Journal of Building Engineering 41 (2021) 102787

Contents lists available at ScienceDirect

Journal of Building Engineering

Evaluation of phosphated superplasticizers in high-performance α-calcium

sulfate hemihydrate-based floor screeds
My Linh Vo, Johann Plank *
Technische Universität München, Lichtenbergstr. 4, 85747, Garching, Germany

ARTICLE INFO ABSTRACT

Keywords: In the present study, the applicability of phosphated comb polymers as high range water reducing agents in a
Gypsum fully formulated α-calcium sulfate hemihydrate-based self-leveling floor screed was evaluated. A phosphated and
Superplasticizer two mixed phosphated-carboxylated superplasticizers were synthesized and compared to a strictly carboxylated
Water reduction
sample (PCE) and a commercial melamine formaldehyde sulfite polycondensate (PMS). Self-leveling screeds of
Compressive strength
variable water content (w/b = 0.41 – 0.25) containing the different polymers were prepared and their key prop-
Shrinkage
erties such as spread flow, fluidity retention, flow speed, shrinkage as well as setting behavior and strength de-
velopment were examined. The results obtained encourage the utilization of phosphate group modified comb
polymers in screeds based on CaSO4-hemihydrate, particularly in high-performance screeds formulated at low
w/b ratio.

1. Introduction
In modern interior design screeds are frequently placed for the pur-
pose of smoothing or leveling floor surfaces [1]. They are defined as
one or more layers of material placed in situ, directly onto a base or onto
an intermediate or insulating layer [2]. Generally, screeds consist of a
binder, aggregates, water and chemical admixtures [3]. The most com-
mon binders for screeds include cement and calcium sulphates (CaSO4 ∙
0.5H2O or CaSO4) [4,5]. Traditionally, cement-based screeds have been
used, but one severe problem associated with them is their shrinkage
during hydration which can cause cracking, bulging and debonding
[5,6]. Furthermore, the manufacture of cement comes with a huge lib-
eration of CO2 and energy consumption is excessive [7–9]. Nowadays,
CO2 emission and energy reductions in the construction industry are in-
creasingly relevant [10,11].
Calcium sulfate-based screeds have been found to present an attrac-
tive alternative as they exhibit almost no shrinkage [12]. Moreover,
gypsum-based materials are one of the most environmentally friendly
binders [13,14] due to the significantly lower calcination temperature
[14] and their availability as by-product from industrial processes, such
as flue-gas desulfurization (FGD) [15]. Another advantage of gypsum
over cement is that it is fully recyclable [14,16]. Moreover, CaSO4-
based materials can provide better thermal and sound insulation as well
as fire resistance [14]. Another advantage of calcium sulfate screeds is
that they develop their strength more rapidly than cement [5], e.g.
nearly 50% of their final strength is gained within 24 h only [12]. Thus,
the benefits of calcium sulfate screeds are obvious, yet they are still less
popular than cement-based ones, simply because CaSO4 screeds are un-
suitable for wet areas [17] and their strength is inferior to that of ce-
ment-based screeds.
Calcium sulfate screeds are based on either anhydrite (so-called
CaSO4 II-E) or α-hemihydrate (CaSO4 ∙ 0.5H2O, in short: α-hh) [3,5,12].
Anhydrite-based screeds are less expensive, but relative to drying time
and strength development they are inferior to those based on α-
hemihydrate [18,19].
The application of self-leveling screeds has become widespread over
recent years, due to their simple process which relives workers from
heavy work [2,20]. To achieve the self-spreading property, a high level
of fluidity must be introduced [2]. For this purpose, fluidizing agents
(also referred to as water reducing agents, dispersants or superplasticiz-
ers) are applied [2,21]. In anhydrite screeds the use of melamine
formaldehyde sulfite polycondensate (PMS) superplasticizer is predom-
inant although its water reducing and dispersing ability are modest and
relatively high dosages are required [22]. Another aspect of PMS is that
it contains formaldehyde which is classified as a human carcinogen
[22,23]. This presents a serious concern, especially in interior construc-
tion [22]. Therefore, polycarboxylate (PCE) superplasticizers which are
popular as high range water-reducing agents in cement-based systems
[24] have been introduced to calcium sulfate screeds.

* Corresponding author.
E-mail address: sekretariat@bauchemie.ch.tum.de (J. Plank).

