José Neto, 2021
José Neto, 2021
h i g h l i g h t s
a r t i c l e i n f o a b s t r a c t
Article history: The use of phosphogypsum as a setting controller for Portland cement is very promising. However, impu-
Received 18 February 2021 rities (such as P2O5 and F-) in its composition reduce its effectiveness and lower mechanical performance
Received in revised form 3 June 2021 at early ages within cementitious systems. This study aimed to evaluate the efficiency of a chemical
Accepted 8 June 2021
purification process based on calcium hydroxide and how this treated phosphogypsum acts as a setting
Available online 17 June 2021
controller in Portland cement systems, with and without the presence of plasticizer admixture. Three
cement types were produced with different sulfate sources: natural gypsum, phosphogypsum, and chem-
Keywords:
ically treated phosphogypsum. The hydration kinetics and reactivity of the phosphogypsum/OPC systems
Phosphogypsum
Chemical treatment
were assessed by isothermal calorimetric and the performance of the sulfate source were compared in
Setting time controller fresh state (Vicat test, mini-slump test, and rotational rheometry) and hardened state (mortar and con-
Portland cement crete compressive strength). It was observed that the presence of impurities such as P2O5 and F- in the
Hydration untreated phosphogypsum delays the hydration and lower strength is achieved in cement mortars.
Rheology The chemical treatment based on Ca(OH)2 reduced the concentration of impurities (the water-soluble
phosphorus decreased by 80.3%) and improve the performance of this alternative sulfate source as a set-
ting controller. Due to the delay in hydration, pastes with phosphogypsum showed the lowest yield stress
and viscosity. The dissolution of fluoride and phosphates through the chemical treatments based on Ca
(OH)2 might be a feasible solution from a technical and economic perspective for the potential valoriza-
tion and re-use of phosphogypsum within the cement industry.
Ó 2021 Elsevier Ltd. All rights reserved.
https://doi.org/10.1016/j.conbuildmat.2021.123935
0950-0618/Ó 2021 Elsevier Ltd. All rights reserved.
José S. Andrade Neto, Jéssica D. Bersch, Thaís S.M. Silva et al. Construction and Building Materials 299 (2021) 123935
phosphogypsum generated is recycled, used as fertilizers, soil sta- Fig. 1 presents a flowchart of phosphogypsum generation and
bilization treatments, or raw material to manufacture building reuse processes.
materials [5]. Among the treatments, washing with dissolved lime is the most
This residue/by-product consists mainly of calcium sulfate dihy- common method applied [9,11]. Water-soluble phosphates are
drate (CaSO42H2O), having a great potential to be used as a setting converted into insoluble calcium phosphates in this treatment,
controller for Portland cement, which can be a suitable substitute which do not significantly affect the cement hydration [9,11].
for natural gypsum [1,4,6]. Natural gypsum reserves are usually con- Other chemical treatments consist of using sulfuric acid [10,12],
centrated in some countries and regions. In Brazil, for instance, it is ammonium hydroxide [13] and aqueous citric acid solutions [7].
concentrated in the north/northeast region. Thus, it is necessary These treatments are effective in removing water-soluble impu-
for cement production in the southeast/south region to transport rities. However, the fraction of the phosphates and fluorides that
the gypsum over long distances, resulting in high costs and environ- replace the sulfate ions in the crystalline structure of gypsum,
mental impacts. These regions have sulfuric acid production indus- forming solid solutions, are difficult to remove [7]. For this, thermal
tries and, therefore, have a high generation of phosphogypsum, treatments followed by chemical treatments are usually needed.
which could be used as a setting controller. Furthermore, the With calcination, gypsum is converted to hemihydrate, which does
replacement of natural gypsum for phosphogypsum would decrease not form a solid solution with phosphates and fluorides, releasing
the environmental impacts of phosphogypsum disposal, such as the impurities from the crystalline structure, which be removed
atmospheric, soil, and groundwater contamination. Besides, the from the chemical treatments mentioned early [7,14].
need for large areas for phosphogypsum disposal and the amount Regarding the physical processes, the impurities can be partially
of natural gypsum extracted also would decrease. Therefore, the removed by particle size separation through sieving. According to
use of phosphogypsum in the cement industry would result in eco- Potgieter et al. [9], particles>170 mm have a high fluoride concen-
nomic and environmental benefits. tration, while particles smaller than 25 mm are rich in organic mat-
However, due to its manufacturing process, it presents impuri- ter and phosphate in the crystalline structure.
