Manuscript Details

Manuscript number JMRT_2019_1637

Title MULTIANALYTICAL APPROACH OF STAY-IN-PLACE POLYVINYL

CHLORIDE FORMWORK CONCRETE EXPOSED TO HIGH TEMPERATURES

Short title APPROACH MULTIANALYTIC CONCRETE IN PVC PANELS EXPOSED TO

HIGH TEMPERATURES

Article type Original article

Abstract
This work presents the first scientific attempt of a comparative study of the variation by exposure to high temperatures
from two stay-in-place polyvinyl chloride (PVC) formwork concrete. In this study, two structural concrete panels with
PVC formwork were prepared, aged for 28 days and then exposed to the fire curve based on the ISO 834: 2014
standard. Deterioration of concrete by exposure to high temperatures was examined. For this, a systematic sampling
based on the proximity of the furnace fire and the spalling of the concrete was carried out. The microstructural,
thermal, crystallographic and spectroscopic changes were studied according to the degree of affectation by fire using
scanning electron microscopy (SEM), Thermogravimetric analysis (TGA-DTA), X-ray diffraction (XRD) and Fourier
transform spectrometry (FTIR). Results show a relationship between the microstructure of concrete paste and
exposure temperature, as well as, the relationship between exposure temperature and dehydration of calcium
hydrates and S-C-H gel, dehydroxylation of Portlandite and decarbonation of Calcite. These reactions can be
considered as tracers of the degree of exposure to high temperatures from stay-in-place PVC formwork concrete.

Keywords Self-compacting concrete; High temperature; Microstructural changes; Phase

transition; Thermal analyses; Spectroscopic analyses

Taxonomy Phase Change, Materials Testing, Heat Treatment

Corresponding Author Leandro Gómez Plata

Corresponding Author's Research group in Environmental Management and Sustainability, Department

Institution of Civil and Environmental Engineering

Order of Authors Leandro Gómez Plata, Bernardo Tutikian, Fernanda Pacheco, Marcos Oliveira,
Michel Murillo, luis silva, Carlos Bergmann

Suggested reviewers Venkatesh Kodur, Jorge Tobón

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The Highlights

 Principal changes in crystalline phases due to exposure to high temperatures

of Stay-in-place polyvinyl chloride (PVC) formwork concrete were identified

 Loss of property by changes in morphology, craking and appearance of news

particles in concrete due to exposure to high temperatures are notorious.

 Quantification of Portlandite and Calcite from Stay-in-place polyvinyl chloride

(PVC) formwork concrete by TGA-DSC, depending on the degree of exposure
to temperature exposed to high temperatures was completed.

 A spectroscopic study with the main changes in the vibrational modes of

concrete as a function of temperature was performed.

 A direct relationship between the amount of Portlandite and Calcite and the
exposure temperature was found.
 MULTIANALYTICAL APPROACH OF STAY-IN-PLACE POLYVINYL CHLORIDE

FORMWORK CONCRETE EXPOSED TO HIGH TEMPERATURES

Leandro Gómez Plata a,b,

lgomez52@cuc.edu.co
a Research group in Environmental Management and Sustainability, Department of Civil

and Environmental Engineering, Universidad De La Costa.

Calle 58 #55-66, Barranquilla, Atlántico, 080002, Colombia
bPostgraduate Program in Mining, Metallurgical and Materials Engineering,
Universidade Federal do Rio Grande do Sul.
Av. Osvaldo Aranha 99, Porto Alegre 90035-190, Brazil.

Bernardo F. Tutikian a,c,

BFTUTIKIAN@unisinos.br
a Research group in Environmental Management and Sustainability, Department of Civil

and Environmental Engineering, Universidad De La Costa.

Calle 58 #55-66, Barranquilla, Atlántico, 080002, Colombia.
cUniversidade do Vale do Rio dos Sinos.
Av. Unisinos, 95, São Leopoldo, 93.022-750, Brazil

Fernanda Pacheco c,
FERNANDAPACHE@unisinos.br
c Universidade do Vale do Rio dos Sinos.

Av. Unisinos, 95, São Leopoldo, 93.022-750, Brazil

Marcos S. Oliveira d,
marcosleandro4321@icloud.com
d Faculdade Meridional IMED.

R. Gen. Prestes Guimarães, 304, Passo Fundo, 99070-220, Rio Grande do Sul, Brazil.

Michel Murillo a,
mmurillo4@cuc.edu.co
aResearch group in Environmental Management and Sustainability, Department of Civil
and Environmental Engineering, Universidad De La Costa.
Calle 58 #55-66, Barranquilla, Atlántico, 080002, Colombia.

Luis F. O. Silva a,
lsilva8@cuc.edu.co
aResearch group in Environmental Management and Sustainability, Department of Civil
and Environmental Engineering, Universidad De La Costa.
Calle 58 #55-66, Barranquilla, Atlántico, 080002, Colombia
Carlos Pérez Bergmann b
bergmann@ufrgs.br
bPostgraduate Program in Mining, Metallurgical and Materials Engineering,
Universidade Federal do Rio Grande do Sul.
Av. Osvaldo Aranha 99, Porto Alegre 90035-190, Brazil.

Correspondence author email: lgomez52@cuc.edu.co

Abstract

This work presents the first scientific attempt of a comparative study of the variation by

exposure to high temperatures from two stay-in-place polyvinyl chloride (PVC) formwork

concrete. In this study, two structural concrete panels with PVC formwork were

prepared, aged for 28 days and then exposed to the fire curve based on the ISO 834:

2014 standard. Deterioration of concrete by exposure to high temperatures was

examined. For this, a systematic sampling based on the proximity of the furnace fire and

the spalling of the concrete was carried out. The microstructural, thermal,

crystallographic and spectroscopic changes were studied according to the degree of

affectation by fire using scanning electron microscopy (SEM), Thermogravimetric

analysis (TGA-DTA), X-ray diffraction (XRD) and Fourier transform spectrometry (FTIR).

