Cement and Concrete Research xxx (xxxx) xxx–xxx

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Cement and Concrete Research

journal homepage: www.elsevier.com/locate/cemconres

Hydration and rheology control of concrete for digital fabrication: Potential

admixtures and cement chemistry
⁎
Delphine Marchona, , Shiho Kawashimab, Hela Bessaies-Beyc, Sara Mantellatod, Serina Nge
a
Department of Civil and Environmental Engineering, University of California, Berkeley, CA 94720, USA
b
Department of Civil Engineering and Engineering Mechanics, Columbia University, New York, NY 10027, USA
c
French Institute of Science and Technology for Transport, Development and Networks (IFSTTAR), Department Materials and Structures (MAST), Université Paris EST,
77447 Marne la Vallée, France
d
Institute of Building Materials, ETH Zurich, 8093 Zurich, Switzerland
e
Concrete Group, Department of Architecture, Building and Construction, SINTEFF Building and Infrastructure, Trondheim, Norway

A B S T R A C T

Concrete digital fabrication is an innovative construction approach where infrastructural elements can be built
additively without using formwork. This represents a significant advantage, but also introduces materials en-
gineering challenges, as the requirements normally fulfilled by the formwork are now imposed on the concrete.
In this paper, it is discussed how admixtures can be employed to achieve the rheological and hydration prop-
erties necessary for printable concrete. An overview of various admixtures currently implemented in standard
practice is presented. Then, the main required concrete states for extrusion and deposition processes are ana-
lyzed with respect to required performances and potential admixtures. Finally, possible side effects and in-
compatibilities are discussed, as well as how they could be unconventionally used for printable concrete pur-
poses. The main objective is to demonstrate how admixtures will be critical in the development of concrete
systems to realize digital fabrication, and to ultimately motivate investigation in the key areas discussed.

1. Introduction
The use of concrete in construction has primarily been limited to
static and standardized formwork casting, where fresh concrete is
poured into formwork, often vibrated to allow sufficient placement, and
left to set. In standard practice, it is expected that concrete reaches
sufficient strength a day later, at which time the formwork is stripped
and the hardening concrete is cured to sustain hydration. The proper-
ties of the fresh mix, which are workability, compactibility, and re-
sistance to segregation, are generally controlled or fine-tuned through
the use of admixtures to facilitate the casting process. On the other
hand, admixtures also allow the control of the hydration kinetics of the
mix: first to avoid premature setting during transport or placement, and
second for the formwork to be removed on time. In general, admixtures
have contributed to numerous essential developments in concrete
technology [1] and will continue to do so in novel approaches that are
part of the emerging concrete digital fabrication [2,3].
Digital fabrication with concrete is a family of novel fabrication
processes that offers greater freedom of shape by combining computer-
aided design with additive, subtractive or forming manufacturing
[3–7]. Many approaches exist, but this paper focuses on those that
allow structures to be built additively and thereby eliminate the need
for formwork. This mainly concerns extrusion printing, although other
techniques, such as slip casting or spraying, could also benefit from the
concepts presented in this analysis.
Building without formworks introduces a number of advantages,
namely savings in cost, time, and materials associated with formwork
construction. However, at the same time, it implies some significant
materials engineering challenges as all the requirements that are nor-
mally fulfilled by the formwork are now directly imposed on the mix
design of the concrete and the way it is deposited. Therefore, in absence
of formwork, controlling the hydration and rheological properties be-
comes even more critical for successful execution [4]. Hydration ki-
netics must be delayed and accelerated in relatively extreme manners
so that the material does not set during the printing process but, in-
stead, right after deposition in order to support its own weight and that
of subsequently deposited layers of material [8,9]. Concerning
rheology, there must be a balance between flowability during printing
and rate of structuration immediately after deposition. In addition,
given the time-sensitive nature of the technique due to the continuous
progression of hydration, prediction of flow rate is important to control
the printing speed.

⁎
Corresponding author.
E-mail address: dmarchon@berkeley.edu (D. Marchon).

https://doi.org/10.1016/j.cemconres.2018.05.014
Received 20 December 2017; Received in revised form 15 May 2018; Accepted 15 May 2018
0008-8846/ © 2018 Elsevier Ltd. All rights reserved.

Please cite this article as: Marchon, D., Cement and Concrete Research (2018), https://doi.org/10.1016/j.cemconres.2018.05.014
D. Marchon et al. Cement and Concrete Research xxx (xxxx) xxx–xxx

The aim of this paper is to discuss how various admixtures can be

employed to achieve the desired properties for successful additive
manufacturing, from the pumping and deposition characteristics to the
hardening and curing stage. The key rheological and hydration prop-
erties for overcoming the challenges of form-free casting are presented
along with required performance properties and potential use of ad-
mixtures. This includes the description of suitable chemical and mineral
admixtures, their attributes and potential side effects with respect to
cement hydration, as well as their possible incompatible combinations.
While this paper mainly focuses on chemical aspects and working me-
chanisms on the physico-chemical level, complementary information
with a focus on the control of structural build-up is offered in another
paper of this special issue [8]. Rheological questions are also then de-
tailed by Roussel [10].

2. Background: rheology, cement hydration and admixtures

2.1. Rheological aspects of hydrating cementitious systems

Controlling the rheological properties, expressed in practical terms

Fig. 1. Relative viscosity (i.e. the ratio between the viscosity of the paste with
as workability, of fresh concretes is important as it will determine the polymer and the viscosity of the reference paste) as a function of relative yield
efficiency of the casting process during construction. In the case of stress (i.e. the ratio between the yield stress of the paste with polymer and the
novel applications like digital fabrication, it will determine its success yield stress of the reference paste). The superplasticizers are different PCEs.
or failure. A standard among field-friendly methods used to quantify Adapted from [35].
concrete workability is the slump test [11]. However, workability is
better described through fundamental rheological parameters, pri-
decrease in liquid content at a constant yield stress, which can decrease
marily yield stress and plastic viscosity. Yield stress is the stress above
the porosity of the hardened material and enhance the mechanical
which flow initiates, or below which flow terminates. It also determines
performance and durability [33]. Also, as many processes of digital
suspension stability [12] and accounts for the results of stoppage tests,
fabrication use mix designs without coarse aggregates, the volume
such as slump or slump flow [13,14]. Plastic viscosity describes the
fraction of finer particulate fractions is increased. Bringing these closer
resistance to flow, which increases with increasing shear rate – an
to the maximum packing density of the mix [34] increases the apparent
important parameter for robustness [15]. In addition, fresh cement-
viscosity and is something that superplasticizers can only partially re-
based materials exhibit thixotropy, which is a time-dependent property.
medy.
It can be generally defined as the continuous decrease of apparent
LSs are natural polymers with relatively moderate water-reducing
viscosity with time under shear and a subsequent recovery at rest [16].
ability [36]. In current applications, these plasticizers are commonly
However, for concretes, it is often used to describe fresh-state structural
employed for mobile concrete extrusion of roads [37]. This is due to
build-up, which can be quantified as an increase in yield stress over
their robustness and ability to induce moderate workability to fill the
time. This, for instance, has important implications on stability and
slip form, and yet maintain its shape within seconds of the initial cast as
formwork filling and pressure [17–21].
slip forms are removed. These features are of great interest for extrusion
In general, the rheology of concretes is affected by the mix design,
or slip forming in digital fabrication. PNSs, polymelamine sulphonates
including the volume fraction of the binding system, its composition
and vinyl copolymers are synthetic polymers with a higher dispersing
(e.g. presence of supplementary cementitious materials) and attributes
ability than LSs [22]. Their mechanism of action is due to both their
of the aggregates (i.e. particle size distribution and shape). Admixtures
electrostatic and steric effects, and not to electrostatic effects alone as
can be used as an effective tool to tailor the rheology. Superplasticizers,
often stated in literature, particularly in the case of LSs [22,30].
which act as dispersants to lower yield stress [22], and viscosity mod-
The most effective superplasticizers for current use are PCEs
ifying agents, which increase plastic viscosity, are now regularly used in
(Fig. 2). These admixtures are comb copolymers composed of an an-
concretes to control workability [23,24]. Clays can also be used as
ionic backbone on which side chains are grafted. The backbone is at the
thixotropy modifiers [25–27]. For successful additive manufacturing, it
origin of the polymer adsorption on the surface of cement particles,
will be key to control rheology through the use of suitable admixtures,
whereas the side chains that tangle into the solution prevent close
likely in combination. Most of them are considered to be chemically
inert as they alter rheological properties through physical effects.
However, they can induce strong physicochemical side effects, as is the
case for superplasticizers that influence the rate of cement hydration
[28,29]. So, in addition to the main properties of these admixtures, it is
important to consider any secondary effects. Given the broader range of
chemical admixtures [30], we provide here an overview that, although
only concerned with additive manufacturing, remains selective and
incomplete.