https://doi.org/10.1016/j.jobe.2021.102787
Received 6 October 2020; Received in revised form 21 May 2021; Accepted 24 May 2021
Available online 1 June 2021
2352-7102/© 2021 Elsevier Ltd. All rights reserved.
M.L. Vo and J. Plank
So far, only few studies have focused on the effects of PCEs in α-
calcium sulfate hemihydrate binder, but no publications can be found
on the performance of these polymers in fully formulated α-
hemihydrate floor screeds. B. Guan et al. [25] and H. Zhao et al. [26]
report that the water content in pure α-hemihydrate binder can be re-
duced to ~ 15% by introducing 0.5% of PMS or PNS (sulfonated naph-
thalene formaldehyde polycondensate) versus 20% when 0.4% PCE are
added. As a result of the reduced w/b ratio, the final strength was in-
creased considerably, ~ 23% for the PNS modified binder and ~ 27%
for the binder admixed with PCE. Furthermore, PNS accelerated hydra-
tion in the early stage, but decelerated it in the later stage whereas the
PCE retarded the hydration of α-hh [25,26].
In a previous study, we presented comb polymers modified with
phosphate groups as novel high-performance superplasticizers for α-as
well as β-calcium sulfate hemihydrate and demonstrated their superior
dispersing performance as well as their significantly higher water re-
ducing capacity as compared to conventional PCEs and PNS. These su-
perior properties are owed to their higher adsorbed amounts in compar-
ison to PCE and PNS [27].
In the present study, the focus is on the application of phosphated
superplasticizers in a fully formulated, ready-to-use, self-leveling and
self-healing floor screed based on α-hh. For this purpose, three different
phosphated superplasticizers holding different amounts of phosphate
and carboxylate groups, a strictly carboxylated PCE representing an in-
dustry standard and a commercial PMS sample commonly applied in
CaSO4 binder systems were investigated. Furthermore, high-strength
screed formulations characterized by ultra-low w/b ratios were tested
with respect to their time-dependent spread flow, flow speed in the flow
channel and shrinkage in the shrinkage drain. Additionally, their set-
ting times (open times) were determined and heat flow calorimetry as
well as compressive strength tests were performed to capture their
hardening properties.
2. Materials and methods
2.1. Materials
A fully formulated α-hemihydrate-based floor screed presents the
basis of this study. Its composition is displayed in Table 1. Different su-
Table 1
Basic formulation of the floor screed used in this study.
component product mass (g)
α-hemihydrate Raddichem 27a 400.0
sand (0.08–2.00 mm) standard sand 585.9
cement CEM I 42.5 R 12.0
water retention agent Tylose® H 300 P2 0.8
defoamer Agitan P803 0.5
retarder Retardan® P 0.2
water deionized water 165.0
a Produced from FGD gypsum.
Fig. 1. Chemical structures of 45P1PC4, 45P0.5PC5 and PMS superplasticizers used in the study.
2
Journal of Building Engineering 41 (2021) 102787
perplasticizers were admixed to this formulation to achieve high fluid-
ity and self-leveling properties.
2.1.1. Superplasticizer samples
In this study, the impact of three different phosphated comb poly-
mers on the screed formulation was compared with that of a carboxy-
lated PCE and a commercial melamine formaldehyde sulfite polycon-
densate (PMS) sample.
Among the phosphated superplasticizers, one was 100% phosphated
whereas the other two contained both phosphate and carboxylate
groups. The strictly phosphated superplasticizer (designated as 45P3)
contained 2-(methacryloyl oxy) ethyl phosphate (MOEP) and poly(eth-
ylene glycol) methacrylate ester (MPEG macromonomer, MM) at a mo-
lar ratio of 3:1 and its side chain was comprised of 45 ethylene oxid
units. The mixed phosphated-carboxylated superplasticizers labelled as
45P1PC4 consisted of 2-(methacryloyl oxy) ethyl phosphate,
methacrylic acid (MAA) and MPEG macromonomer at a molar ratio of
1:4:1 whereas the second sample (45P0.5PC5) was composed of the
same monomers, but at a molar ratio of 0.5:5:1. Their syntheses are de-
scribed in detail in Ref. [28]. The ratio of anionic charge per side chain
was fixed to six for all comb-shaped superplasticizers, as different an-
ionic charges would impact the dispersing performance. Phosphate
groups bear two negative charges whereas carboxylate groups possess
only one.
The first reference sample was a strictly carboxylated PCE (45PC6)
prepared from methacrylic acid and MPEG macromonomer at the same
molar ratio of 6:1 as for the phosphated copolymers. A detailed descrip-
tion of the synthesis of this PCE is presented in Ref. [29]. The PMS refer-
ence sample was a commercial product, Melment® F 15 G supplied by
BASF Construction Additives GmbH, Trostberg, Germany. It is com-
posed of melamine, formaldehyde and sodium sulfite at a molar ratio of
~ 1:2.9:1.2 and exhibits a relatively low molecular weight. Its principle