ties such as soluble phosphate (P2O5) and fluoride (F-), in addition Among all the treatments to remove the impurities of phosph-
to HPO2- 2- 2-
4 and FPO3 which substitute the SO4 ions in the crystal lat- ogypsum, mixing and grinding it with solid hydrated lime seems
tice of calcium sulfate dihydrate, resulting in solid solutions [7]. promising as it does not require water, calcination, or expensive
During the hydration of the cement with phosphogypsum, these materials, which can be highly feasible from an economic point
impurities react with the calcium ions, precipitating Ca3(PO4)2 of view within a large scale application. Mixing and grinding the
and CaF2 on the surface of the cement grains. This results in the phosphogypsum with hydrated lime reduces the harmful effects
formation of a layer that reduces the flow of water and ions, delay- of impurities on the hydration of Portland cement, decreasing the
ing the dissolution and hydration of cement [4,7,8]. As a result, initial (up to 46%) and final (up to 37%) setting times and increasing
lower mechanical performance at early ages can be identified the mechanical performance of the matrix at early ages (up to 120%
[1,4]. These effects end up restricting the use or the amount of compressive strength at 2 days, up to 83% at 7 days and up to 29%
phosphogypsum used in the cement industry. at 28 days) [9,15]. The purification treatment with hydrated lime
Removing the impurities of phosphogypsum as a purification has also been shown to effectively reduce the negative effect of
process can be carried out by chemical, physical or thermal pro- phosphogypsum, such as longer delays of setting and lower com-
cesses or a combination of these [9,10], which can be considered pressive strength at early ages (increases up to 30% in the compres-
necessary for its valorization in the Portland cement industry. sive strength at 7 days) of supersulfated cements [16,17].
Fig. 1. Flowchart of phosphogypsum generation and reuse processes. Icon made by Smashicons, Those Icons, Freepik, Pixel perfect, turkkub, Vectors Market, iconixar,
DinosoftLabs, Flat Icons, dDara, fjstudio from www.flaticon.com.
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José S. Andrade Neto, Jéssica D. Bersch, Thaís S.M. Silva et al. Construction and Building Materials 299 (2021) 123935
However, to the best of the authors’ knowledge, no study (12.33), which is expected due to the presence of hydrated lime
regarding the effect of this treatment on the hydration and the rhe- during the purification process and agrees with the results found
ology of Portland cement has been published yet. Furthermore, few by Chen et al. [11] and by Liu et al. [18]. This is probably due to
studies [9,15] have assessed the mechanical properties of Portland the direct contribution of the hydroxide introduced by Ca(OH)2
cement with lime-purified phosphogypsum, requiring further [18], and, according to Liu et al. [17,18], purification with lime
studies with other phosphogypsum and cements to validate the removes a portion of the acidic material in the phosphogypsum,
results. Finally, there are no studies on the interaction of purified such as H3PO4, which may also have contributed to the increase
phosphogypsum with lime and plasticizer admixtures and, as in the pH.
pointed out by Holanda et al. [4], there is still a knowledge gap The content of phosphorus and fluoride - impurities responsible
about the effects of phosphogypsum impurities in cement mix- for delaying the hydration of the cement - present in the NG, PG,
tures with plasticizer admixtures. These admixtures are widely and CTPG were determined by X-ray fluorescence (PANalytical
used to adapt the rheology of cement mixtures for their applica- equipment, model Axios). Soluble phosphorus was quantified
tion. Therefore, to enable the use of phosphogypsum as a setting through Inductively Coupled Plasma Atomic Emission Spec-
regulator, it is necessary to understand its behavior in the presence troscopy (ICP-OES) using Thermo Icap 6000 with a wavelength of
of these admixtures. 213.618 nm, power of 1300 W, and flow rate of the auxiliary and
Thus, the present work aims to evaluate the purification of nebulization gas (argon) of 0.5 L/min. For this analysis, the method
phosphogypsum with lime, representing a more straightforward proposed by Holanda et al. [4] was followed, where total phospho-
and economical alternative for the cement industry when com- rus was determined after dissolving the samples in nitric acid and
pared to the purification processes reported in the literature. The soluble phosphorus after dissolving the samples in deionized
objective is to identify the influence of this purification process water.
