - Low chlorides content
- Low sulphates content

Interfacial region between the cement matrix and the

medium-coarse aggregate (mean thickness 50 μm) with
higher porosity and different distribution of hydrated
phases. Formation due to wall effects (accumulation of
clinker finer granulometric fractions around the coarse
aggregate particles) and bleeding (water confinement
under the coarse aggregate particles due to gravity
effects) during the first hydration stages.
Microstructural consequences: higher porosity (higher
water amount), enrichment in AFm and Aft phases and
lower CSH (higher amount of interstitial phase in the
smaller particles), higher portlandite crystal growth (more space). Mechanical and durability consequences:
preferential area for microcracking formation, lower rigidity, easier penetration of aggressive agents.

Chemical compounds, mainly of polymeric nature, added in low amounts to the fresh paste and capable of modifying
specific cement properties during setting and hardening. Mostly used are superplasticizers (chemical compounds
with dispersant action toward the cement particles in water solution). Cement particles within fresh concrete are
coagulated in agglomerates due to electrostatic interactions between the clinker particles (necessity to put more
water with respect to the proper stoichiometric amount). Addition of superplasticizer is adsorption of the additive in
the surfaces of the clinker particles, with consequent prevention of the agglomeration. Possibility to increase
workability at a fixed w/c ratio and/or to gain strength and durability lowering the w/c ratio. Discovering of
superplasticizers happened during the 1930s (lignin-sulphonates, hydroxycarboxylic acids, hydroxylated polymers,
dispersion due to electrostatic repulsion). Modern superplasticizers are acrylic/acrylate copolymers (dispersion
due to a combination of electrostatic repulsion and steric
hindrance).

Historic times: manual mixing of the components to

obtain an even mixture.
Today: automatic mixing in the construction site (concrete
mixers), production in readymixed concrete production
plants and transportation to the production site with truck mixers.

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 Steel embedded within concrete in the portions subjected to higher tensile stresses. Variable diameter of the rebars
(5-32 mm). Used both as longitudinal reinforcement and as stirrups perpendicular to the longitudinal rebars
(increase of shear strength). Adequate concrete thickness over the rebars (concrete cover) to prevent steel oxidation
(passivating layer due to the alkaline environment of concrete). Use of both plain and shaped rebars to increase
adherence.
The combined utilization of such heterogeneous materials is justified by two relevant factors:
♢ The adherence between steel and concrete allows a transmission of the tensions between the two
materials. Steel absorbs the tensile stresses, while concrete withstands the compressive ones.
♢ The thermal expansion coefficients of the two materials are similar at standard temperatures.

Reinforced concrete production: Construction of formworks to shape the

concrete. Placement of rebars and concrete pouring. Homogenization of poured
concrete to avoid segregation of the constituents (external vibration of formworks
and/or internal homogenization with needle vibrators). Concrete curing (preservation
of humid conditions by water sprinkling and covering of the poured elements to
facilitate the hydration processes avoiding cracking phenomena). Removal of
formworks after setting.
♡ Prefabrication – Pouring and shaping ex situ of modular structural
elements. Transportation in the construction site. Placing of the
elements with cranes. If necessary, soldering and cementation of the
structural elements. Advantages: better control of the concrete
production process. Disadvantages: logistics of transportation.

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 7.2.2. Degradation

Like all materials, binders, mortars and cements undergo , , and

, as they tend to equilibrate with the thermodynamics of the surrounding. The amount and kinetics of
the degradation processes depend on the nature of the binder, and on the environmental conditions acting upon it. In
most cases the degradation processes of chemical nature are slow and continuous, though of course catastrophic events
and mismanagement can severely and abruptly damage the artifact.
As a first approximation, most of the alteration and degradation processes are caused or mediated by water,
therefore the prime parameter affecting the speed of degradation is the porosity of the material, that is its capacity to
absorb and diffuse water in the bulk.
In the binder, the amount and distribution of the pores is controlled by the nature of the paste and the aggregate
system. Key factors affecting porosity are:
- The water/binder ratio in the paste
- The paste/aggregate ratio in the composite mortar or concrete
- The nature of the aggregate
- The use of additives as dispersants and surfactants
- The environmental conditions of setting and hardening
Water percolation causes, among other effects:
- Dissolution of structural components and binder phases
- Dissolution and re-crystallization of soluble salts
- Formation of secondary phases (volume expansion/contraction)
- Progression of the carbonation reactions
- Corrosion of the steel reinforcements
In the case of masonry and binders, humidity and temperature fluctuations are natural components of the
environment. Day/night and seasonal climatic changes induce thermal gradients, expansion shocks, and numerous
cycles of evaporation/condensation through the dew point, inducing water formation and transport through the
structures. We may distinguish between weakly physiosorbed (absorbed) water molecules from the more tightly
chemisorbed (adsorbed) water molecules. In all cases the changes in the water content of the material is going to
activate chemical reactions, mobilization of components, and mechanical damages.
The most common ones are related to the soluble salts already dissolved in the water, such as in marine spray (i.e.
sulphates, chlorides), or dissolved in the material by the presence of water. The salt recrystallization within the pores and
the micro-fractures of the binder is one of the most pernicious alteration mechanisms of building materials:
The exerted by the salt growing in confined spaces is not dissimilar to the
one produced by the freeze and thaw cycles of water and ice: the volume of the crystal is always larger
that the volume of the same amount of molecules in the liquid state, because of the ordered
arrangement due to chemical bonding in the crystal lattice.
however induces other damages related to differential thermal expansion, osmotic
swelling of clays, hydration pressure, and enhancement of wet/dry cycles. The use of surfactants as
agents interfering with the salt crystallization behaviour is being tested.