synthesis is described in Ref. [30]. This powder presents an industry
standard in CaSO4-based building materials. The chemical structures of
45P1PC4, 45P0.5PC5 and PMS are shown in Fig. 1. The molecular
structures of 45P3 and 45PC6 have been displayed in our previous work
[27].
2.1.2. α-Hemihydrate sample
The α-hemihydrate sample (Raddichem 27) was supplied by Casea
company (Ellrich plant, Germany). Raddichem 27 is produced from flue
gas desulfurization (FGD) gypsum.
2.1.3. Sand
CEN standard sand [31] obtained from NORMSAND GmbH
(Beckum, Germany) was used to prepare the floor screed samples.
2.1.4. Cement
An ordinary Portland cement sample (CEM I 42.5 R) provided by
Südbayerisches Portland-Zementwerk Gebr. Wiesböck & Co. GmbH
(Rohrdorf, Germany) was used.
M.L. Vo and J. Plank
2.1.5. Water retention agent
A hydroxy ethyl cellulose sample (Tylose® H 300 P2 from SE Tylose
GmbH & Co. KG, Wiesbaden, Germany) was utilized which is com-
monly applied in self-leveling compounds to achieve water retention
and sag resistance.
2.1.6. Defoamer
Most superplasticizers (with the exception of PMS) entrain air into
the building product which necessitates addition of a defoaming agent
[32]. Here, a commercial powder defoamer (AGITAN® P 803 from
Münzing Chemie GmbH, Abstatt, Germany) was employed.
2.1.7. Retarder
Retardan® P (Sika GmbH, Leimen, Germany) was admixed to retard
the hydration of α-hemihydrate and to prolong the setting time and ex-
tend the open time.
2.1.8. Water
Deionized water from a Synergy® water purification system (Milli-
pore GmbH, Germany) was used.
2.2. Methods
2.2.1. Characterization of polymer samples
The self-synthesized superplasticizers were characterized via size
exclusion chromatography (SEC) using a Waters 2695 gel permeation
chromatography separation module equipped with the three
UltrahydrogelTM columns 500, 250 and 150, a refractory index detector
2414 module (Waters, Eschborn, Germany) and a Dawn EOS 3 angle
static light scattering detector (Wyatt Technology Corporation, Clinton,
SC/USA). The polymer samples were dissolved at 10 g/L concentration
in 0.1 N NaNO3 solution (pH = 12) as eluent and then filtered through
a 0.2 μm filter. Samples were measured at a flow rate of 1 mL/min and
number (Mn) as well as weight average molecular weight (Mw) and
polydispersity index (PDI = Mw/Mn) were calculated by using the dn/
dc value of polyethylene glycol. The SEC spectra of the synthesized
comb polymers are displayed in Fig. 2, and the characteristic properties
obtained from this analysis are tabulated in Table 2.
Fig. 2. SEC spectra of the self-synthesized copolymers.
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Journal of Building Engineering 41 (2021) 102787
2.2.2. Characterization of α-hemihydrate sample
A Cilas 1064 laser granulometer (Cilas Company, Marseille, France)
was used to determine the particle size distribution of the α-
hemihydrate sample which was found to be 1.6 μm (d10), 22.3 μm (d50)
and 56.0 μm (d90). Its specific density as investigated via Helium pyc-
nometry (Ultrapycnometer 1000, Quantachrome Instruments, Boynton
Beach, USA) was 2.79 g/cm3 and its specific surface area according to
the Blaine method was 3100 cm2/g. Additionally, the XRD pattern of
the α-hh sample was taken on a D8 Advance instrument (Bruker AXS,
Karlsruhe, Germany) and is presented in Fig. 3. The XRD diagram con-
firms phase-purity of the α-hh sample.
2.3. Preparation of floor screed
All components presented in Table 1 were dry-blended before
adding the appropriate amounts of water and superplasticizer to
achieve a spread flow of 26 ± 0.5 cm. The screeds were prepared via
an eccentric agitator (ToniMIX, Toni Technik Baustoffprüfsysteme
GmbH, Berlin, Germany) according to DIN EN 13454-2 standard [34].
Water holding the superplasticizer was filled into the mixing bowl be-
fore adding the preblended dry components within the first 15 s There-
after, the mixture was homogenized for 1 min 45 s at 145 rpm resulting
in a total mixing time of 2 min. Here and in the following, all superplas-
ticizer dosages given are meant in % by weight of α-hemihydrate
binder. Thus, for simplicity, dosages are presented only as %.
2.4. Spread flow measurements
A Vicat cone (height 60 mm, upper diameter 70 mm, bottom diame-
ter 100 mm) placed on a glass plate was used to perform the spread
flow experiments as defined in DIN EN 13454-2 [34]. The freshly mixed
screeds were poured into the cone which then was removed vertically.
The final spread diameter was measured at two directions perpendicu-
lar to each other and then averaged.
An important requirement for flow screeds is an open time of >
30 min [35]. Therefore, the spread flow values were also determined at
15, 30, 45 and 60 min after the start of the mixing. Prior to each mea-
surement the formulation was stirred again for 5 s at high speed
M.L. Vo and J. Plank Journal of Building Engineering 41 (2021) 102787