on the hydration kinetics (calorimetry analysis) and the rheology Table 1 also shows the amounts of total fluoride and phospho-
(spread, viscosity and yield strength) of cement pastes and the rus, determined by XRF, and the amount of total and water-soluble
compressive strength of mortars and concretes. For this, a set of phosphorus, determined by ICP-OES. As expected, PG had higher
different Portland cements were produced using three sulfate amounts of fluoride (up to > 0.16%) and phosphorus (up
sources as a setting controller: natural gypsum, natural phospho- to > 1.65%) than NG.
gypsum (as received) and a chemically treated phosphogypsum The effectiveness of phosphogypsum purification is analyzed by
(mixed with hydrated lime). Complementary, the effect of these the amount of fluoride and phosphorus remaining after the chem-
sulfate sources under the performance of polyfunctional ical treatment. Regarding the fluoride, a reduction of 25.0% is
lignosulfonate-based plasticizer were also assessed. observed with the purification process with hydrated lime. The
same behavior was observed for total phosphorus with a reduction
of 22.1% (determined by XRF) and 15.1% (determined by ICP-OES).
2. Materials The amount of water-soluble phosphorus decreased by 80.3%
with a mixture of phosphogypsum and hydrated lime, showing
2.1. Calcium sulfate an excellent efficiency of the process. This behavior possibly
occurred due to reactions between calcium hydroxide and soluble
In this study, three sources of calcium sulfate were evaluated: phosphates, resulting in calcium phosphates insoluble in water
natural gypsum (NG), phosphogypsum (PG), and chemically trea- and do not significantly delay the cement hydration [4,8,11], as
ted phosphogypsum (CTPG). For the purification of phosphogyp- presented in equations (1) and (2) [8]. These reactions were possi-
sum, 12 tons of the material was spread on an industrial floor, ble due to the high humidity of phosphogypsum (approximately
and then 600 kg of hydrated lime (5%, concerning the phosphogyp- 20 wt%). Therefore, the process effectively reduced the amount of
sum mass) were placed on this material. Then, the materials were water-soluble phosphorus, but it did not show the same efficiency
mixed with the aid of a loader. The proportion of hydrated lime in reducing the amount of total phosphorus and fluoride that are
used (5%) was chosen according to Liu et al. [18] results, which also responsible for delaying the hydration of the cement.
showed that this is the optimum content to treat the phosphogyp-
sum for use as a setting controller in the supersulfated cements. CaðOHÞ2 þ H3 PO4 ¼ Ca3 ðPO4 Þ2 þ 6H2 O ð1Þ
According to the method adopted by Chen, the pH of NG, PG,
and CTPG solutions with deionized water (1:10, by mass) were
analyzed with a pH meter mPA210 from the brand MS TECHNO- CaðOHÞ2 þ 2CaHPO4 ¼ Ca3 ðPO4 Þ2 þ 2H2 O ð2Þ
PON et al. [19]. Table 1 shows the pH values of the solutions. NG The mineralogical composition of the NG, PG, and CTPG were
and PG solutions showed similar values (7.37 and 7.33). Phospho- determined by X-ray diffraction on a Bruker D8 Advance diffrac-
gypsum, when initially stored, is usually acidic (pH close to 1) due tometer with Cu K radiation, Ni filter. A step of 0.020° was used
to the presence of residual acid from the phosphoric acid produc- in a 2h interval between 5° and 70°, with a speed of 0.72°/min.
tion, but its pH increases over the time of storage due to acid evap- The X-ray diffractograms are shown in Fig. 2, in which it is possible
oration and leaching with rainwater (if is weathering to observe that all sulfate sources present gypsum (CaSO42H2O) in
exposed/stored) [20]. The CTPG solution shows a basic pH their composition. In addition, the NG also shows the presence of
calcite (CaCO3), and the CTPG presented peaks related to calcium
Table 1
carbonate (CaCO3) and calcium hydroxide (Ca(OH)2). The quantifi-
pH values of solutions in deionized water and phosphorus concentrations and fluoride cation by the Rietveld method is presented in Table 2.