2.1.1. Superplasticizers
Dispersing agents and superplasticizers, such as lignosulfonate (LS),
polynaphthalene sulfonate (PNS), and polycarboxylate ether (PCE), are
polymeric dispersants used in cementitious materials to reduce yield
stress and viscosity at a constant solids content (Fig. 1) [30–32]. The
enhancement of the material workability is essential for mixing, casting
and extrusion in concrete digital fabrication. Moreover, it allows for a
Fig. 2. Schematic representation of a PCE superplasticizer (left) with its de-
scriptive structural parameter, C/E, n and P (right). n represents the number of
side chains/repeat units in one molecule. C/E represents the number of car-
boxylate functions C per ester group E through which a side chain with P
monomers is grafted. Adapted from [29].

2
D. Marchon et al.
contact between particles through steric hindrance, reducing attractive
forces [38,39]. The successful use of these comb copolymers comes
from their molecular structure (described in Fig. 2) and composition,
which can be readily tailored to provide a broad range of properties and
performances [30,31].
The adsorption of these superplasticizers on cement surfaces is the
fundamental process involved in their mechanism of action [22,40].
Furthermore, it is important to keep in mind that these admixtures can
perturb the hydration of cement particles and alter the performance of
the material in the hardened state, as will be discussed in Section 2.2.1
[28].
2.1.2. Viscosity modifiers
Viscosity modifying agents (VMAs) are commonly used in industrial
practice to control water transport and porous structure in both the
fresh and hardened state [23,24,41]. The most commonly used VMAs in
cementitious systems are cellulose-ether derivatives, such as welan gum
and diutan gum. Anionic polyacrylamides are also used in the con-
struction field for their high flocculating efficiency [30,42]. Such ad-
mixtures are essential for controlling the risk of segregation of highly
flowable concretes, improving the water retention, and in some cases
for promoting particle flocculation, such as for shotcrete applications.
VMAs can enhance the yield stress of cementitious materials and ef-
fectively reduce material deformation under its own weight, which is
critical for additive manufacturing concrete.
Most VMAs are able to adsorb simultaneously on several cement
particles and bridge them, which increases the macroscopic yield stress
of the suspension to a certain extent [42,43]. Their efficiency as floc-
culants depends on their molecular weight and their affinity with the
cement surface (Fig. 3). For example, low molecular weight VMAs are
unable to adsorb on multiple particles and can be at the origin of a yield
stress decrease through steric hindrance [35,44–46]. According to Ta-
dros [47], the particle surface covered by the polymer is a key para-
meter for controlling polymer efficiency and, specifically for adsorbing
VMAs, the optimum bridging flocculation is attained at half surface
coverage. Also, Bessaies-Bey et al. [42] demonstrated that poly-
acrylamide adsorption is enhanced by its anionicity, whereas cellulose
ether adsorption decreases when the average number of substituted
hydroxyl groups per glucose unit (i.e. degree of substitution) increases
[42,48]. In both cases studied in cement pastes, the yield stress in-
creases with the molecular weight of the VMA. Furthermore, by com-
paring the flow onset of cement pastes containing polyacrylamide and
cellulose ethers, pastes containing polyacrylamide were found to ex-
hibit a higher elastic modulus [42,48]. Therefore, polyacrylamide limits
Fig. 3. Relative yield stress (i.e. the ratio between the yield stress of the paste
with polymer and the yield stress of the reference paste) as a function of VMA
dosage. Reproduced from [35].
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Cement and Concrete Research xxx (xxxx) xxx–xxx
the deformation of the deposited material under its own weight, making
it the most suitable VMA for printable concrete.
2.1.3. Clays and inclusions as thixotropic agents
Inorganic additions, namely clays, and organic inclusions, such as
polymeric fibers, can also be effective rheological modifiers. Clays
themselves exhibit shear thinning (i.e. decrease of the apparent visc-
osity by increasing the shear rate) due to their opposing surface
charges, which gives rise to a house of cards structure that can form at
rest and break down under shear [49]. They have a wide range of ap-
plications as rheological modifiers, including paints and drilling fluids
[50]. Among the different families of clays, attapulgite (or paly-
gorskite), bentonite (montmorillonite-based), kaolinite, sepiolite and
contaminated clays have been studied as rheological modifiers for ce-
ment-based materials [25,26,51–57].
In nature, clay particles are micron in size and consist of multilayer
stacks of crystalline layers or fibers with nanometer thickness [58]. This
is the form in which most of the clays in the aforementioned studies
were in, i.e. layered or fibrous particles. Clay surfaces can be modified,
by either intercalation or exfoliation, so that plates and fibers can be
discretely dispersed as nano-clays in cementitious matrices [59].
Through this modification, clay particles are then reduced in size down
to 100 nm (nanoclays) [60]. For instance, bulk attapulgite, a family of
fibrous hydrous magnesium silicates, can be chemically exfoliated to
remove impurities and swelling clays and produce rod-like particles
[61]. These resulting particles have an average diameter of 30 nm and
average length of 1.5 μm. Nanoclays can be dispersed from bulk clays
through the use of surfactants such as sodium dodecylsulphate (SDS)
and octadecyltrimethylammonium bromide (ODTMA) [62,63]. They
act by adsorbing onto the surfaces of the clay particles and preventing
re-agglomeration or restacking of the clay layers onto each other in
solution, with different affinities for different clay types [64]. It is also
worth mentioning that clays can be contaminated by organics or heavy
metals that may influence the inherent properties of the mix [65–67].
Due to the great diversity and non-consistency of the material, prop-
erties of contaminated clays can vary from batch to batch and material
to material, rendering them less suitable for digital fabrication appli-
cations without further processing or identification of the material.
Generally, clays are hydrophilic, which facilitates their incorpora-
tion in a concrete mix, but can also thicken it because of the water
absorption and the flocculated structure they may adopt. Their corre-
sponding aggregation behavior, and thereby rheological effect, is af-
fected by pH, which changes during the progression of hydration [68].
A number of studies have demonstrated the potential of clays to tailor
the rheology of fresh concrete mixes to facilitate extrusion [25], re-
duction in self-compacting concrete (SCC) formwork pressure [26] and
slipform paving [27], where a balance between flowability during
casting and stiffening at rest is desired. Fundamental studies on the
fresh state microstructure have tied these properties to an increase in
flocculation induced by clays [51,69]. In particular, a chemically ex-
foliated attapulgite nanoclay was found to be effective at modest
amounts (0.3% by mass of cement). Many approaches have been ap-
plied to quantify their influence on thixotropy, including steady-state
protocols [52], creep protocols [53,54], and large amplitude oscillatory
shear [55]. Generally, these studies have shown that attapulgite na-
noclay can significantly accelerate the rebuilding kinetics and rate of
increase of static yield stress over time, which is translated to a fresh-
state stiffening of the overall system. Similar effects on rebuilding ki-
netics were shown using bentonite, although not as pronounced, likely
due to their lower external specific surface area [56]. This demonstrates
the potential of utilizing clays, particularly nanoclays, for additive
manufacturing, since they can provide rapid fresh-state stiffening to
control shape stability immediately after deposition with no adverse
effects on the flowability during printing. In fact, some early results
were presented by the Contour Crafting group at University of Southern
California, where attapulgite nanoclays were found to show beneficial
D. Marchon et al. Cement and Concrete Research xxx (xxxx) xxx–xxx