Results show a relationship between the microstructure of concrete paste and exposure

temperature, as well as, the relationship between exposure temperature and

dehydration of calcium hydrates and S-C-H gel, dehydroxylation of Portlandite and

decarbonation of Calcite. These reactions can be considered as tracers of the degree of

exposure to high temperatures from stay-in-place PVC formwork concrete.

Keywords: Self-compacting concrete, High temperature, Microstructural changes, Phase

transition, Thermal analyses, spectroscopic analyses.

1. INTRODUCTION

Fire resistance is applied to the construction elements and not to their materials, but the

properties of the constituent materials of a construction element directly affect the

performance of the element [1–3]. Concrete is a construction material with good fire

resistance to high temperatures because not experience combustion, or ignition

processes besides being a bad thermal conductor at high temperatures, since it is dry,

so it takes considerable time for the heat to reach a certain depth will bring it to the face

of the building system, and does not generate toxic gas emissions [1,2,4–8]. However,

concrete subjected to fire during its service experiences some problems such as

deterioration of mechanical properties, explosive detachment, reduction in section size

and exposure to a temperature of reinforcement steel [2,8–12]. Cracking and spalling

are other processes of deterioration of concrete exposed to high temperatures widely

studied [1,4,13–18]. Exposure to high temperatures of concrete affects compressive

strength and modulus of elasticity, loss of its capacity to load, reduction in durability,

structural cracking and aggregate fracture [5,6,8,19,20]. Exceeding certain

temperatures, as well as certain exposure times, can lead to irreversible changes in the

concrete, even a structural collapse [21]. Many of these changes can be explained by

the study of the internal microstructure and physicochemical properties of concrete. For

this reason, the systematic study of the change of microstructure and physicochemical
properties of concrete experienced by concrete-based structural elements when

exposed to high temperatures, such as would occur in an accidental fire but under

controlled conditions is of great importance.

The common approach to study concrete and similar construction materials exposed to

fire is based on the application of heating at programmed temperatures and time inside

a furnace. It is well known that changes experienced by concrete construction systems

exposed to high temperatures in properties are directly related to changes in chemical

properties [19]. Thus, residual properties of concrete can be assessed by experimental

techniques that identify physical, chemical and mineralogical changes.

Researchers who study the behavior of concrete construction elements exposed to high

temperatures have focused on the effect of temperature on the mechanical properties of

concrete from the experimental [3,4,22] and numerical modeling [13,23,24]. Other

studies have been devoted to the changes of the physical properties as thermal

conductivity [4] or porosity [6,25] and some have also been found about the chemical

changes that occur in the concrete [6,19]. Cement paste [26], fly ash based rubberized

geopolymer concrete [27], fiber reinforced concrete [10,28,29] are some of the

construction materials recently evaluated against high temperatures. However, the

thermal behavior of formwork concrete of prefabricated stay-in-place (SIP) polyvinyl

chloride (PVC) has few studied.

The thermal effects on concrete and changes in pre and post-fired concrete by a

systematic studies on the simulated conditions of temperatures such as that in which

there was an accidental fire in concrete can be done using Scanning electron
microscopy (SEM), X-ray diffraction (XRD) [5,19,30–32], DTA/TGA [5,33], Scanning

electron microscopy (SEM) [6,34–37] and FTIR spectroscopic [38–43].

Prefabricated SIP PVC formwork concrete is a good alternative for the single storey

house of the economic segment [44]. Due to the growing demand for housing and the

need to reduce construction times has been looking to develop and add more

sustainable technologies that reduce the impact without compromising the performance

of buildings [45–47]. This constructive system is made up of lightweight and modular

profiles of PVC and is filled with concrete and steel, resulting in a product of high

strength and numerous constructive qualities [45–47]. PVC concrete offers high

productivity as it facilitates material management, labor, and transportation [46]. It

provides quick and clean construction, avoids waste and reduces impact and PVC is a

recyclable product [48]. Despite the advantages of industrialized concrete-PVC

construction systems, there is not much knowledge about their useful life behavior.

The fire behavior and phase changes and microstructure in the concrete of novel

construction systems such as SIP PVC have been poorly addressed. So, it is evident

the need to multi-analytic approach that allows more accurately describe the

physicochemical changes that the concrete-PVC when exposed to high temperatures.

This research is expected to understand the relevant changes in properties of the

industrialized concrete-based construction systems SIP PVC subjected to high

temperatures of fire through a multi-analytical approach to describe the microstructural,

mineralogical and vibrational changes to understand the performance of these materials.

2. METHODS

2.1. Sample collection and preparation

The samples correspond to new vertical sealing systems with structural function.

Formed by modular profiles of PVC coupled to each other and filled with self-compacting

concrete. In this paper two systems were studied: one with the strength of concrete (fc)

of 20 MPa (RES001.03 system) and another of 11.6 MPa (RES001.02 system). The

dimensions of the systems were 2.13 m x 0.8 m and 0.08 m thick. The PVC wall had a

dimension of 1.7 m and the maximum diameter of the aggregate used was 9.5 mm. The

supplementary file shows the manufacturing process from stay-in-place PVC

formwork. The construction systems were subjected to the fire resistance test based on

the Brazilian standard for evaluation of structural sealing systems ABNT NBR

5628:2001 [49]. A detailed description of the thermal behavior of these construction

systems was published by Murillo et al. [50]. Exposure of high temperatures caused the

melting of the PVC profile on the face of the sample exposed to the fire, as well as the

displacement and spalling of the concrete. In its face not exposed to high temperatures,

superficial changes in the material were observed, such as bubbles and deformations of

the PVC (Fig. 1). Based on the level of degradation suffered by the system after the fire

resistance test two areas of the constructive system were selected for sampling. The

most affected (SS) by the fire, corresponds to the region where the smoke release

occurred during the fire test and the least affected (S) corresponding to the area where

there were no events. Fig. 1 shows the location of the areas. For each area, samples

were collected from the exposed directly to the fire part (3) heating at temperatures
above 800 °C, part of the middle (2) and not directly exposed to the oven (1), whose

maximum temperature does not exceed 106 °C. Table 1 shows a description of the

samples collected. Immediately, samples were immersed in isopropyl alcohol to interrupt

the hydration process of the cement ground with a ball mill until obtaining powders with

a size of lower particle sieved the # 325 mesh and then kept in an oven at 50 °C for 24

hours.
2.2. Characterization

2.2.1. Chemical characterization

Initially, elemental chemical composition was determined by X-ray fluorescence

spectrometry (FRX) using a Shimadzu XR 1800 sequential X-ray fluorescence

sequential spectrometer using Ru tube.