in the different materials. Fig. 3 shows the TG and DTG curves of NG, PG, and CTPG,
- NG PG CTPG
obtained in a thermobalance, model TGA Q50 from TA Instruments,
using platinum vessels without a lid in an inert atmosphere (N2),
pH 7.37 7.33 12.33
Total fluoride (%F-) - XRF 0.00 0.16 0.12
with a flow rate of 40 mL/min. The test was carried out up to
Total phosphorus (%P2O5) - XRF 0.10 1.36 1.06 900 °C, with a 10 °C/min heating rate. It is possible to observe, in
Total phosphorus (%P2O5) – ICP-OES 0.07 1.72 1.46 all samples, a peak of weight loss between 85 °C and 180 °C, related
Soluble phosphorus (%P2O5) – ICP-OES 0.00 0.01 0.00 to the decomposition of calcium sulfate dihydrate (CaSO42H2O) in
Soluble phosphorus (ppm) – ICP-OES 6.00 39.00 7.70
hemihydrate (CaSO41/2H2O) and then, in anhydrite (CaSO4) [21].
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José S. Andrade Neto, Jéssica D. Bersch, Thaís S.M. Silva et al. Construction and Building Materials 299 (2021) 123935
Fig. 2. X-ray diffractogram of the sulfate sources analyzed (G - Gypsum, C - Calcite, Table 3
P - Portlandite). Results of the physical characterization of the cements.
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José S. Andrade Neto, Jéssica D. Bersch, Thaís S.M. Silva et al. Construction and Building Materials 299 (2021) 123935
Table 5
Percentage of phases present in the cements, determined by X-ray diffraction using the Rietveld method.
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José S. Andrade Neto, Jéssica D. Bersch, Thaís S.M. Silva et al. Construction and Building Materials 299 (2021) 123935
Fig. 4. Rheometry test procedure based on the shear rate as a function of time.
Table 6
Consumption of materials, in kilograms per cubic meter of concrete.
Concrete Cement Fine sand Medium sand 19.0 mm gravel Water Plasticizer w/c ratio
Without admixture 330 409 339 1082 193 0.00 0.59
With 0.75% of plasticizer 330 417 344 1099 181 2.31 0.52
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José S. Andrade Neto, Jéssica D. Bersch, Thaís S.M. Silva et al. Construction and Building Materials 299 (2021) 123935
Table 7
Initial and final setting times of the cements, determined by the Vicat needle method.
an initial setting time 9.1% and a final setting time 23.3% shorter
than the OPC PG, showing that the purification process reduced
the delay caused by phosphogypsum.
Fig. 8 shows the spread in the mini-slump test obtained for
pastes with and without admixture. It is possible to observe that
the OPC PG and OPC CTPG pastes showed the highest spread.
Besides, there is an increase in spreading when using the
lignosulfonate-based plasticizer, which is adsorbed on the cement Fig. 8. Spread of pastes with and without plasticizer in the mini-slump test.
particles and dispersed due to electrostatic forces [36].
Fig. 9A to 9F show the shear stress as a function of the shear rate
gite formation and, therefore, mechanical strength development. In
curves of the different cement pastes, with and without admixture,
addition, as also observed by Potgieter et al. [9] and Potgieter and
obtained by rotational rheometry. The addition of plasticizer
Howell-Potgieter [15], the purification process with hydrated lime
admixture reduced the torque values, showing a greater fluidity.
was effective, reducing the delay in mechanical development at
Besides, the OPC PG and OPC CTPG presented lower torque values
early ages, which corroborates the calorimetry results.
when compared to the OPC NG.
Figs. 10 and 11 show the yield stress and plastic viscosity
results at 50 rpm (the maximum rate used in this work), deter-
mined by rotational rheometry, of pastes with and without admix- 4.3. Study in concretes
ture. It is possible to observe that the plasticizer reduced the plastic
viscosity and the yield stress, which was expected due to electro- This section presents the compressive strength results in con-
static repulsion [36]. crete. As detailed in section 3.3, it was decided to fix the consis-
From the rotational rheometry and mini-slump results, it was tency in this work, adjusting for this the amount of water. Thus,
possible to observe that the OPC PG and OPC CTPG cements pre- as the amount of water required to reach 120 mm of slump was
sented a greater fluidity, with lower plastic viscosity and yield different in concretes with and without admixture, these results
stress. This result is probably due to the delay caused by phospho- should not be compared with each other. However, the differences
gypsum and purified phosphogypsum in cement hydration, as in rheology observed for pastes (section 4.1) did not significantly
observed in the calorimetry and setting time result. Due to the influence the workability of concretes, and the amount of water
presence of fluoride and phosphates in PG and CTPG, the precipita- used for concretes with different cements was the same. For each
tion of the hydrated phases (mainly ettringite in the first hours) is group (with and without admixture), the results obtained between
delayed. The precipitation of ettringite, which has a high surface the different cements can be compared, which is the focus of this
area, results in increases in viscosity and the yield stress of the section.