results on printing properties [70].

Polymeric fibers, such as cellulose, polyvinyl acetate, polypropylene
or polyethylene fibers, are well known to have a profound effect on
rheology and therefore may be considered as a tool to obtain the de-
sired flow characteristics in additive manufacturing. Although they
increase the viscosity, they improve the homogeneity and stability of
the mix [71]. During an extrusion process, fibers would tend to align,
leading to a shear thinning behavior, whereas after extrusion they can
be expected to help the material remain in place. For such situations,
one would mainly be concerned about the aspect ratio of the fibers and
their dosage. In addition to enhancing the tensile strength of the con-
crete in the hardened state, fibers can enhance resistance to cracking
due to drying shrinkage, which structures made without formwork may
suffer more from, as discussed later in Section 2.3.
Finally, although primarily utilized to mitigate freeze-thaw damage,
entrained air can also have an effect on concrete rheology [72,73]. This
effect will depend on the ability of the bubbles to deform, which is
governed by their size and applied shear forces [74]. If the bubbles
deform, the air entrainment should reduce the viscosity and increas-
ingly so with rising shear forces and bubble size. Otherwise, if bubbles
do not deform, they act rather as solid inclusions and increase both the
viscosity and yield stress. In this sense, air entrainment would con-
tribute to raising the yield stress at rest after extrusion and reducing it
during extrusion in a similar way as fibers. Whether this effect can be
exploited and, if so, to what extent, must still be examined in detail. In
doing so, it would be crucial to examine interactions that air entrainers
are known to have with other chemical admixtures, in particular PCEs
and defoamers often used when formulating products for commercial
superplasticizers [75,76].

2.2. Cement hydration chemistry

In this section, we deliberately chose to only describe ordinary

Portland cement (OPC) hydration as it is, at present, the main binder
used to develop mix designs for concrete digital fabrication. However,
characteristics of alternative binders and supplementary cementitious
materials are also discussed later on in Section 4.1.
Ordinary Portland cement is mainly composed of three families of
phases: the silicates, including impure tricalcium silicate (C3S, also
called alite) and dicalcium silicate (C2S, belite), the aluminates, in-
cluding tricalcium aluminate (C3A) and tetracalcium aluminoferrite
(C4AF), and the sulfates, typically gypsum that can dehydrate to hemi-
hydrate during cement production [77,78]. It may also be present as
anhydrite initially depending on its sourcing. Fig. 4 represents a sim-
plified view of the main chemical reactions occurring in the first hours
of hydration of a model cement [29]. The main mechanisms involved in
hydration are first the dissolution of the main anhydrous phases, then
the nucleation of the hydrates once their respective supersaturation
level is reached, and finally their growth [79,80]. The main phases
involved at the beginning of hydration are C3A and calcium sulfate,
which lead to the precipitation of ettringite, and C3S, which forms
calcium silicate hydrate (C-S-H) and a crystalline phase called por-
tlandite (Fig. 4).
The hydration of C3S, which is the main component of OPC, is re-
sponsible for the binding properties of cement as its hydration leads to
the finely structured and highly cohesive phase known as C-S-H. At the
very beginning of hydration, C-S-H precipitation is one of the me-
chanisms responsible for the increase in thixotropy, as its particles form
bridges between cement grains [81,82]. The resulting percolation is
reversible as long as the mixing power can break these bridges [82].
However, after the so-called induction period during which the hy-
dration reactions are considered slow, an onset of massive precipitation
of C-S-H occurs, which leads to the general setting and hardening of the
cement. Recent results indicate that a clear transition exists between
both regimes. This can be demonstrated through the quantification of a
clear onset point that is linked to a mechanism change or initiation of
Fig. 4. Schematic representation of the different reactions of dissolution (D),
nucleation (N) and growth (G) occurring during hydration of a model cement
composed of hemihydrate (1), tricalcium aluminate (2) and tricalcium silicate
(3). The products of hydration are ettringite (4), portlandite (5) and calcium
silicate hydrate (6). The dashed line indicates that, in certain conditions, alu-
minate ions may influence the dissolution reaction of silicates. Reproduced
from [29].
the rate governing hydration reaction [83].
C3A is the most reactive phase in cement. Although it is present in
small amounts, typically 5 to 10% of cement weight, its hydration
impacts both rheological properties and mechanical performance.
Without any sulfate source to control its hydration, C3A would lead to
rapid setting of the cement in the first few minutes called “flash set” due
to the precipitation of calcium aluminate hydrates on the clinker sur-
face [77,84,85]. Calcium sulfate is added to the clinker to avoid this
uncontrolled hardening. Calcium sulfate ion pairs are expected to ad-
sorb onto tricalcium aluminate and reduce the overall reaction rate,
which provides a longer period of fluidity for the casting [86,87]. With
sulfates in the system, ettringite, whose morphology is generally de-
scribed by prisms or needles offering a high specific surface area, pre-
cipitates and remains stable as long as sulfates are still available in
solution [88]. This precipitation maintains a low concentration of alu-
minum ions in the pore solution, which is desirable as they negatively
impact C3S hydration by inhibiting its dissolution [89–92].
The sulfatation level and subsequent balance between the main
phases are important key aspects during cement hydration [29,93,94].