Table 2 2.6. Dry shrinkage/expansion

Molecular properties of the self-synthesized superplasticizer samples.
Polymer Molar ratio MOEP:MAA:MM Mw (g/mol) Mn (g/mol) PDI (Mw/Mn) Shrinkage/expansion behavior was assessed on 1 m long shrinkage
drains (Schleibinger Geräte Teubert u. Greim GmbH, Buchbach, Ger-
45P3 3:0:1 91,700 37,100 2.5
many) as shown in Fig. 5. In experiment, 5 kg of each floor screed sam-
45P1PC4 1:4:1 44,200 19,100 2.3
ple were prepared and then immediately placed in the shrinkage drain
45P0.5PC5 0.5:5:1 33,100 15,700 2.1
45PC6 0:6:1 25,600 13,500 1.9 which was covered with a removable neoprene rubber sheet. On one
side of the shrinkage drain a movable anchor was fixed. The movement
of this anchor was monitored automatically via a digital probe. The
measurement started 24 h after preparation and the length of the speci-
men was recorded every 1–2 min over a period of 70 days. During the
measurements the shrinkage drains were stored in a climate chamber at
20 °C and 6% relative humidity.

2.7. Setting times

Fig. 3. XRD pattern of the α-hemihydrate sample Raddichem 27 used in the
study (black) and reference pattern PDF 00-036-0617 (D) – Bassanite [33]
(red). (For interpretation of the references to colour in this figure legend, the
reader is referred to the Web version of this article.)
(285 rpm). Between individual measurements the screed was stored in
the mixing bowl covered with a wet cloth to prevent drying out.
2.5. Flow channel experiments
For floor screeds not only the spread value is important, but also the
speed at which the screed spreads out. Therefore, tests were carried out
in a flow channel (Fig. 4) from FORM + TEST Seidner&Co. GmbH
(Riedlingen, Germany) following DIN EN 13395-2 [36]. This method
allows to capture the speed at which a screed spreads out. In experi-
ment, 1 L of flow screed was prepared as described in section 2.3 and
transferred to the funnel of the flow channel. After 30 s, the rod was
lifted up causing the screed to flow along the flow channel. The spread
value was taken every 30 s until flow ceased. The flow rate was calcu-
lated by dividing the spread flow value obtained after 30 s by 0.5 min.
Initial and final setting times of the screed formulations were deter-
mined using a Vicat needle apparatus according to DIN EN 13454-2
[34]. For this purpose, fully formulated screeds were prepared as de-
scribed in chapter 2.3 and then filled into a Vicat cone placed on a
plate. Subsequently, initial and final setting times as defined by DIN EN
13454-2 standard [34] were recorded at the conditions of 20 °C and
65% relative humidity.
2.8. Isothermal heat flow calorimetry
Heat release from the hydrating floor screed samples was monitored
using a TAM Air isothermal heat conduction calorimeter (Thermomet-
ric, Järfälla, Sweden). For this purpose, the samples were prepared by
mixing and homogenizing 16 g of the dry blended floor screed with the
appropriate amounts of water and superplasticizer for 120 s and trans-
ferred into glass ampoules which were then placed in the calorimeter.
During the experiments temperature was constant at 20 °C, and heat
flow curves were recorded until heat release ceased. The calorimeter
captures the exothermal heat flow of the samples. The cumulated heat
Q was obtained by integrating the heat flow yields.

Fig. 4. Conventional flow channel used to assess the flow speed of the floor Fig. 5. Shrinkage drain equipped with a movable anchor connected to a digital
screed sample. probe as used in the experiments.

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M.L. Vo and J. Plank Journal of Building Engineering 41 (2021) 102787

2.9. Compressive strength
Compressive strength of the floor screeds was tested after 4 h; 1; 3; 7
and 28 days following DIN EN 196-1 standard [31]. For each mix, three
sets of mortar prisms (40 × 40 × 160 mm dimension) were prepared.
The specimens were first stored for 24 h in a sealed plastic box and
placed above 1 cm of water to ensure 90% humidity. After 24 h, the
samples were removed from the molds and stored in a climate chamber
at 20 °C and 65% relative humidity. To capture the mechanical proper-
ties, at first the flexural strengths and thereafter, the compressive
strength data were obtained. From the results, the average of all values
was calculated and reported.
3. Results and discussion
3.1. Water reducing effect of phosphated superplasticizers in floor screed
This experiment was carried out to investigate the water reduction
power of the five different superplasticizers in the α-hemihydrate-based
floor screed. For this purpose, the water-to-hemihydrate ratio (w/b ra-
tio) was stepwise lowered from 0.41 (0% water reduction; labelled as
WR0) to 0.25 (corresponding to 40% water reduction; abbrev. as
WR40) and polymer dosages were adjusted such as to maintain a spread
flow value of 26 ± 0.5 cm which satisfies the requirement according to
the standard. There, a spread flow of at least 22 cm is specified [35].
The amount of water of the different screed formulations is tabulated in
Table 3.
Table 3
Water reduction rate, w/b ratio and amount of water used in the preparation
of the floor screed formulations.
From the results displayed in Fig. 6 it is obvious that polymer
dosages generally increased with ascending water reduction rate. More-
over, all polymers containing phosphate groups (45P3, 45P1PC4 and
45P0.5PC5) were capable to reduce the amount of water by as much as
40% whereas the strictly carboxylated sample 45PC6 reduced the water
content by max. 30%, and PMS achieved a water reduction rate of 10%
only. In the initial formulation (≙ 0% water reduction) the dosages of
all comb polymers were comparable (~0.05%), only the polyconden-
sate PMS required a higher dosage of 0.3% to achieve the target spread
flow of 26 cm. However, when the amount of water was decreased,
then significant differences between the comb polymers occurred. For
example, at 20% water reduction, the lowest dosages were found for
the phosphated samples 45P3 and 45P1PC4 (~0.10%) and 45P0.5PC5
(0.12%), whereas for the carboxylated comb polymer 45PC6 addition
of 0.15% were required. This gap even widened at further decreased
water reduction rates. At the ultra-low w/b ratio of 0.25 (water reduc-
tion 40% !) the completely phosphated sample 45P3 performed best
(required dosage 0.95%) while the mixed phosphated-carboxylated
polymer 45P1PC4 demanded 1.3%. For the comb polymer with the
least amount of phosphate 45P0.5PC5 even 2.3% were needed to
achieve the target spread flow of 26 cm.
The results demonstrate that when phosphate groups are incorpo-
rated into the polymers, then a superior water reducing capability is
achieved as compared to the strictly carboxylated sample 45PC6 and
the polycondensate PMS. Thus, not only in pure α-hh but also here in
the fully formulated screed composition their dispersing effectiveness is
far superior over conventional superplasticizers. The reason for their
superior water reducing capability is their higher adsorbed amount on
the binder [27]. As such, partially or completely phosphated copoly-
mers allow ultra-high water reduction rates which are completely inac-
cessible by conventional fluidizers.