2.2.2. Mineralogical analysis

X-ray diffraction was selected (XRD, X'Pert MPD, Philips) using 40 kV, 40 mA and

a Cu-K source. Samples were analyzed using a step size of 0.05°, dwell time of 5

s per-step and a 2θ range of 5 to 70º. ICDD data banks were used for the

identification of the resulting crystalline phases.

2.2.3. Electron microscopy analysis (SEM)

The morphology and chemical composition of microparticles, nanoparticles and

minerals were analyzed by scanning electron microscopy (SEM) in backscattered

electrons (BSE) and secondary electrons (SE) mode while the distribution of the

elements in the samples was studied by dispersive energy spectroscopy (EDS)

using a Carl Zeiss EVO 40 - Oxford INCA X-Act EDS at an acceleration voltage of

15 kV. Moisture was removed by drying in a stove for a week at 60 °C for a week.

Sample powders were mounted rigidly on a specimen holder (stub) using carbon

tape and gold was used as a coating.

2.2.4. Fourier transform infrared spectroscopy analysis (FTIR)

Samples were studied with an infrared spectrophotometer to complement the

information obtained by these techniques. Transmittance spectra were obtained by

a BOMEM MB-series FTIR Hartmann & Braun Michelson spectrometer equipped

with DTGgS detector at the Institute of Physics of the Federal University of Rio

Grande do Sul. Fifty scans of transmittance spectra with a resolution of 4 cm−1

were performed in the range of 400–4000 cm−1.

2.2.5. Thermogravimetric analysis

The TGA-DTA tests were used to provide information on the chemical reactions of

the concrete due to the heating and calculates the Calcite and Portlandite contents

without reacting. The thermal decomposition of the samples was analyzed with the

TGA and the DTG curves. The apparatus used was a TA INSTRUMENT, SDT

Q600 model. The temperature of the furnace was programmed to rise a constant

heating rate of 5 °C/min up to 1150 °C. The tests were performed under an airflow

of 80 ml/min [33].

The percentage of portlandite (P) in the reference samples and samples exposed

was calculated for the following reaction Ca(OH)2 → CaO + H2O, as [51].

P = f ⋅Δwtp eq.1

where; f is the mole ratio Ca(OH)2/H2O equal 4.11 and Δwt is the weight loss in

The TGA curve due to the dehydration of Portlandite. In the same way, the
percentage of Calcite was calculated based on the reaction CaCO3 → CaO + CO2.

using an analogous equation but with the CaCO3 /CO2 (f) molar ratio equal to 1.35.

Calcium hydrates, C-S-H, ettringite, and calcium aluminate hydrates, do not have a

well-known crystalline structure that allows obtaining ratios that permit quantitative

determination of their percentage. Alternatively, it was assumed that the relative

proportions of calcium hydrate species (C-S-H, ettringite and calcium aluminate

and aluminosilicate hydrates) are the same for a cement paste of concrete under

the same condition. Therefore, the rate of dehydration of calcium hydrates in

concrete exposed to high temperature will be constant. Consequently, the

approximate percentage of residual calcium hydrates in the concrete exposed to

high temperature at a given temperature in relation to the amount of calcium

hydrates without exposure can be calculated as [26]:

Percentage of calcium hydrates decomposition = 100 – [(Δwtf / Δwt)*100] eq. 2

where: Δwt is the weight loss in TGA curve corresponding to dehydration of

calcium hydrates for without exposure to fire, and Δwtf is the weight loss

corresponding to dehydration of calcium hydrates for concrete at a given level of

fire exposure

3. RESULTS AND DISCUSSION

3.1. Mineralogical variation

The elemental composition of the different samples of concrete extracted was

analyzed by EDS and FRX. Table 2 presents the fraction of the majority elements

in the samples. Si, Ca, Al, Fe, S, K, Ti, Mg, P, and Mn were identified.

Table 2 shows the composition obtained by FRX of the samples of concrete

exposed to temperature, too. SiO2, CaO, Al2O3, Fe2O3, SO3, K2O, TiO2, MgO, P2O5

and MnO are relatively constant for all samples and did not show a significant

difference between a layer of each zone (2.1, 2.2 and 2.3, student's t-test at 0.05

level). XRD technique was used to obtain a better understanding of the possible

transformation in original materials as well as the samples exposed to high

temperatures. XRD results by R2R and R3R samples are plotted in Fig 2. Quartz

(SiO2, ICDD: 01-089-8935), Anorthite (Ca (Al2Si2O8), An, 00-041-1481), Periclase

(MgO, 00-045-0946), Calcite (CaCO3, CC, 00-005-0586), Calcium oxide (CaO, 00-

028-0775), Portlandite ( Ca(OH)2, CH, 00-001-1079), Calcium Silicate Hydrate

(CSH, 00-018-1206), Gypsum (CaSO4.2H20, Gy, 00-003-0053), Ettringite

(Ca6Al2(SO4)3 (OH)1225H2O, Et, 00-009-0414), Calcium Silicate anhydrous

(Ca2SiO4, C2S, 00-009-0414) and Dolomite (Ca(Mg,Fe) (CO3)2, Do, 00-034-0517)

were found in both samples. R2 also shows calcium aluminum oxide carbonate

Hydrate as a hydration product (CAC, 00-014-0083). Quartz and Anorthite are the

most abundant and crystalline phases. These phases are coming from the

aggregates. Quartz comes from the sand, while Anorthite is a Feldspar. Both

common constituents of fine siliceous aggregates of Concrete [5,29,52]. Many

minor phases experiencing peak overlaps with Quartz and Anorthite as seen in the
enlargement in the region 25-37 ° in Fig. 2. This mineral association and their

relative abundances are in good agreement with the findings of Tutikian et al. [53],

Pen and Huang [54] and Caetano et al. [29].