4
D. Marchon et al.
Once the sulfate depletion point is reached, C3A hydration is no longer
controlled and its dissolution accelerates. This increases the aluminum
ions concentration in the pore solution and leads to the precipitation of
aluminate hydrate phases. If this happens before the acceleration of C-
S-H precipitation in a case where the optimum sulfate content is not
controlled, the flash set occurs and the silicate hydration is then
strongly delayed, ultimately adversely impacting the early strength.
This is why in OPC the sulfate content is well controlled, in order to
have the sulfate depletion point occur after the main precipitation of C-
S-H.
2.2.1. Retarders
Retardation or acceleration of cement hydration can be achieved by
the addition of chemical admixtures. Among the organic admixtures
that have the sole purpose of retarding hydration, carbohydrates are
very effective retarders [28,95,96]. They prolong the induction period
by delaying the onset, but once the onset occurs, they usually accelerate
the reaction rate in the acceleration period. This family of sugar deri-
vatives offers a certain flexibility in structural variations, i.e. functio-
nalization and degree of polymerization. Therein, we more often
identify glucose, sodium or calcium gluconate, sucrose and sugar al-
cohols [97–100]. Other organics have also shown retarding abilities,
such as carboxylic acids, more specifically citric acid and tartaric acid,
or phosphonates that induce more extensive retardation [96]. Concrete
dispersants may also show a retarding action on cement hydration. This
is the case for low range water reducing agents, such as LSs, but also for
high range water reducers, such as PCEs, that have been described in
Section 2.1.1.
The way through which most of these compounds induce retarda-
tion is still a subject of debate. Different mechanisms have been pro-
posed, including complexation of ions in pore solution [101–104], in-
hibition of dissolution of anhydrous phases [29,91,105], or inhibition
of nucleation and/or growth of hydrates [97,106]. For most of the
admixtures described above, their impact on cement hydration is not
trivial and important aspects are still not well understood. In general, in
the case of sugar derivatives, the retarding ability strongly differs de-
pending on their reducing or non-reducing nature, degradation degree
in alkaline environment, complexing capacity, or adsorption affinity on
silicate or aluminate surfaces [28,99,100,107–109]. For example, su-
crose, which is one of the most used and effective retarders, does not
suffer from chemical modification through ring opening or degradation
at high pH, as observed in the case of glucose. Therefore, it has a lower
calcium binding capacity than glucose, which shows a lower retarding
ability. This fact proves that ionic complexation alone cannot be at the
origin of the retardation and that one or both of the other mechanisms
must be accounted for [99,100,110]. It also means that for any re-
tarding admixture, the adsorption of molecules on the anhydrous
phases, hydrates or both plays an important role. In the case of comb-
shaped superplasticizers, recent results indeed showed that PCEs can
strongly inhibit dissolution of C3S, most likely through adsorption on
active dissolution sites [29]. Moreover, a quantified correlation, re-
presented by the master curve in Fig. 5 (left), was found between the
induced retardation of an OPC and molecular structure of PCEs
[29,111]. More specifically, it was found that the retardation of the
silicate hydration depends on the dosage of the polymer and on the
local spatial density of functional groups (i.e. the carboxylates that have
the anchoring function in the adsorbed state) in the vicinity of the
surface. In other words, the correlation is the product between the total
number of repeat units (Fig. 2) introduced in the system and the
blocking capacity of each repeat unit, which depends on the electric
field induced by their charges on the surface, as illustrated in Fig. 5
(right). Combining this result with an empirical analysis of the depen-
dence of the rheological properties on the molecular structure allowed,
for the first time, the development of a molecular optimization tool
conciliating the main dispersive property of the PCEs with their most
important side effects on cement hydration [29,111].
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Cement and Concrete Research xxx (xxxx) xxx–xxx
2.2.2. Accelerators
This section is not intended as a comprehensive review of accel-
erators commercially available, as this has been more deeply described
elsewhere [112,113]. Its scope is rather to describe the main accel-
eration mechanisms, with some related examples of admixtures, that
are of interest for printable concretes.
Acceleration of cement hydration is achieved in different ways that
can be divided into physical and chemical actions. The first physical
action that we may consider regarding the previous Section 2.2.1 in-
volves the desorption of retarders from the reacting surface, as in the
case of sucrose in the presence of portlandite. Indeed, it was demon-
strated that the molecules of sucrose tend to desorb from the cement
surface where they originally cause retardation and diffuse in the so-
lution to preferentially adsorb onto the portlandite, for which sucrose
has the highest affinity [28,114]. It has to be mentioned that this use
could be limited by the high amount of portlandite needed to effectively
uptake the sucrose for a significant acceleration of hydration. The same
kind of uptake phenomenon, explained in more detail in Section 4.4,
occurs with PCEs when a certain type of clay is added.
A second physical mode of acceleration was observed by Thomas
et al. [115] after the addition of C-S-H seeds in cement paste. Specifi-
cally, this addition strongly increases the surface available for further
hydrate precipitation, which leads to an earlier onset and a faster ac-
celeration period. Based on this principle, a new generation of accel-
erators based on C-S-H seeds suspensions has been recently introduced
on the market [116].
The list of most common products that chemically accelerate the
hydration of cement is quite significant and is generally divided into
two different types: soluble inorganic salts and organic compounds
[96,112]. Among the inorganic salts, calcium chloride (CaCl2) is the
most efficient. However, despite having been widely used, its exact
mechanism of acceleration is not fully understood, although the addi-
tion of calcium ions must clearly affect nucleation and growth of hy-
drates [117]. One mechanism described in the literature is the forma-
tion of a more permeable C-S-H with a higher specific surface area,
which enhances the diffusion of ions. Furthermore, higher rate of hy-
dration observed in the induction period would also mean that the
calcium chloride enhances C-S-H nucleation [96]. However, the nega-
tive point of using CaCl2 is the addition of chloride ions in the system,
responsible for pitting corrosion of steel that compromises the long-
term durability of reinforced concrete [118]. This is why, depending on
the country and its standard, CaCl2 use is limited or absolutely pro-
hibited for reinforced concrete [112]. Other salts, such as bromides,
carbonates, nitrates, are also common accelerators for concrete with
lower performance than CaCl2. Most commercial accelerators also
contain sodium/calcium nitrates or nitrites [113]. Calcium nitrate, (Ca
(NO3)2), for example, increases the concentration of calcium ions
leading to a faster supersaturation with respect to the silicate hydrates,
and also interacts with the aluminates reaction by decreasing the sulfate
content, reducing ettringite formation and accelerating the sulfate de-
pletion. This latter effect would generally be a negative side effect but,
in the case of 3D printing, could represent an advantage, as presented in
Section 4.2. However, from a durability point of view, although calcium
nitrate is known to be an effective inhibitor against chloride induced
corrosion, there is a possibility that it might enhance corrosion through
carbonation [119, 194].
At this point, it has to be noted that accelerators targeting mainly
silicate hydration might show some limitations as it would require very
high quantities to achieve sufficiently fast strength gain for additive
manufacturing, which could interfere with rheological or durability
properties. Therefore, a category of accelerators that presents inter-
esting features for printable concrete is shotcrete accelerators
[112,120]. For sprayed concrete, they are usually added in the nozzle of
the equipment during spraying, allowing a very quick setting as soon as