water reduction rate w/b ratio amount of water

[%] [g]
3.2. Workability retention

0 0.41 165.0 In practical application, sufficient workability (fluidity) over at least

10 0.37 148.5 30 min [35] and preferably for 1 h is required to place the screed.
20 0.33 132.0
Therefore, the spread flow of the screed formulations was measured at
30 0.29 115.5
40 0.25 99.0
15; 30; 45 and 60 min after preparation. Table 4 displays the change

Fig. 6. Dosages of the different superplasticizers required to reach a slump flow of 26 ± 0.5 cm at different water-to-hemihydrate (w/b) ratios of 0.41; 0.37; 0.33;
0.29 and 0.25.

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M.L. Vo and J. Plank Journal of Building Engineering 41 (2021) 102787

Table 4 boxylated PCE was noticeably inferior (flow rate 94 cm/min and final
Initial and 60 min spread flow values for the floor screed formulations tested. flow of 56.5 cm).
admixture spread flow [cm] At 20% water reduction, the flow rate and final flow values of all
screed formulations decreased. Generally, polymers containing phos-
0% WR 10% WR 20% WR 30% WR 40% WR
phate groups outperformed the strictly carboxylated one (45PC6).
2 60 2 60 2 60 2 60 2 60 Again, 45P3 produced by far the highest flow speed (74 cm/min) and
reached a final flow value of 61 cm which much exceeded that of all
45P3 26.1 24.4 26.3 25.0 25.8 24.0 26.1 25.1 26.4 25.7
45P1PC4 26.1 24.3 26.0 24.5 26.3 24.3 25.8 24.7 26.3 25.8
other samples (54 – 55.5 cm), with 45PC6 exhibiting the lowest effec-
45P0.5PC5 26.3 24.7 26.4 24.4 26.0 24.5 25.6 24.8 25.7 25.2 tiveness relative to flow speed.
45PC6 26.1 25.3 25.8 25.6 26.2 24.9 26.2 24.3 – – At the highest water reduction of 40%, flow rate and final flow de-
PMS 26.4 24.1 26.1 23.9 – – – – – – creased again. The flow rates were remarkably low (33 – 26 cm/min)
indicating “sticky” consistency whereas the final flow values were sur-
from the initial spread flow (26 cm) to the flow value recorded after prisingly high. Such flow behavior is well known e.g. from concretes
60 min. prepared at ultra-low water-to-cement ratios of ≤0.3 [37,38]. Appar-
The results corroborate that all formulations admixed with com- ently, such highly solids loaded suspensions like the screed at 40% wa-
pletely or partially phosphated comb polymers successfully nearly re- ter reduction are characterized by high plastic viscosity which greatly
tained their initial workability over 60 min (decrease only 0.5 – decelerates the flow speed, as was established in cementitious systems
2.0 cm), independent of the water reduction rate which is quite remark- before [39].
able. In comparison, the strictly carboxylated sample 45PC6 revealed a The flow channel experiments clarify that at 0% WR 45P3 and PMS
slightly stronger decrease of workability in the system with 30% water produced the highest flow rate as well as the highest final flow values.
reduction, and the PMS sample produced a more noticeable decline to The mixed carboxylated-phosphated polymers were inferior as com-
23.9 cm already at 10% water reduction. pared to them, but still outperformed the conventional PCE superplasti-
In summary, all formulations are able to retain acceptable fluidity cizer 45PC6. However, when the w/b ratio was reduced stepwise, then
over at least 60 min however the phosphated copolymers outperform the superiority of the phosphated comb polymer 45P3 became even
the conventional superplasticizers because only they are able to achieve more evident, and the performance gap to the carboxylated samples
this at water reduction rates of up to 40%. widened considerably. Apparently, the stickiness of floor screeds for-
In the following, only the formulations with WR0, WR20 and WR40 mulated with a high solids volume can be overcome by incorporating
were looked at to limit the number of tests. phosphate as a functional group into the superplasticizer.