Fig 3 (a) shows the diffractograms of the R3S2.1/R3S2.2/R3S2.3 samples. In all

diffractograms, the loss of CSH due to reflection 101 (13.65 ° 2θ) is observed in

comparison with R3R due to dehydration [55,56]. CSH is like minerals Tobermorite

and Jennite [31] and its decomposition starts at the temperature of 150 °C [57].

Loss of ettringite is also observed too. Ettringite decomposes at the temperature

range of 65 °C – 75 °C [58]. While, α- Quartz remains constant with temperature,

although there is an α-β transition at 573 °C [29,59]. Further, Fig (3b) shows the

diffractograms of the R2S2.1/R2S2.2/R2S2.3 sample collected. The loss of CACH

is observed in all samples. For this system, Dolomite, MgO, and α- Quartz do not

change in intensity depending on the temperature. Fig 3(c) and 3(d) shows DRX

peak patterns of R3SS2.1/R3SS2.2/R3SS2.3 and R2SS2.1/R2SS2.2/R2SS2.3

system. Similar behavior of the phases depending on the temperature was found.

For this system C-S-H neither is present. While Portlandite is present in the

samples not exposed directly to the oven and a greater amount in the intermediate

samples, R3SS2.2 and R2SS2.2.

Gypsum is constant in all the samples, although to the overlap of the main peak at

29.4 ° (2θ) with CC. While CH, MgO, Do and Anorthite increase with the increase
in exposure temperature, 2.1 and 2.2., while the hydrated phases CSH and

Ettringite disappear. The relative intensity of the Portlandite depending on the

temperature [5,19,26,60]. It is known that increases in the content of portlandite by

heating at temperatures is observed up to 450 °C for being a product of the

progressive dehydration of the cement paste [55,61]. Subsequently, C2S increases

slightly between 2.2 and S.3 samples, as a decomposition product of CSH [54].

CSH decomposes completely up to 800 °C [56] and the temperature of R3S2.3 e.

g. is greater than ~ 920 °C. At the same time, CH, CC and Anorthite decrease in

R3S2.3 samples and R2S2.3 with the increase in exposure temperature and CaO

increase. CaO appears as a decomposition product of Calcite and CH [61].

Despite, CC is another product of CH decomposition formed when in the cooling

process CaO reacts with the CO2 [56], and that is why it is found at higher

temperatures. CH normally disappears at temperatures close to 750 and 800 °C

[58,62]. However, in this study, it is found when heating above ~920 °C. Lopez-

Perales [52] suggests that CH is observed in temperatures higher than 800 °C

because it is formed again in the cooling process and distingue due to changes in

the 2θ value, but nevertheless this phenomenon was not observed. Also, Handoo

[5] suggests that gradual loss of CH as the temperature increases occurs faster on

the surface than inside the concrete, however R3S2.3 was collected from the

surface of the constructive system.

The middle layer of the construction system, R2S2.2, and R3S2.2 present a

greater amount of Portlandite, while the layer inside or directly exposed to furnace

experiences a reduction. This is possibly due to the variation in exposure time. The
difference in the time of exposure to the defined temperature and in the method of

cooling the sample. 30 minute, [62], 2 h [58], 3 h [61] and 5 h [5] are commonly

used. While the large-scale thermal test used follows the approaches of the

Brazilian standard ABNT NBR 5628: 2001, it seeks to define the exposure time

without thermodynamic equilibrium being reached.

3.2. Microstructure

As a complement, scanning electron microscopy analysis was performed to find

out possible microstructural changes. This technique allows us to visually identify

the morphological, mineral and textural alterations of the concrete exposed at high

temperatures [62]. The appearance of the R3SS2.1 sample is shown in Fig 4a. It is

clearly observed that the vitreous appearance of the matrix is interrupted by the

presence of porosity caused by the partial dehydration of C-S-H, which starts

above 100 °C [55,57]. In addition, carbon-rich particles immersed in the matrix are

observed. Fig 4b shows the appearance of the intermediate sample, R3SS2.2. It

shows a much rougher matrix due to the thermal alteration of the C-S-H as well as

the formation of phases in the form of scales and cracks in the aggregates

[56,63,64] On the other hand, figure 4c shows that deterioration by exposure to

high temperature of the C-S-H gel of the concrete matrix of the sample R3SS2.3 is

greater than that of the others. The rough, cohesive and discontinuous appearance

of the material, resulting from dehydration and transformation of silicates, can be

observed. Well-defined prismatic particles are also seen in this figure. The increase

in the magnification and mapping by EDS of the sample R3SS2.3 (Fig. 5a) shows
that the prismatic papules are rich in calcium. Possibly correspond to carbonates

[55]. On the other hand, Figure 4d shows the micrograph of the R2SS2.1 sample.

The characteristics of this sample are like the equivalent for the R3 system; a

continuous matrix is observed with slight roughness due to the dehydration of C-S-

H. As well as carbon-rich scales. In turn, the moderately exposed sample R2SS2.2

Fig 4e shows a greater alteration of the amorphous phase and the presence of

more marked cracks in the aggregates. While Fig 4f, corresponding to the sample

most exposed to fire R2SS2.3, shows a complete alteration of the concrete matrix

that allows the visibility of a variety of crystals with diffuse grain edges and an

apparent degree of sintering. The increased mapping of these grains (Fig. 5b)

shows that Cl, Ca, Ti and S are the major elements present [61].