the concrete is sprayed and applied on the wall surface. Silicate and
aluminum salts are among the most commonly used types of shotcrete
D. Marchon et al.
Fig. 5. Master curve of retardation of the maximum rate of hydration, Δt, as a function of PCE structure and dosage obtained for an ordinary Portland cement (left)
and schematic representation of sub-molecular scale characteristics of an adsorbed PCE molecule (right, reproduced from [29]). The retardation is proportional to the
number of repeat units cPCE , where cPCE is the dosage in mass of PCE and MRU is the mass of one repeat unit, and to a function of the polymer structure given by
MRU
3/2
( C/E
C/E+1 ) , where C/E represents the number of carboxylate charges per repeat unit (Fig. 2). This function is proportional to the linear charge density of the
backbone, C/E
C/E+1
, and inversely proportional to an average distance of the backbone to the surface of cement,
accelerators [120]. Silicates were first used but they have a lower
performance than aluminum-based products. The latter are divided into
two classes: alkali and alkali-free products. They are both composed of
salts of aluminum but the alkali-free accelerator is simply an acidic
solution of these salts, which has the advantage of not being hazardous.
With their high concentration in aluminum and sulfate, alkali-free ac-
celerators promote the precipitation of ettringite, causing a fast floc-
culation of the system and allowing the placement of thick layers of
shotcrete on tunnel walls [121]. Therefore, this very basic principle is
of great interest for additive manufacturing, in cases where very fast
setting is needed. These admixtures, as well as potassium carbonate, are
also known to promote the flash-setting of C3A at moderate or high
dosages, something that might present interesting features for extruded
concrete (see Section 4.2).
2.3. Curing stage
In digitally fabricated concretes, transport properties of the freshly
placed concrete must be carefully controlled since no fixed formwork
can prevent water loss. Indeed, early water loss can limit the hydration
degree, in particular at low w/c ratio. This can affect adhesion between
deposited layers [122] and induce plastic shrinkage cracking to ad-
versely affect final performance. The specific aspect of water loss for
additive manufacturing has not yet been investigated, as there is a clear
change with respect to conventional concrete applications where water
loss at very early ages does not occur due to the presence of formwork.
However, it is expected that there will be parallels to the casting of
horizontal slabs or flooring systems since they also exhibit relatively
high exposed surface areas. Thus, important knowledge may be gained
from experience in such applications. For example, additive manu-
facturing may benefit from using saturated lightweight aggregates for
internal curing or chemical compounds, such as expansive agents and
shrinkage-reducing admixtures [123–125].
Still, challenges and solutions are expected to be unique for additive
manufacturing. For instance, curing compounds can be utilized but
their impact on the adhesion properties between printed layers must be
considered for extrusion-based techniques. Water loss due to increased
wind speed and/or temperature during printing must be addressed to
6
Cement and Concrete Research xxx (xxxx) xxx–xxx
C / E + 1 1/2
( C/E ) [29].
facilitate on-site applications. Apis Cor performed 3D concrete printing
within a temperature-controlled tent due to cold temperatures – similar
approaches can be taken to control water loss [126]. Finally, in utilizing
admixtures and alternate binders to control rheology and hydration
aspects for additive manufacturing, it will be essential to ultimately
consider their effect on water transport properties [127–129].
3. Properties evolution for printable concrete
The aim of this section is to describe the main stages of the rheo-
logical state of concretes used for digital fabrication. The focus is
mainly related to extrusion printing, which represents the most in-
vestigated and implemented digital fabrication technique [4]. How-
ever, as stated by others [4,8,10], the fundamental questions about the
control of the material properties are shared by other approaches, e.g.
slip forming [4]. Fig. 6 schematically represents the expected evolution
of the yield stress of a printable concrete, dividing it into four stages,
while Table 1 summarizes the admixtures properties needed for the
different stages. The principle described below is mostly focusing on
batch by batch material preparation with an activation of hydration.
Continuous mixing is considered as well, but it is more challenging to
ensure a constant quality in material delivery. On this subject, a more
detailed discussion is given by Reiter et al. [8].
A generic and simplified depiction of the desired performance of a
cement-based system for extrusion printing is presented in Fig. 6, where
the evolution of fluidity, expressed as yield stress (Pa), is divided into
four main stages. It is necessary to clarify that dynamic yield stress is
the stress necessary to terminate flow under shear, while static yield
stress is the stress necessary to initiate flow from rest and thixotropy
accounts for the difference between the two. For extrusion printing,
static yield stress is expected to be critical for load bearing capacity and
shape stability [130] and thus it is depicted in Fig. 6. While the trend
shown here might appear intuitive, it conceals the effect of ongoing
hydration reactions on the rheological properties, that only recently
have been quantitatively proven in the presence of PCEs [83,111].
Depending on the mix constituents, conditions, and other parameters,
some of which will be discussed, the evolution of fluidity will change.
Concretes with low initial yield stress values are typically needed for
D. Marchon et al.
Fig. 6. Evolution of the static yield stress, reported in log-log scale in relation to
the properties of printable concretes. The direction of concrete deposition is
schematically represented traveling from right to left, with fresh concrete in
light grey and hardening concrete in black. Stage 0 represents the timeframe
during which high shear through mixing, pumping and extrusion is exerted to
fresh concrete. Starting from the deposition in stage 1, concretes show intrinsic
structural build-up at rest. The dashed line shows the structural build-up in
presence of thixotropic agents.
digital fabrication applications to guarantee an easier control of dif-
ferent processing steps, such as pumpability, extrusion and casting
(described in stage 0 in Fig. 6) [131,132]. We deliberately numbered
the stage before deposition as 0 to differentiate between the concrete
undergoing high shear through mixing, pumping and extrusion, and the
concrete at rest after deposition showing intrinsic structural build-up
starting at stage 1. For an admixed system, the initial yield stress
needed for good workability depends on the superplasticizer type, such
as PCEs, dosage and structure. As explained in Section 2.1.1, the
working mechanism of superplasticizers involves first its adsorption on
cement particles, where they play a key dispersing role at the solid-
liquid interface by controlling the state of flocculation and therefore the
rheological properties. Specifically, the yield stress decreases to some
extent when the dosage of superplasticizers increases at a given w/c
ratio. It is worth noting, however, that this simple relationship can be
altered by the incompatibility of superplasticizers with cements or
other admixtures. This will consequently reduce the amount of super-
plasticizer available per unit surface of fine particles in suspension, as
Table 1
Summary of the requirements of the main stages described in Fig. 6 and potential admixtures to reach the properties.
Stage Concrete properties
0 Pumping and extrusion High fluidity
Mix stability
1 Deposition Rapid structural build-up to retain its own shape
and weight
2 Green strength Controlled open time
3 Rapid gain strength Setting through hydration reactions
Curing Concrete hardening
Cement and Concrete Research xxx (xxxx) xxx–xxx
detailed in Section 4.3.
Attaining a high stability of the system is not always an easy task at
high dispersion degrees. This implies that it is necessary to prevent
possible segregation and bleeding of the cementitious matrix. For ad-
ditive manufacturing, this would mainly be of concern before place-
ment, since the (activated) extruded mix is supposed to be sufficiently
cohesive to not suffer from these effects. However, mix instability might
be a detrimental issue occurring just after an uncontrolled addition of