3.3. Behavior in the flow channel 3.4. Expansion and dry shrinkage behavior

In actual application not only the final spread flow, but also the
speed of flow presents a critical factor. When the flow rate of a screed is
high, then it spreads out fast and placement time for a given area is
shorter. Flow channel experiments can reveal the flow speed of individ-
ual floor screeds. The results are exhibited in Fig. 7 and Table 5.
In the initial formulation (0% WR), both 45P3 and PMS produced
the highest flow speed (99 or 100 cm/min) and final flow value
(61.5 cm). The partially phosphated PCEs performed slightly less (flow
rate 96 cm/min and final flow value of 59 cm) while the strictly car-
Shrinkage presents a major problem associated with cement-based
floor screeds, because it can result in cracks and bulges. Generally,
screeds based on calcium sulphates usually exhibit a very minor shrink-
age, thus large areas can be produced without joints. The shrinkage of
cement-based products normally is ~ 0.6 mm/m [40], whereas CaSO4 ∙
n H2O-based screeds exhibit values of ±0.2 mm/m only [35]. The ex-
pansion/dry shrinkage values of the screeds admixed with the different
superplasticizers at 0 – 40% water reduction was measured and the re-
sults are plotted in Fig. 8. There, positive values correspond to an ex-
pansion and negative values signify shrinkage.

Fig. 7. Flow rate of the different floor screed formulations tested in the flow channel.

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M.L. Vo and J. Plank Journal of Building Engineering 41 (2021) 102787

Table 5 idizer. Maximum expansion was reached after about 10 – 15 days, with
Flow rate and final flow values of the floor screeds as determined in the flow values ranging between 0.02 and 0.025 mm/m only and shrinkage val-
channel. ues of - 0.08 mm/m to - 0.1 mm/m were reached at the end of the test-
polymer WR flow rate final flow ing period. Among the comb-shaped polymers no clear trend became
sample [%] [cm/min] [cm] visible, apparently the substitution of carboxylate with phosphate
groups has no impact on the volume changes of the screed. Interest-
PMS 0 100 61.5
45P3 0 99 61.5
ingly, the expansion of the screed admixed with PMS was slightly
45P1PC4 0 96 58.5 higher (~0.03 mm/m).
45P0.5PC0.5 0 96 59.0 At 20% water reduction, maximum expansion was observed after 15
45PC6 0 94 56.5 – 20 days, with values ranging from about 0.035 to 0.045 mm/m, and
45P3 20 74 61.0 after 70 days the shrinkage value for the 45P3 modified screed was
45P1PC4 20 66 55.5
0 mm/m whereas all other formulations recorded values of ~ -
45P0.5PC0.5 20 66 54.0
45PC6 20 64 54.0
0.015 mm/m. Yet, again only minor differences between individual su-
45P3 40 33 57.5 perplasticizer samples were observed.
45P1PC4 40 28 53.5 Remarkably, at 40% water reduction initial expansion became much
45P0.5PC0.5 40 26 53.0 more severe and attained values of between 0.15 mm/m and almost
0.2 mm/m after 10 – 25 days. Furthermore, the completely phosphated
It can be seen that all floor screeds initially expand and later turn comb polymer 45P3 exhibited the lowest expansion (0.15 mm/m), fol-
into shrinkage. However, all dimensional changes remain within the ac- lowed by the mixed derivatized sample 45P1PC4 (0.17 mm/m) while
ceptable range of ±0.2 mm/m. Second, it becomes evident that expan- the copolymer holding the lowest amount of phosphate groups
sion generally increases at decreased w/b ratios, and this effect is par- (45P0.5PC5) produced the strongest shrinkage (almost 0.2 mm/m).
ticularly strong at 40% water reduction. The differences in the expansion/shrinkage behavior of the WR40 sys-
Relative to the superplasticizers, in the initial formulation (no water tems are attributed to the noticeably high superplasticizer dosages
reduction) all comb-shaped polymers developed comparable expan- which impact the size and morphology of the gypsum crystals.
sion/shrinkage profiles which were similar to the system without flu-

Fig. 8. Expansion and shrinkage of the floor screeds prepared at various water reduction rates of 0%; 20% and 40% and admixed with different superplasticizers
(top) enlarged presentation of values for 0% and 20% (bottom).