Concerning historical gypsum-based mortars, even the low humidity may be a problem if combined with high
temperature. As a matter of fact gypsum is a dihydrate phase, and at T>30 °C and RH<30-40% it may undergo slow
dehydration. The process has been detected in the plaster of the Nefertari tomb in the King’s Valley, Egypt. The
chemical equilibrium of lime-based mortars is related both to absorbed water and to atmospheric carbon dioxide. The

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CO2 dissolved in the water forms carbonic acid, which
dissolves calcite and produces soluble calcium bicarbonate
that migrates and re-precipitates elsewhere as Ca
carbonate, in many cases producing a thin white veil on the
surface. Such a carbonate layer frequently covers frescoes
and cave paintings. The major problems involving wall
paintings of all ages are: pigment alteration and fading,
detachment of the painted layer and plaster support,
surface corrosion, and salt precipitation.

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 Gel pores: few nm in diameter, they are due to the fibrous shape of
C-S-H crystals.
Capillary pores: diameter between 10 nm and 10 μm, they constitute
the interstitial spaces between the hydration products of the hardened
cement paste. Capillary pores potentially dangerous (tensile stresses under
freeze/thaw cycles due to their reduced diameter).

Formed after inclusion of air bubbles during mixing and casting.

Homogeneously dispersed within concrete.
Dimensions: < 1 mm (generally 1/10 mm).
Spherical shape: connected with capillary pores, fluids migration
from capillary pores to entrained air voids, absorption of freeze/thaw
tensional states.

Origin: inclusion of air macrobubbles during mixing and casting of concrete, accumulation and subsequent
evaporation of excess water (bleed water).
Position: concrete surface (wall effect of the formwork), around coarse aggregates, around rebars.
Dimensions: millimetric-centimetric
Shapes: from spherical to irregular/channel like.
Potentially dangerous (overall reduction of compressive strength).

According to dimensions: macrocracks (>0.1mm), fine cracks (between 0.01 and 0.1 mm), microcracks (<0.01).

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 Plastic shrinkage cracks: accumulated toward the surface. Formed after excessive superficial evaporation of water,
few hours after casting.
Drying shrinkage cracks: radial to the aggregate fine fraction. Formed after a slow water loss within concrete.
Highly dangerous (loss of mechanical strength, higher permeability to degrading agents). The can be avoided
through accurate curing. Generated by dimensional variations of concrete due to water evaporation and chemical
shrinkage.

CARBONATION

Due to the interaction between SO42- ions and hydration products within the cement matrix. Formation favored in
humid, cold and CO2-rich environments.
♢ Sulphate ions coming from the external environment: ESA (external sulphate attack). Sulphates found in
marine water, coastal aerosols, air polluted by industrial gases, mainly oil refineries (extraction of sulphates
from petroleum)

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 ♢ Sulphate ions present within concrete: (internal sulphate attack). In form of gypsum
contaminating the aggregate fraction or formed after thermal decomposition of primary ettringite during
steam curing
♢ Secondary phases formed after sulphate attack: gypsum (from CH), secondary ettringite (from AFm),
thaumasite (from C-S-H)

Effects: Expansive processes in the concrete cortical layer causing detachments from the internal unperturbed
nucleus. Dissolution of C-S-H phases responsible for the mechanical properties of concrete (thaumasite).

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Effects on concrete: cracking, delamination and pulverization due to expansive processes induced by rebars
corrosion, higher incidence of freeze-thaw phenomena, formation of expansive oxychloride.