3.3. Fourier transform infrared spectroscopy analysis (FTIR)

FT-IR is a useful, non-destructive and easy technique to study the phase

composition of construction materials in initial conditions as well as the evolution

under different conditions. This technique has proven useful for the analysis of

crystalline but also amorphous phases [42]. Infrared spectroscopy is used both to

collect information on the structure of the compounds of concrete and as an

analytical tool to evaluate in the qualitative and quantitative analysis [38,41,43].

FTIR spectra are shown in Fig 6 and Table 3 shows the assignment of the main

bands found in the FTIR spectra. Water absorption bands in the region 1600-1700

cm-1 and above 3000 cm-1. Broadband with a maximum around 3500 cm-1
corresponds to the chemically bound water due to ν1 H2O to concrete hydration

products (C-S-H, ettringite, hydrates of calcium) while the prominent sharp peak at

3640 cm-1 due to the presence of OH stretching of Portlandite [26,40,65]. The

bands at 1100 and 1200 cm−1 which are attributed to ν3 asymmetric stretching

vibrations of the sulfate group (SO4 2− ) [65]. It is difficult to interpret this area of the

spectrum because sulfates generate numerous peaks and overlays are generated.

Ettringite can be confirmed by a very strong anti-symmetrical stretching frequency

of the sulfate ion (ν3 SO4) centered towards 1115 cm-1 [38] however bands found

corresponds to gypsum with maximum to 1144 cm-1 [26,40]. The bands for calcium

carbonate due to the planar CO3-2 ion of the Calcite or Anorthite phase are present

between 1570 and 1220 cm-1. There vibrational modes in the CO3- 2 ions are

present: the asymmetric stretch v3[CO3] at 1420 and 1490 cm-1 [40]. The low-

intensity peak at 2515 cm-1 also demonstrates the presence of this ion.

The region between 1100 and 800 cm-1 is in which the most representative

intensities of silicates. This range corresponds to numerous possible bond

environments. Broadband between 1100 and 800 cm-1 refer to the Si-O elongation

vibrations [27,39]. In this region are present characteristic peaks of C-S-H to 971

cm-1 [40] and the bands assigned to quartz as the crystalline phase to 809 cm-1

[38,63]. Another minor band of other phases like the split in-plane bending

vibrations ν4[CO3] about 875 cm-1; the symmetric stretching, ν1[CO3] at 1063 cm-1

and the out-of-plane bend, ν2 [CO3] 700 cm-1 also appear in this region [65,66]. By

last, peak around 573 cm-1 corresponds to the presence of the Al-O group. the

peak in this frequency is more characteristic of calcium mono-sulfoaluminate and

the band below 487 cm-1 is to typical of the vibrational mode of stretching Si-O of

the silicate groups present in the quartz [67].

Although FTIR spectra do not change much for samples, slight differences in the

intensity of vibrational modes with the exposure temperature can be identified.

R3SS2.3, R3S2.3, R2SS2.2, and R2S2.2 show a decrease in the bands

associated with the vibrational modes of the OH bond due to the dehydration of

calcium silicates CSH, calcium aluminate hydrates and ettringite, which is

consistent with the observed by electron microscopy. An increase in the

carbonates ions as the temperature of concrete increases is also observed. R3R,

R3S2.1, R2R, and R2S2.1 have a lower peak intensity at 2515 than the other

samples. While in the samples with temperature, R3SS2.3, R3S2.3, R2SS2.3 and

R3S2.3, this peak has a higher intensity.

3.4. Thermogravimetric analysis

TGA allows a quantitative analysis based on the reactions experienced by the

samples as a function of temperature, even at lower concentrations than those

determined by DRX. TGA analysis was used to evaluate the residual content of

thermally unstable phases such as Portlandite. Four mass losses were clearly

identified by TGA curves shown in Fig 7 and quantified by DTA curves in Fig. 8.

The first loss of mass is observed between 57 and 100 °C corresponding to the

loss of unbound water adsorbed on concrete pores and the loss of ettringite [31].

While a second mass loss starts from this temperature up to 225 ° which

corresponds to the dehydration reaction of calcium silicates C-S-H and calcium

aluminate hydrates[58]. Firstly, the capillary and free water not influenced by the

Van der Walls attraction forces, evaporate; afterward, the loss of physically and

chemically combined water, associated with the C–S–H phase, occurs [21].

The third loss occurs up to temperatures between 370 and 470 °C. This

corresponding corresponds to the dehydroxylation of residual Portlandite [33]. The

fourth loss of weight in the temperature ranges 600 - 730 °C corresponds to the

decarbonation of calcium carbonate. These results are consistent with those found

by [33], [55], [32] and [29].

Fig. 9a shows the variation of the decomposition of mass losses of the construction

systems according to the level of the temperature exposure to the area found by

TGA-DSC for the second, third and fourth mass loss. A linear trend between the

layer exposure to temperature and the percentage of calcium hydrates

decomposition is found for all samples collected. Decomposition by dehydration of

C-S-H is greater in samples exposed to higher temperatures, S2.3 and SS2.3.

Similar behavior of thermal decomposition by dehydration of calcium hydrates and

C-S-H gels was also observed by SEM. It is also observed that R2S shows a lower

loss of carbohydrates by exposure to temperature than the other samples.