paste [52]. Thus, the probable greater formation of ettringite in Fig. 13A shows the results of compressive strength in concretes
the first minutes in OPC NG, justifies the lower fluidity observed without admixtures. After 1 day, OPC PG concrete had the lowest
compared to cements with phosphogypsum. strength, representing 64.1% of the highest, obtained with OPC
However, it is interesting to note that, even with 80.3%, 22.1%, NG. The concrete with OPC CTPG showed intermediate strength.
and 25.0% less, in the amounts of soluble phosphorus, total phos- This is following the results of the calorimetry and compressive
phorus, and total fluoride, the OPC CTPG showed lower yield stress strength tests in mortars, which show a shorter delay in hydration
and plastic viscosity when compared with OPC PG. This behavior and strength development at the first ages with the use of purified
may have resulted from the smaller surface area and larger particle phosphogypsum concerning the non-purified one, indicating that
diameters (as shown in Table 3). Vikan et al. [53] noted that for the the purification process was efficient. At later ages, as observed
same clinker or clinkers with a similar mineralogical composition for mortars, the strengths of the different types of concretes are
(as is the case of this work), the smaller the Blaine surface area similar, with the strength of concrete with OPC PG, at 2 days,
of the cement, the higher the fluidity of the paste. 94.7% of that obtained with OPC NG.
Fig. 13B shows the results of compressive strength in concrete
with the lignosulfonate-based plasticizer admixture. In general,
4.2. Study in mortars the samples presented higher strength than the samples without
admixture. This is due to the lower water/cement ratio (0.52 for
Fig. 12 shows the results of compressive strength in mortars concretes with plasticizer and 0.59 for concretes without
produced with different types of calcium sulfate and without plas- admixture).
ticizer admixture. After 1 day, the mortars with OPC PG and OPC Among all evaluated ages, at 1 day, the differences between the
CTPG showed strengths 24.9% and 16.5% lower than those obtained three calcium sulfate sources are more pronounced. OPC PG con-
with OPC NG, respectively. In later ages, the difference in the crete presented compressive strength of 2.9 MPa at 1 d, 75.8%
strength between the OPC PG and OPC CTPG mortars and the and 82.1% lower than the OPC CTPG (12.0 MPa) and OPC NG
OPC NG mortar decreases, being 3.5% and 5.3% at 28 days, (16.2 MPa), respectively. At the ages of 2, 7, and 28 days, this dif-
respectively. ference reduced, showing that the negative effect of phosphogyp-
The lower compressive strength in phosphogypsum mortars at sum in mixtures containing admixture occurs only at early ages,
early ages was also observed by Potgieter et al. [9], Singh et al. [13], probably due to the delay in the reaction. As shown by paste
Singh and Garg [54] and Potgieter et al. [55]. This behavior is due to calorimetry results, this result is consistent and reinforces that
the impurities of phosphogypsum, which delays C-S-H and ettrin- the use of the admixture delays the onset of hydration reactions.
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José S. Andrade Neto, Jéssica D. Bersch, Thaís S.M. Silva et al. Construction and Building Materials 299 (2021) 123935
Fig. 9. Shear stress as a function of shear rate curves, obtained in the rotational rheometry test, from pastes (A) and (B) OPC NG without and with admixture, (C) and (D) OPC
PG without and with admixture, (E) and (F) OPC CTPG without and with admixture.
Fig. 10. Yield stress, determined by rotational rheometry, of pastes with and Fig. 11. Plastic viscosity at 50 rpm, determined by rotational rheometry, of pastes
without plasticizer. with and without plasticizer.
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José S. Andrade Neto, Jéssica D. Bersch, Thaís S.M. Silva et al. Construction and Building Materials 299 (2021) 123935
Acknowledgments
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José S. Andrade Neto, Jéssica D. Bersch, Thaís S.M. Silva et al. Construction and Building Materials 299 (2021) 123935
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