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 8. ANALYSIS OF BINDING COMPOSITES

How do we investigate cement

materials? At the industrial level, most
quality controls are done by optical
microscopy, X-ray fluorescence (XRF)
and XRPD, with the quantitative phase
analysis by XRPD offering a number of
crucial advantages over bulk chemical
analysis by XRF. Cement producers are
among the most active users of advanced
on-line testing protocols and
instrumentation using automatic XRPD,
including full-profile refinement of all
clinker phases.
At the research level, the cement system is complex enough that one experimental technique alone is hardly
sufficient to unveil the fine interplay between all chemical reactions acting simultaneously during hydration.
Furthermore, the system is extremely sensitive to any environmental perturbation, especially dehydration, so that
sample preparation without artefacts is a crucial part of any experiment. Virtually all experimental techniques have been
employed to characterize and understand the behavior and evolution of cement systems. Time-resolved XRPD is one
of the most powerful techniques for following the evolution of the cement/water system during hydration. It allows
appropriate quantification of the phases and evaluation of reaction kinetics. If reaction enthalpies are sufficiently well
known, then it is possible to back-calculate the measured curves from isothermal calorimetry and discriminate the
underlying reactions.
The use of synchrotron radiation, of course, allows access to much faster reaction times with respect to laboratory
instruments, down to the millisecond timescale. Synchrotrons offer the advantage of highly brilliant and coherent
radiation, so that experimental techniques can be designed flexibly to suit complex samples. Simultaneous and
combined investigations are thus possible only at large scale-facilities. Concerning cements, ultra-high-resolution
imaging and sub-micron computed tomography provide considerable advances in understanding the 3D evolution
of the microstructure of the material in a totally non-invasive mode. Furthermore, the innovative combination
afforded by diffraction-enhanced tomographic imaging proved to be an extremely powerful tool for the
investigation of complex materials, and allowed, for the first time, direct imaging of nucleation processes.
As a further link between the cement world and mineralogy, there is only one known natural occurrence of the
calcium silicate phases (hatrurite, larnite) that are commonly produced in cement kilns. It is from a geological formation
called the Hatrurim Formation, and it is exposed in various areas around the Dead Sea in Israel (Hatrurim Junction,
near Arad), Palestine and Jordan (Maqarin). It is interpreted to occur as the result of pyrometamorphism of marls
and limestones derived from gas or bitumen ignition in the underlying hydrocarbon-loaded formation. The natural
combustion produced this unique rock formation of thermally metamorphosed ‘cement zones’ which are very close
analogues of industrial cements. In the Hatrurim Formation the calcium silicate phases occur together with a number of
exotic high-temperature mineral phases (shulamitite, bentorite, gazeevite, stracherite, zoharite, zuktamrurite, and
others), most of them found only in this unique type locality.

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 The Maqarin site, located along the Yarmouk river near the Jordan-Syria border, has been investigated extensively
because the subsequent interaction with groundwater caused the formation of hyperalkaline waters and CSH phases in
the fractures of the HT-metamorphosed rocks. Such unique features were studied in detail in order to understand the
long-term leaching and cation mobility in the only known natural analogue of a modern radioactive-waste repository.
The investigation project was called The Maqarin Natural Analogue Project. This is another example showing the
interplay of knowledge between natural and synthetic systems. This knowledge encompasses mineralogy, geology,
hydrology, crystal chemistry, geochemistry and a number of other disciplines, and it is fundamental when tackling
problems at a large or global scale.

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8.1. Petrographic analysis of binding composites

We need this analysis because:

♡ To define what was the ancient builders’ awareness of the resources available in their territory
♡ To determine when the functionality criterion prevailed over that of availability or vice versa
♡ To answer all those “whys” that follow the provenance issue’s resolution and require a thorough
knowledge of both the territory and the ancient production techniques (which type of binder? where
the aggregates were collected?)
♡ To find rational explanations to technologically choices (i.e., How they manufactured the mixture? Do
they need to waterproof? They searched for a structural reinforcement?)

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 9. MORTARS AND PLASTERS: THE INFORMATION FROM
ARCHAEOLOGY

The literary sources:

♡ Language – Latin texts, Greek texts.
♡ Chronology – few texts dated to the Classical and Hellenistic Age; increase from the 2nd century BC
onwards (connected to the burgeoning structural use of mortar in Italy)
♡ Types of texts – mainly architectural and agricultural treatises, but also poems, letters, medical texts,
encyclopediae, historic and geographic treatises.

The Greek literary sources:

The Roman literary sources:

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9.1. Literary sources

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9.2. The use of mortars in ancient building contexts: foundations, walls, vaults

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