the accelerator due to an extra quantity of liquids in the mix. The ad-
dition of inorganic fines in the mix design, such as fly ash, slag, silica
fume or calcined clays, is essential to easily obtain extrudeable mixes.
The corresponding modifications in the composition of the fine fraction
of particles change their size distribution and packing density, thereby
affecting both yield stress, plastic viscosity and thixotropy [133–137].
Stage 1 in Fig. 6 represents the yield stress immediately after ex-
trusion and deposition, within a time period after mixing of water and
binder where there are no particular hydration effects on yield stress.
Although extrusion introduces shearing, which is tied to dynamic yield
stress, as soon as the layer is deposited, its ability to retain its shape is of
primary interest. Therefore, static yield stress is still considered here.
The structural build-up needed in this early stage after extrusion can
also be further tailored through the use of flocculation and/or thixo-
tropic agents (Section 2.1.3), which particularly allows a lower yield
stress at the very beginning and a rapid structural build-up right after
deposition. This is represented by the dashed line in Fig. 6. On the other
hand, an admixed system with no thixotropy is represented by the solid
line.
Stage 2 in Fig. 6 shows a transition period where static yield stress
increases over time. If left at rest, fresh concrete develops a certain
green strength through thixotropic build-up. The term green strength is
most commonly used in metallurgy or ceramics to define the strength of
compacted powders to withstand any mechanical operation that would
modify their shape before sintering [138]. In our case, the term might
define the strength of a concrete in its fresh state needed to retain its
own shape and some eventual next layers before the initial setting. A
linear increase is commonly observed in concretes [21,139–141], which
is depicted in Fig. 6. Although this green strength is typically not suf-
ficient to support multiple layers for the construction of structures taller
than 150 cm [4,8], it is essential for bridging the time gap between the
extrusion and deposition process (stage 1) and the rapid strength gain
(stage 3). In practice, stage 2 also represents the open time during
which concretes can still be easily placed and shaped and the mix ex-
hibits constant dynamic yield stress. This has also been observed in
Admixtures
Type Targeted requirements
SPs (PCEs) Dispersion
VMAs Water retention
VMAs Flocculation of particles
(Nano-) clays Flowability during extrusion, “House of cards” effect at
rest
Polymeric fibers Shear thinning during extrusion, 3D structure at rest
Entrained air
PCEs Hydration retardation
Sugar derivatives Duration of open time
Portlandite Inhibition of retarders action by either sucrose or PCEs
Clays uptake
Inorganic salts Enhanced chemical reactions
PCEs Promoted formation of hydrates and development of
C-S-H seeds new surfaces
Shotcrete accelerator
Saturated lightweight aggregates Reduction of early water loss
Expansive and shrinkage-reducing Minimization of plastic shrinkage cracking
admixtures
7
D. Marchon et al.
Fig. 7. a) Ternary diagram of CaO-Al2O3-SiO2 representing the typical composition of Portland cement, CAC, CSA and most common supplementary cementitious
materials, such as slag, fly ash, silica fume, natural pozzolan and clays. b) Ternary diagram of calcium aluminate cement, ordinary Portland cement and calcium
sulfate representing the main zones of composition of calcium aluminate cement used in practice (in dark) and the zone of composition where uncontrolled expansion
is expected.
admixed cement pastes that have been remixed with an equivalent
rotational speed before spread flow measurements [83]. This procedure
mimics the usual operative conditions on job sites before placement,
since concretes are subject to high shear rates when pumped [17]. The
almost constant yield stress measured in this stage evolves in-
dependently of hydration reactions and corresponds to the induction
period observed in isothermal calorimetry experiments [83]. When
using copolymerized PCEs, the duration of this stage was found to in-
crease linearly with the number of added functional groups [83], with a
slightly more complex relation for grafted PCEs [29,111]. Besides the
retarding effect induced by superplasticizers, the duration of the open
time may be tuned with the combination of retarders and accelerators,
as proposed in the Smart Dynamic Concrete production process [142].
The sudden increase of the yield stress shown in stage 3 (Fig. 6)
represents a crucial point for the construction of 3D printing structures.
After this point, it is known that the material is prone to supporting
more weight due to rapid strength gain but, at the same time, the
casting should be sufficiently fast, or at least precisely controlled, to
prevent the formation of surface defects, if not deep cracks. For this
reason, it becomes necessary to further investigate the properties of the
concrete system in this timeframe. Various authors have reported an
exponential increase in yield stress over time after the period of con-
stant fluidity, as indicated in stage 3 of Fig. 6 [143–147]. In this con-
text, a valuable new approach uses the relation between yield stress and
heat rate, as shown by isothermal calorimetry to determine an onset
point. Beyond this point, the yield stress increases exponentially with
the heat rate and in an irreversible way. This discriminates the two
distinct processes governing stages 2 and 3, namely, reversible and ir-
reversible structural build-up [83].
While the initial fluidity can be varied in a simple way according to
the required performances, the subsequent evolution over time is con-
sidered to be a greater challenge for practical applications. Indeed,
when the yield stress starts to increase, the control of the system be-
comes problematic. Mantellato was, however, able to rationalize much
of this behaviour in relation to the formation of new surfaces by on-
going hydration and the ability of the admixture type and dosage to
modify it [83]. More specifically, she found that it is the combination of
additional contact points and reduction in surface coverage that ap-
pears to account for the rapid increase in yield stress observed in stage 3
(Fig. 6). Although pumpable concretes are often necessary for digitally
designed structures, the depiction proposed appears valid for a broader
range of initial yield stress values and therefore for different admixtures
contents, such as superplasticizers. Indeed, different PCE dosages and
8
Cement and Concrete Research xxx (xxxx) xxx–xxx
structures affect not only the initial fluidity, but also the timeframe
available for the pumping and extrusion processes (stage 0), and in
turn, the extent to which covered cement particles interact. Being very
fundamental, this mechanism likely represents a basic principle that
may be used to rationalize, in a broader sense, the yield stress gain of
concretes used for additive manufacturing.
4. Strategies for the control of hydration and rheology and
possible limitations
4.1. Potential alternative candidates for the binding matrix
The previous sections describe the properties expected from a con-
crete used in some of the new technologies of digital fabrication and
potential admixtures that can be used to target them. Another aspect to
consider is the choice of the binding material to easily reach the ex-
pected properties. As an example, for the transition from stages 2 to 3
(Fig. 6), OPC can show limitations in terms of rate of surface devel-
opment for fast structuration. The seemingly slow structuration build-
up of OPC that would lead to a too long stage 2 can be balanced by
complementary rapid setting cements [148], such as calcium aluminate
cement (CAC) [149,150] and calcium sulfo-aluminate cement (CSA)
[151–153]. Both CSA and CAC are commonly employed in situations
where fast placement, shrinkage compensation and resistance to che-
mical attacks are needed [154,155]. Their property is driven by the
inherently rich amounts of calcium and aluminum, as depicted in
Fig. 7a. Due to the high solubility of the components, swift dissolution
of the Ca and Al ions occurs, with the subsequent formation of calcium
aluminate hydrates and ettringite (due to the presence of sulfates in
CSA). This causes a rapid surface development and exponential struc-
turation that is translated to both quick set/stiffening and rapid gain in
early strength, typically observed in CAC and/or CSA systems
[150–152]. The hydration of these binders is greatly dependent on the
moisture, temperature, duration of reaction, and presence of nucleating