Fig 9b shows the weight fractions of Portlandite calculated from the weight losses

in TGA. The relationship between the position in the constructive system of the

sample and the Portlandite content was found. It is known that dehydroxylation of

Ca(OH)2 occurs through Ca(OH)2 → CaO + H2O around 460 °C [26,51]. Content of

Portlandite follows the decreasing order S2.2 > S2.1 > S2.3 and SS2.2 > SS2.1 >
SS2.3. This trend is consistent with the intensity of the reflection (001) of the

Portlandite found by DRX (see Fig 2 and 3). The variation in the residual content of

Portlandite in the samples exposed directly to the oven is related to the exposure

temperature. Temperatures reached in the center of the construction systems

promote an increase in the crystallinity of the Portlandite and the R3 system

experiences greater Portlandite loss due to fire exposure than R2. Portlandite

remains unchanged until 350 °C [52]. Between 460 and 540 °C its decomposition

occurs [5,7,33,60,68,69]. However, in real fires the temperature can rise from 25

°C to ~ 1000 °C in a few minutes and thermodynamic equilibrium is not achieved

and the decomposition of the Portlandite is not total. On the other hand, the

thermal decomposition of carbonates (Fig 9c) tends to decrease as a result of

increasing position in the constructive system of the samples. The loss of

carbonates in the R3SS and R2SS samples is greater than in the R3S and R3S

samples because they are in the area of greatest temperature. The formation of

CaCO3 as a product of decomposition of the paste of the hydrated cement is

dependent on the presence of CO2 formed by combustion in the fire [70].

4. Conclusion

Utilized analytical techniques to monitor the microstructural and compositional

change within the concrete of stay-in-place polyvinyl chloride (PVC) formwork

concrete induced by exposure to a temperature of a real fire. Accordingly, the main

conclusions are: (i) Quartz, Anorthite, C-S-H, Portlandite, Calcite, and lime were

identified as major crystalline phases present in the crystalline systems. (ii) The
decomposition temperature ranges of common phases present and coexisting in

the concrete were identified: 54- 251°C for C-S-H gels, calcium hydrates and

ettringite, 376- 462 °C to Portlandite and 603 – 727 °C to calcium carbonates.

(iv)The degree of decomposition of the C-S-H, ettringite and calcium hydrates

phases by exposure to temperature was observed by electron microscopy. (iv)

Direct quantitative relationship between the percentage of decomposition of the

phases C-S-H, ettringite and carbohydrates and the temperature of exposure to fire

that was found by TGA/DSC analysis (v) In addition, an increase in the crystallinity

of the Portlandite is found in the center of the construction system, as well as a

loss of carbonates.

Declaration of competing for interest

The authors declare that they have no known competing for financial interests or

personal relationships that could have appeared to influence the work reported in

this paper.

Acknowledgments

The authors acknowledge the support of Universidad de la Costa. To the

Technological Institute in Civil Construction Performance of the Unisinos University

(itt-Performance) and the Interdisciplinary Center for Characterization of Matters

(CIAM) of the Universidade Federal do Rio Grande do Sul for supporting this

research work.
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 S

SS

Figure 1. Final appearance of the surface not exposed to the fire and areas selected for

sampling of R2 system.
 Q Q
An
R3R Et CSH

CSH Et
An CSH
CaO
An Do Gy C2S
Gy
Intensity (a.u.)

Et CC Gy C2S
Gy
CSH C2S Et
CH

CaO
25 30 Q 35
CSH

Gy An Q
Et An Q CaO Q Q
Q
Q Q Q
MgO
MgO
CSH CH An CH
CH Gy C2S Q Gy
Et Gy

10 20 30 40 50 60
2 (°)

An
R2R Q CSH

CSH
An CaO
Et
Et
CSH
Intensity (a.u.)

Gy Gy
Q CSH An C2S
CSH
Et Do
Gy Et
CSH Gy CH
Et Et

25 30 35
Q
Q
Q
An Q
Gy AnQ Gy
CACH CaO Q
CH
Q Q An
Et MgO
CSH MgO CH CH
Gy C S Q
Et 2 Gy

10 20 30 40 50 60

2 (°)

Fig 2. XRD peak patterns of the initial samples, not exposed to temperature, R3R
and R2R.
CSH = Jennite gel
Et = Etringite
CH = Portlandite

Q = Quartz

An = Anorthite

CaO = Calcium oxide

Gy = Gypsum

C2S = Calcium Silicate (Ca2SiO4)

MgO = Magnesium Oxide

CC = Calcite

Do = Dolomite

CACH = Calcium Aluminum Oxide Carbonate Hydrate

 An
Q Q Q Et
R3S2.3 R2S2.3
Gy CH
Gy C2S
CH Gy CC
CC CH
MgO
An
An

Intensity (a. u.)

R3S2.2
Intensity (a.u.)

CaO R2S2.2
Do An
CSH MgO
C2S

R3S2.1 CSH R2S2.1

CaO
Do

10 15 20 25 30 35 40 45 10 15 20 25 30 35 40 45
2 (°) 2 (°)

R3SS2.3
R2SS2.3
An
Gy
CaO
CaO C2S

R3SS2.2
Intensity (a.u. )

R2SS2.2
An
Intensity (a. u.) Gy

Gy

R3SS2.1 Q R2SS2.1
Q

CH
CH CSH
An An

10 15 20 25 30 35 40 45
10 15 20 25 30 35 40 45
2 (°) 2 (°)

Fig. 3. XRD peak patterns at different degrees of exposure to temperature of R3 system.

 (a) (b) (c)

(d) (e) (f)

Fig 4. photomicrographs of samples exposed to fire at different levels (a) R3SS2.1, (b)

R3SS2.2, (c) R3SS2.3, (d) R2SS2.1, (e ) R2SS2.2, (f) R2SS2.3 at 1000x

 Ca Si
(a)

C Al Al

Cl Ca
(b)

Ti Si

Fig. 5. Micrographs of visible particles after exposure to temperatures greater than 900 ° C. (a) R3SS2.3 y (b) R2SS2.3
 R2R R2S2.1 R2S2.2 R2S2.3
R2SS2.1 R2SS2.2 R2SS2.3

Transmitance (%) O-H

2515
SO4

3640
CO3 Al-O
Si-O
O-H

4000 3500 3000 2500 1500 1000 500

Wave R3S2.1
R3R number (cm -1)
R3S2.2 R3S2.3
R3SS2.1 R3SS2.2 R3SS2.3
Transmitance (%)

4000 3500 3000 2500 1500 1000 500

Wave number (cm-1)

Fig 6. FTIR spectrum of concrete samples of (a) R2 and (b) R3 Concrete-PVC

system exposed to elevated temperature.