7
M.L. Vo and J. Plank
To summarize, the expansion and shrinkage values of all formula-
tions tested fulfilled the requirements laid down in the standard [35] as
they were ≤0.2 mm/m and therefore confirmed the practical applica-
bility of the screed formulations designed for this study.
3.5. Setting times
The initial and final setting times of the formulations holding differ-
ent superplasticizers were measured using the Vicat method. The re-
sults are illustrated in Fig. 9.
Initial set of the reference sample (w/b ratio = 0.41) holding no
dispersing agent occurred at 1 h 50 min, and its final set was recorded
10 min later. When superplasticizers were admixed to this system, then
the initial and final setting times increased slightly, with PMS produc-
ing the largest increase (final setting at 2.4 h vs. 2.1 h for 45P3 which
still presents a quite moderate change. The differences recorded might
also be stem from the different dosages of the superplasticizers admixed
to the system. It is also evident that generally final set occurred quickly
after the initial set.
As expected, at 20% water reduction setting times were slightly re-
duced as compared to the initial system, and a lower content of phos-
phate groups in the comb polymers led to shorter setting times. Still,
only a difference of 10–15 min as compared to the reference samples
was encountered. Here, the reduced water content beat the slight re-
tarding effect of the superplasticizers although these formulations con-
tained higher dosages of the polymers.
However, most striking were the setting times recorded for the
screed exhibiting 40% water reduction. Here, much longer setting times
reaching from ~ 15 h for the strictly phosphated comb polymer 45P3 to
~ 22 h for the slightly phosphated sample 45P0.5PC5 were encoun-
tered. Obviously, the trend is that a higher content of carboxylate
groups extends the setting time whereas phosphate functionalities
somewhat can control this excessive retardation which is attributed to
the high polymer additions (0.95%–2.3%) and renders this system im-
practical.
The measurements suggest that the significant amounts of super-
plasticizers required in the system with 40% water reduction delay the
setting times disproportionally. More specific, the setting times of the
mixtures with 40% less water were retarded from 2 h to 15 – 22 h.
Fig. 9. Initial and final setting times of the screed formulations; water reduction rate = 0%, 20% and 40%.
8
Journal of Building Engineering 41 (2021) 102787
It is noteworthy that the floor screeds at 0% and 20% water reduc-
tion rate set rapidly although their open time was maintained for at
least 60 min. From a practical point of view, this appears to be ideal as
it provides ample time for the worker to spread the floor screed, yet still
short walk-on times are achieved. These two properties facilitate a sim-
ple and fast construction process which helps to save time and costs.
However, this advantage no longer applies to ultra-high strength α-hh
floor screeds which are formulated at 40% water reduction rate.
3.6. Isothermal heat flow calorimetry
Isothermal heat flow calorimetry presents a common method to in-
vestigate the influence of polymers on the hydration kinetics. In the fol-
lowing, the heat flow curves of the formulations with 0, 20 and 40%
water reduction admixed with the different superplasticizers will be
discussed.
According to Fig. 10 (top), in the initial system (WR = 0) all super-
plasticizers led to a prolonged induction period and reduced height of
the peak. The effect was particularly strong for PMS and quite compara-
ble for all comb polymers including the carboxylated one. Yet, the total
heat of hydration remained unchanged in comparison to the reference
formulation, with the exception of the PMS treated system which pro-
duced a slightly reduced cumulative heat. This behavior can be ex-
plained by the significantly higher dosage of PMS (0.3%) as compared
to the comb polymers (0.042 – 0.050%).
At 20% water reduction, the induction period was extended only for
the copolymers containing higher amounts of phosphate (45P3 and
45P1PC4) whereas the two other polymers produced induction times
comparable to those of the non-admixed system (Fig. 10, middle).
Again, the cumulative heat release of all screeds was rather compara-
ble, and no significant impact of individual superplasticizers was de-
tected.
Completely different observations were made in the screed formu-
lated at 40% water reduction (Fig. 10, bottom). There, all phosphated
polymers caused a very significant extension of the induction period
from <2 h for the initial screed (0% WR) to 15 – 22 h, with the trend
being that the lower the phosphate content in the comb polymers, the
longer was the induction time. This trend is opposite to the behavior
recorded in the system of 20% water reduction. Consequently, at 40%
M.L. Vo and J. Plank
Fig. 10. Isothermal heat flow calorimetry of floor screed compositions containing different superplasticizers formulated at a w/b ratio of 0.41 (top), of 0.33 (mid-
dle) and of 0.25 (bottom); differential heat flow (left) and cumulative heat flow (right).
water reduction within the first 15 – 20 h the total heat release for all
screeds was much reduced as compared to the untreated sample, but
later started to increase and after 60 h reaches ~ 90% of the total heat
release by the reference.
The calorimetric tests reveal that all superplasticizers retard the hy-
dration of α-hemihydrate which is in line with the results obtained from
the setting times (Fig. 9). Retardation is particularly strong for the
melamine superplasticizer. For the comb polymers, a higher carboxy-
late content prompts a stronger retardation except for the screed with