agents [156–158]. When blended with OPC, the CSA and/or CAC ac-
celerate the setting time progressively with increasing OPC replacement
level and can considerably vary it, depending on the composition of the
OPC, as well as amount and type of sulphates. Furthermore, both al-
ternative binders are compatible with most chemical admixtures, in-
cluding superplasticizers, retarders and accelerators [159]. One aspect
that cannot be neglected when dealing with blends of OPC with CSA,
however, is the possibility of undesired expansion. This depends on the
ratio between the cements and components used, and more particularly
D. Marchon et al.
on the available amount of calcium sulfate in the system [155,160]. The
dashed areas in Fig. 7b shows the composition of the calcium aluminate
cements used in practice, whereas the dashed line represents the limit
above which an appropriate binder composition might induce an un-
controlled expansion.
The use of supplementary cementitious materials (SCMs) is quite
common in concrete. When partially replacing cement, they can help to
achieve the rheological and packing properties needed for stage 1 and 2
in Fig. 6, as mentioned earlier. However, their slower reaction rate may
show some limitations for the development of binders used in additive
manufacturing. Geopolymers intrinsically require some form of che-
mical activation, which in a certain sense make them good candidates
for the setting on demand needed in additive manufacturing. However,
the level of chemical activation needed might be quite high. Therefore,
it may not be trivial to efficiently deliver the needed activator without
excessively diluting the system and subsequently compromising
strength. On the other hand, initial and partial activation of a system
that contains a limited amount of SCMs could be considered. However,
as discussed in more details in Section 4.3, PCEs suffer from competitive
adsorption in the presence of some activators and therefore cannot be
used optimally.
Another possible area of interest for geopolymers is in powder bed
printing [4,161,162]. In this approach, the activator would be delivered
by the spray head. An advantage over OPC would be that the powder is
less sensitive to humidity and likely easier to recycle. However, there
are issues that must be addressed. The activators typically used are
NaOH, KOH, Na2SiO3, K2SiO3, Na2CO3 and Na2SO4 [163]. It is worth
recalling that geopolymers activated with silicate solutions have a high
viscosity, which has been mainly attributed to the activator solution
[164]. So, for powder bed printing, the high viscosity of the activator
solution may be difficult to dispense. In addition, for extrusion-based
printing, the high viscosity of the activated geopolymer should be ac-
counted for, which cannot be resolved by using other admixtures, such
as superplasticizers.
4.2. Al-Si-S chemical balance
One of the most promising solutions to improve the structuration
build-up right after deposition is to activate or enhance the aluminate
hydration reactions. This can be done by adding shotcrete-type accel-
erators or replacing part of the cement with a calcium (sulfo) aluminate
cement, as seen in the previous sections. However, playing with the
aluminate hydration by either promoting ettringite nucleation or
mixing a calcium aluminate cement with a normal Portland cement can
present some risks as this might strongly influence the sulfate con-
sumption and silicate hydration [165]. As introduced in Section 2.2 and
demonstrated already decades ago [93,94], the sulfatation level of a
cement is one of the most important aspects that controls the reaction
balance between the silicate, aluminate and sulfate phases. If the
amount of the sulfate phase in a cement is too low or its consumption is
too fast, the sulfate depletion point occurs before the main hydration of
the silicate and a flash set occurs. This results in a very rapid stiffening
and subsequent loss of fluidity, which could be detrimental if it occurs
before extrusion. Furthermore, the normal hydration of the aluminate
phase reduces the silicate hydration [89,96,111,166]. Some ad-
mixtures, such as PCEs or retarders, are also well known to favor et-
tringite nucleation in the first few minutes of hydration and effectively
increase its specific surface area [29,111,167–169]. This leads to a
faster consumption of sulfates with potential important consequences
with respect to mechanical strength if the sulfate availability is not well
controlled and its depletion occurs too early [170]. In particular, the
silicate hydration becomes strongly delayed, the early mechanical
strength decreases drastically, and this can also ultimately affect late
mechanical performances. With this in mind, and for applications
where high strength gain is not required, being able to control a pro-
moted “flash set” right after deposition would be interesting since, for
9
Cement and Concrete Research xxx (xxxx) xxx–xxx
example, it decreases the duration of stage 2 in Fig. 6 and allows earlier
placement of the next layer faster in 3D extrusion. As mentioned earlier,
shotcrete accelerators are known to promote the flash-setting of the C3A
phase at moderate or high dosages. In the application of extruded
concrete, however, their actions may be too rapid unless their dosage is
strongly reduced, their addition is located very close to the outlet and/
or they are used in combination with a retarder. In regard to late
strength, it should be noted that alkali free shotcrete accelerators are
considered to have little to no negative effect at normal dosages, while
their alkali counterparts do. This effect is strongly dosage dependent, so
in utilizing shotcrete accelerators for 3D extrusion, specific effects will
have to be examined since the dosages would clearly be lower than for
shotcrete applications.
Furthermore, similar action in shortening stage 2 by a rapid stif-
fening could be obtained by accelerating the hydration of a system with
CAC cement right at the exit of the nozzle. Finally, although all these
applications represent interesting features and advantages for printing
concretes, stability of the cementitious systems with respect to hydra-
tion and mechanical performances are still very crucial and need more
investigation.
4.3. Competitive adsorption and the related important physical aspects
One of the most important aspects coming from this analysis is that
a system needed for digital fabrication applications tends to be very
complex with different kinds of binding materials, as well as several
sources of admixtures added and acting at different times. From such
systems, undesired side effects, such as strong interactions among dif-
ferent admixtures, are also expected.
The mechanism of action of most of the chemical admixtures used in
the production of concrete is very sensitive to their adsorption behavior
on the surface of cement particles. The blending of these chemical ad-
mixtures can generate a competitive adsorption on surface sites of
particles, which will influence their performances. As shown in the
literature, competitive adsorption can be an advantage leading to sy-
nergetic effects between adsorption species [171] but, on the other
hand, can in some cases reduce the desired performances [171–174].
Many examples of competitive adsorption between a superplasticizer
and sulfates ions [175,176], hydroxides [177,178], citrates [172] and
other organic admixtures [172–174] have been studied in the literature
of cementitious materials. By adsorbing on the surface of cement par-
ticles, these displacers restrict the adsorption of polycarboxylate-type
superplasticizers and therefore affect their dispersion efficiency from a
macroscopic point of view, as shown in Fig. 8 in presence of sodium
gluconate. It was also shown in [171] that superplasticizers can, in
some cases, limit the adsorption of a cellulose ether and inhibit its
flocculating behavior.
To control the outcome of competitive adsorption, many works
studied the possibility of modifying the chemical structure of the mo-
lecules [167,179–181]. Furthermore, it should be kept in mind that
competitive adsorption is not only a matter of the admixture chemical
structure or surface affinity, but is also very dependent on the avail-
ability of sites for potential adsorption on the surface of the binder. In
the literature dealing with polymers at interfaces, three main adsorp-
tion regimes have been identified where competitive adsorption is more
or less pronounced. At low surface coverage, competitive adsorption is
not observed and all organic admixtures can adsorb on the surface
[182]. In contrast, getting closer to surface saturation (high surface