 100 R3SS2.3

Weight Percent (%) R3S2.3

98
R3SS2.2
R3S2.2
96
R3SS2.1

94 R3R
R3S2.1
92

200 400 600 800 1000

Temperature (°C)

100
Weight Percent (%)

R2SS2.3

98 R2S2.3

R2SS2.2
96
R2S2.2 R2SS2.1

94 R2R

92 R2S2.1

200 400 600 800 1000

Temperature (°C)
Fig. 7. TGA curves of system exposed at fire. Samples collected of different layer and
zones.
 0,04 421°C
0,00
-0,04
-0,08
-0,12 422°C 429°C
-0,16 423°C
-0,20 R2SS2.1
DTA (% min-1)

R2SS2.2
R2SS2.3
R2R
0,04
0,00 424°C

-0,04
-0,08
430°C
-0,12 R2S2.1
R2S2.2
-0,16 423°C
R2S2.3
-0,20 R2R

200 400 600 800 1000

TEMPERATURE (°C)

0,04
428 °C
0,00
-0,04

-0,08
411 °C
-0,12 430 °C

-0,16 428 °C
DTA (% min-1)

R3R
-0,20 R3SS2.1
R3SS2.2
R3SS2.3

0,04
0,00
-0,04
-0,08
394 °C 430 °C
-0,12 R3R
423 °C R3S2.1
-0,16 R3S2.2
420 °C R3S2.3
-0,20

200 400 600 800 1000

TEMPERATURE (° C)

Fig. 8. DTA curves of system exposed at fire. Samples collected of different layer and
zones for R3 (left) and R2 (right) construction systems.
 R2S R2SS R3S R3SS R2S R2SS R3S R3SS R2S R2SS R3S R3SS
2,0 2,5
100
1,8
Calcium hydrates (%)

90 1,6

Portlandite (%)
80 1,4 2,0

Calcite (%)
70 1,2
1,0
60 1,5
0,8
50 0,6
40 0,4
0,2 1,0
30
0,0
20
1 2 3 0 1 2 3 0 1 2 3
Fire exposure level Fire exposure level Fire exposure level
(a) (b) (c)

Fig. 9. Variation of the mass losses of the construction systems according to the level of fire exposure to the area found by TGA-DSC.

(a) Decomposition of calcium hydrates (b) Portlandite dehydration and (c) decarbonation.
 Table 3. Characteristic absorption bands of FTIR spectra.

B band, P peak, vs very strong, s strong, m medium, w weak, - not found

Phase Band center, cm−1 Reference

C-S-H 971 B-Vs, 680 P- w, 641 P- w [40]
Quartz 1024 B-Vs, 809 P-m [38], [63].
Gypsum 1150 P-w, [26], [40].
Calcite 1490 P-s, 1420 P-s [40]
Water 3467 B-Vs, 1642 B-m [42]
Portlandite 3669 P-w [54]
Table 1. Classification of subsamples collected for analytical studies according to

the area, side and degree of fire affectation

System Zone Side Temperature reached Sample

(°C)
Control --- R2R
sample --- R3R
Reference ----
Control
sample
Outside 90 R3SS2.1
More affected
Medium --- R3SS2.2
(SS)
Inside 960 R3SS2.3
RES001.03
Outside 106 R3S2.1
Less affected
medium ---- R3S2.2
(S)
Inside 920 R3S2.3
Outside 52 R2SS2.1
More affected
medium --- R2SS2.2
(SSS)
Inside 860 R2SS2.3
RES001.02
Outside 73 R2S2.1
Less affected
medium ---- R2S2.2
(S)
Inside 810 R2S2.3
Table 2. Quantitative elemental composition of the samples extracted from construction systems expressed as weight

percentages (% w/w) of their respective oxides.

Samples SiO2 CaO Al2O3 Fe2O3 SO3 K2 O TiO2 MgO P2O5 MnO
R3R 58.73 20.04 9.02 7.14 1.35 1.45 0.94 0.79 0.22 0.12
R2S2.1 51.77 25.19 9.10 8.05 1.93 1.39 1.01 0.92 0.21 0.13
R2S2.2 56.64 21.50 8.41 7.68 1.56 1.18 0.81 0.85 0.17 0.12
R2S2.3 55.50 23.20 8.97 7.10 1.62 1.39 0.95 0.88 0.20 0.12
R2SS2.1 52.59 26.14 8.98 6.80 1.81 1.38 0.95 0.96 0.19 0.11
R2SS2.2 51.84 25.38 9.30 7.67 1.87 1.37 1.00 1.04 0.22 0.13
R2SS2.3 43.24 31.03 10.04 9.45 2.04 1.46 1.16 1.13 0.23 0.16
R2R 57.39 19.72 9.50 8.10 1.36 1.49 1.02 0.81 0.22 0.13
R2S2.1 56.77 21.96 9.18 6.28 1.54 1.34 0.85 0.90 0.18 0.11
R2S2.2 56.44 22.35 9.28 6.55 1.59 1.29 0.88 0.91 0.19 0.10
R2S2.3 58.06 20.70 8.99 6.83 1.54 1.16 0.76 0.93 0.17 0.10
R2SS2.1 57.23 21.42 8.68 6.46 1.51 1.32 0.86 0.83 0.17 0.11
R2SS2.2 55.54 22.33 9.65 6.94 1.60 1.36 0.92 0.92 0.19 0.11
R2SS2.3 58.03 17.61 10.22 8.88 0.98 1.53 1.18 0.95 0.26 0.14
Declaration of interests