20% water reduction. There, surprisingly and similar to the results on
the setting times exhibited in Fig. 9, an opposite trend is observed for
which no explanation is apparent.
3.7. Compressive strength development
Floor screeds are categorized according to their compressive
strength. The classes C5, C7, C12, C16, C20, C25, C30, C35, C40, C50,
9
Journal of Building Engineering 41 (2021) 102787
C60 and C80 (C = compression followed by the value for 28 day com-
pressive strength in N/mm2) are listed in the standard [35]. For calcium
sulfate-based screeds as minimum class C12 and as maximum class C60
are recommended [35]. On the market, self-leveling CaSO4-screeds of
the classes C25, C30 and C35 are most common.
Fig. 11 presents the progressive development of the compressive
strength of screeds at 0%; 20% and 40% water reduction after curing
periods of 4 h; 1 day; 3 days; 7 days and 28 days.
In the initial system (0% WR), within 4 h a substantial increase of
the compressive strength to ~ 23 N/mm2 was achieved, independent of
the kind of superplasticizer admixed.
Interestingly, over the following 3 days compressive strength re-
mained constant and after 7 days increased by ~ 30% until it rose fur-
ther to ~ 40 N/mm2 after 28 days.
At 20% water reduction, again a very substantial increase within
4 h–33 N/mm2 which is characteristic for CaSO4 floor screeds was fol-
lowed by a relatively “dormant” period up to 7 days and after 28 days
M.L. Vo and J. Plank
Fig. 11. Compressive strengths of the floor screed samples holding the different superplasticizers after 4 h, 1 d, 3 d, 7 or 28 days of curing; w/b = 0.41 (0% WR); w/
b = 0.33 (20% WR) and w/b = 0.25 (40% WR).
compressive strength had risen to no less than 55 N/mm2. Also here, all
admixed screeds produced the same values of strength.
Similar to the heat flow calorimetry and setting time investigation,
again a major difference was observed for the system formulated at
40% water reduction. Here, after 4 h no strength could yet be mea-
sured, and only after 1 day the highly phosphated copolymers 45P3 and
45P1PC4 recorded exceptionally high compressive strength values of ~
50 N/mm2 whereas the mostly carboxylated sample 45P0.5PC5 pro-
duced an almost negligible value of ~ 3 N/mm2. However, after 3 days
of hydration this polymer reached almost the same strength values as
for the other two polymers. Remarkably, the strength of the screed for-
mulated at 40% water reduction just barely exceeded that of the system
with 20% less water (58 vs. 55 N/mm2), thus signifying that from a
practical point of view an excessive water reduction of 40% does not
provide sufficient benefit.
4. Conclusion
In this paper, the behavior of a fully phosphated superplasticizer,
two mixed phosphated-carboxylated comb polymers, a 100% carboxy-
lated polymer and a commercial PMS polycondensate as an industry
standard was studied in a fully formulated α-hemihydrate-based self-
leveling floor screed. From the test results, the conclusions as follow
can be drawn:
1. Introduction of a phosphate group into a comb polymer allows up
to 40% water reduction in the flow screed whereas the
carboxylated PCE achieves only up to 30% and PMS is limited to
10% water reduction.
2. Phosphated comb polymers also enhance the flow speed of floor
screeds, thus optimizing spreading and placement times in actual
application. The effect is more pronounced at high water reduction
rates.
3. Phosphated comb polymers induce less expansion and less
shrinkage than carboxylated polymers or PMS. Yet, the shrinkage
10
Journal of Building Engineering 41 (2021) 102787
values for all polymers are low (<0.2 mm/m) and relatively minor
as compared to cement-based systems.
4. The WR0 and WR20 floor screeds exhibit a setting time of ~ 2 h
which is ideal in actual application. However, at 40% WR for the
phosphated polymers excessively long setting times of ~ 15 – 22 h
are observed which is owed to the high dosages applied.
5. When admixing the phosphated comb polymers to the α-
hemihydrate floor screed, an increase of nearly 50% for the final
compressive strength (~60 N/mm2 vs. ~ 40 N/mm2) can be
attained.
The results signify that the introduction of phosphate groups into
comb polymers provides significant benefits in CaSO4 ∙ 0.5H2O-based
floor screeds. Extremely high water reduction rates which are not acces-
sible with common PCEs or a benchmark melamine superplasticizer can
be achieved, thus opening new possibilities in the application of such
eco-friendly screed systems. In future studies, the effect of phosphated
comb polymers in anhydrite-based floor screeds which are also com-
mon in interior construction should be investigated.
Funding
This research did not receive any specific grant from funding agen-
cies in the public, commercial or not-for-profit sectors.
Author statement
My Linh Vo: Conceptualization, Data curation, Project administra-
tion, Validation, Visualization, Writing-original draft, Writing-review
and editing.
Johann Plank: Project administration, Supervision, Validation, Writ-
ing-original draft, Writing-review and editing.
M.L. Vo and J. Plank
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
The authors would like to thank Casea (Lünen, Germany) for supply-
ing the α-hemihydrate sample, Solvay (Lyon, France) for providing the
phosphate-based monomer MOEP and Münzing Chemie GmbH (Ab-
statt, Germany) for the defoamer. Furthermore, the authors would like
to thank SE Tylose GmbH & Co. KG (Wiesbaden, Germany), BASF Con-
struction Additives GmbH (Trostberg, Germany), Südbayerisches Port-
land-Zementwerk Gebr. Wiesböck & Co. GmbH (Rohrdorf, Germany)
and Sika GmbH (Leimen, Germany) for providing the remaining com-
ponents for the floor screed formulations used in this work.
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