coverage), organic admixtures start to compete for adsorption sites.
Under the latter condition, the competitor with the highest affinity
would preferentially adsorb, whereas the other species may have only
access to residual surface sites. Based on this principle, adsorption re-
gimes, governing the competition among species, might be varied by
tuning the polymer dosage, adsorbed conformation or adsorption en-
ergy. It should, moreover, be kept in mind that some adsorbed species
could leave an abundance of unoccupied adsorption sites in the area
D. Marchon et al.
Fig. 8. Desorption of a superplasticizer (PCE) in the presence of a retarder (sodium gluconate) (left) and the rheological consequences (right). Adapted from [171].
they cover, which may be occupied by the other admixture without any
desorption. In addition, we would expect that the continuous formation
of adsorption sites over time due to ongoing chemical reactions may
significantly affect the extent of these adsorption regimes. From this
point of view, the use of blends such as OPC/CAC/CSA can also provide
a rapid growth in specific surface area owing to the inherently high
reactivity of these systems and the high affinity of aluminate hydrate
surfaces for PCEs. Consequently, the distribution of admixtures may be
changed between silicate surfaces and aluminates, the balance of
competitive adsorption would be shifted and the overall dispersion of
the system reduces, leading to yield stress growth.
Furthermore, it must be kept in mind that adsorption and desorption
kinetics could be at the origin of the evolution of material reactivity and
rheological behavior over time, which could be interesting for concrete
digital fabrication. In some cases, the exchange could be rapid and
reversible, as with the desorption of a superplasticizer by sulfate [47] or
sodium gluconate [46] necessary for the rapid structural build up in
stage 1 (Fig. 6), for example. However, the desorption of an already
adsorbed polymer could also, in some cases, be a very slow process in
the order of hours, days or even years, as it requires the simultaneous
desorption of the anchor groups of the macromolecule [183].
4.4. Depletion of chemical admixtures through intercalation
Aluminate phases, and more particularly layered structures, such as
layered double hydroxides (LDHs), and clays may involve another type
of disturbing interaction with some admixtures. LDHs are a class of
layered materials with a chemical composition expressed by the general
formula [M2+ 3+
1-x Mx (OH)2]
x+
[An- x-
x/n · yH2O] , where M
2+
and M3+ are
divalent and trivalent metal cations and An- is a counter anion or an-
ionic polymer possessing a charge of n- [77]. When hydrating, C3A can
form different layered phases: aluminate hydrates, C4AH13 and C4AH19,
and AFm phases, such as Ca4Al2(OH)12SO4 ⋅ 6H2O and
3CaO ⋅ Al2O3 ⋅ CaCO3 ⋅ 11H2O in the presence of sulfates and carbo-
nates, respectively. Likewise, similar layered structures such as C2AH8
(Fig. 9) are formed during CAC and CSA hydration. These unique
layered structures make specific chemisorption of anionic molecules
10
Cement and Concrete Research xxx (xxxx) xxx–xxx
from solution possible and are therefore considered as anionic ex-
changers with properties very similar to those of clays [184].
Anionic polymers such as PCEs have been shown to intercalate into
these LDHs to form layered organo-mineral phases (OMPs) [186–188].
The degree of intercalation is generally proportional to the charge
density of the LDHs and inversely correlated to the molecular weight of
the incoming anionic polymers [189–191]. Commercial PNS are also
highly susceptible to intercalation in LDH, whereas LSs are usually in-
sensitive due to their steric sizes. Under normal paste conditions, it is
expected that the polymer-LDH phases will be exfoliated and dispersed.
In any case, the presence of these layers provides for a high consump-
tion potential of anionic organic compounds, modifying their impact on
rheology and hydration kinetics.
On the other hand, clays are hydrous aluminum silicates usually
defined as “phyllosilicate minerals”. Most clays possess a mica-type
structure, while clay flakes consist of stacked platelets where a single
platelet is a unit layer [192]. As mentioned earlier, the immediate
impact of clays is a strong reduction in workability due to an important
retention of water by its high surface area, and an additional major
impact on yield stress owing to their flocculation. Furthermore, clays,
particularly smectites, attract and consume PCE superplasticizers. The
dominating driving force is governed by chemisorption of the PEO side
chains in the PCE structure into the clay layered structure via hydrogen
bonds, along with water molecules anchored by the silanol groups be-
tween the aluminosilicate layers (Fig. 10) [193]. This contrasts with the
mobilization of PCEs by LDH phases, which is driven by backbone
adsorption and for which the side chains should be expected to provide
steric hindrance. In the case of clays, the primary consumption rate is
proportional to the length of the side chain. Surface adsorption of the
PCE onto the clay surfaces through electrostatic attraction accounts
only for a minor portion of PCEs consumed by clays.
The sequestration of organics, such as PCEs, by aluminate hydrates
and clays depletes the dispersants from the pore solution, thereby re-
ducing their effectiveness. When this is not mitigated by some means,
i.e. the addition of sulfates that stabilize calcium aluminate sulfates or
the addition of sacrificial compounds as PEG polymers to be adsorbed
on the clays, this phenomenon can become a major drawback in more
Fig. 9. Schematic illustration of the layer structure
present in a hydrocalumite mineral, e.g. C2AH8.
Reproduced from [185].
D. Marchon et al.
Fig. 10. Conceptual illustration of PCE side chain intercalation between the aluminosilicate layers of montmorillonite. Reproduced from [193] with permission.
common concrete technology. However, for digital fabrication, this
may be an important and desirable property. Added in-line, clays can
cancel the dispersing effect of PCEs, causing yield stress to increase
quite rapidly and even accelerate hydration, as PCEs are no longer
adsorbed on reacting cement phases. This would first accelerate the
structural build-up in stage 1 (Fig. 6), but also the initial setting ne-
cessary in stage 3 for a rapid strength gain. Here again, the very fast
rate at which this occurs constrains the timing and/or location of the
clay addition.
5. Conclusion
Nowadays, chemical admixtures are essential for the production of
modern concretes, for which good initial fluidity, workability retention
and relative easiness of placement are some of the fundamental re-
quirements. For digital fabrication, in addition to the same require-
ments, a precise control of the fluidity and of the structuration building
rate are the new challenges that mainly come from eliminating or
substantially reducing the use of formwork. In this paper, we outlined
some chemical and physical solutions offered by common admixtures
for managing these needs for fast yield stress growth, resulting from the
delicate interplay of hydration kinetics and rheology. This is described
by Fig. 6 and summarized in Table 1.
Therefore, in controlling all phenomena leading to the structuration
at the precision necessary for digital fabrication, both hydration and
colloidal effects must be considered and controlled. This requires a
combination of material design and processing strategies. In this paper,
we focused on the first aspect and underlined existing mechanisms as
well as promising approaches to quantify their impacts. In particular,
we advocate that systematically studying how the concrete mix design
and admixture formulation affect hydration kinetics and structural
build-up will provide the knowledge-based robust digital fabrication
processes using concrete. It will also facilitate the use of a broader range
of raw materials, nonetheless targeting concretes with a lower en-
vironmental footprint, something according to which digital concrete
will undoubtedly be measured in the future.
Acknowledgements
Funding for D. Marchon was provided by an Early Postdoc.Mobility
grant (no. P2EZP2-172177) from the Swiss National Science
Foundation (SNSF). Funding for S. Mantellato was provided by the
SNSF project no. 140615 and the NCCR Digital Fabrication, funded by
the SNSF (NCCR Digital Fabrication, Agreement #51NF40-141853).
The authors would like to thank Prof. Robert J. Flatt and Dr. Nicolas
Roussel for their constructive comments on the manuscript.
11
Cement and Concrete Research xxx (xxxx) xxx–xxx
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