☐ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

The authors of paper “MULTIANALYTICAL APPROACH OF STAY-IN-PLACE POLYVINYL CHLORIDE

(PVC) FORMWORK CONCRETE EXPOSED TO HIGH TEMPERATURES”; Leandro Gómez Plata,
Bernardo F. Tutikian, Fernanda Pacheco, Marcos S. Oliveira, Michel Murillo, Luis F. O. Silva, and
Carlos Pérez Bergmann, declare that have no known competing for financial interests or personal
relationships that could have appeared to influence the work reported in this paper
 November 01, 2019

Editors:
JOURNAL OF MATERIALS RESEARCH AND TECHNOLOGY

Subject: Manuscript for Consideration

Dear Editors:

The manuscript titled “MULTIANALYTICAL APPROACH OF STAY-IN-PLACE

POLYVINYL CHLORIDE FORMWORK CONCRETE EXPOSED TO HIGH
TEMPERATURES” is submitting by Leandro Gómez Plata, Bernandro F. Tutikian,
Fernanda Pacheco, Marcos Oliveira, Michel Murillo, Luis F. O. Silva and Carlos
Pérez Bergmann.

This investigation is the first multi analytical study of phase chages and microstruture
of concrete of stay-in-place polyvinyl chloride (PVC) formwork concrete constructive
system by exposure to high temperatures.

We certify that the investigation is original, we approve the submitted final version
and, it complies with the scientific and ethical regulations. Consent is given for your
consideration in the JOURNAL OF MATERIALS RESEARCH AND TECHNOLOGY

Thank you for your time and attention.

Sincerely,

Leandro Gómez Plata

Corresponding Author
Table 1. specifications of construction systems exposed to fire.

System RES001.02/RES001.03

Dimensions (mm) 200 x 80

Wall thickness (mm) 1.7

Profile Spacing of reinforcements (mm) 70

Density (kg / m³) 1450

Charpy impact strength (kJ / m²) 18.5

Mechanical resistance (MPa) 20

bulk density (kg / m³) 2300

Concrete
Maximum diameter of the aggregate
9.5
(mm)

Graphic representation

Fig 1. Building concrete-PVC wall (a) top view and (b) front view.
 Description of the fire test

The furnace is controlled by differential pressure, with total heating power of 65.4 kcal / h,

with 396 kcal / h in the lower part and 258 kcal / h in the upper part, programmed to carry

out automatic heating according to with the fire curve in buildings described by the standard.

More details of the furnace's operation are presented by Gil (2018; 2017). The samples were

exposed to the fire by the standardized temperatures of ISO 834 (ISO, 1980). The heating

curve is described by equation 1. Where t is the time, in minutes, and T is the average furnace

temperature in ° C. All tests lasted for 80 minutes, the initial temperature (To) being 21.6 °

C reaching external temperatures of 986 ° C.

𝑇 = 345 𝑥 𝑙𝑜𝑔10 (8𝑡 + 1) + 20 𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 1

Systems were continuously monitored by 5 K-type thermocouples, 1.5 mm in diameter, on

their face exposed to fire, and 5 T-type thermocouples, 0.7 mm in diameter, on their non-

exposed surface. by nine thermocouples placed in the non-exposed side of the wall. The

arithmetic average of the temperature of the main thermocouples cannot pass the limit of 140

°C and/or one of the nine thermocouples must not overpass 180 °C.

Samples maintained the thermal insulation defined by standard throughout the test period.

Systems R3 present a fire resistance time (TRF) of 64 minutes, while the R2 system presents

fire resistance time of 20 minutes, according to ABNT NBR 5628: 2001, during which time

the requirements of mechanical resistance, water tightness and thermal insulation were met.

Variation of temperature captured with a thermal chamber at the beginning of the test and

after 80 minutes showed that the temperature reached by the external surface of the

construction system does not exceed 100 ° C. Regarding the thermal insulation, no significant
increase of the temperature on the external face was verified, besides the normative

limitations for the tests of resistance to the fire, throughout the period of test. However, there

were cracks in the sample, and then the flames passed through the fissures, characterizing the

leakage of the system at 26 minutes of the test.

Thermal monitoring of the constructive system was carried out using a thermographic camera

FLIR / A325. Temperature characterizing the sample as thermal insulation during the entire

test period for both samples. Not significant increase in the external temperature it was

reached, and limits of temperature not were reached according to the resistance test curve.

Fig. 1. Thermographic images of R2 systems exposed to fire. (a) 5 minutes (b) 15 minutes

and (c) 80 minutes.

Table 2. Loss of weight (%) and weight fractions of Portlandite ad Calcite

Samples Calcium hydrates Portlandite Calcite
Mass Decomposition Mass Ca(OH)2 Mass CaCO3
change percent (%) change (%) change (%)
(%) (%) (%)
R3R 1.87 --- 0.27 1.09 0.92 2.09
R3S2.1 1.23 34.3 0.29 1.18 0.90 2.05
R3S2.2 0.68 63.7 0.38 1.58 0.37 0.85
R3S2.3 0.11 93.9 0.01 0.04 0.81 1.85
R3SS2.1 0.41 57.3 0.23 0.93 0.60 1.37
R3SS2.2 0.80 77.8 0.43 1.77 0.45 1.02
R3SS2.3 0.00 100.0 0.01 0.05 0.44 0.99

R2R ---- 0.31 1.26 1.02 2.32

1.69
R2S2.1 0.70 74.1 0.31 1.27 0.76 1.72
R2S2.2 1.25 61.0 0.40 1.63 0.76 1.72
R2S2.3 1.03 41.5 0.38 1.56 0.83 1.90
R2SS2.1 1.21 71.5 0.29 1.21 0.90 2.05
R2SS2.2 0.68 40.5 0.39 1.62 0.74 1.68
R2SSS2.3 0.13 7.8 0.39 1.62 0.69 1.56