Durability of Concretes with Marble Powder

Rabah Chaid1,

, Arnaud Perrot2 and Youcef Ghernouti

1

1Laboratory of Mineral & Composite Materials, University of Boumerdes, Algeria

2University of Brittany the South of Lorient, French

Abstract. The aim of this study is to examine the valorisation of mineral residues as addition in building

materials with cementious matrix, and contributes to sustainable development. The study is based on

experimental work carried out at the Civil Engineering and Mechanical Engineering Laboratory (INSA-

Rennes, France) and at the Mineral and Composite Materials Laboratory (University of Boumerdès, Algeria).

The use of recyclable industrial waste as a partial replacement of Portland cement in concrete allows

reduction of greenhouse gas emissions (GGE) and results in the manufacturing of a concrete with less

environmental impact. Applying various experimental techniques, the behaviour of finely crushed marble

powder addition with Portland cement, with limestone addition, is studied. This study confirmed the

improvement of the physical and chemical properties of concretes with marble powder addition; this

indicates the potential advantage of using this supplementary cementitious materials.

Keywords: HPC, marble, durability, sulfate

1. Introduction

The management of waste and industrial by-products is crucial for the technical, economic and

environmental benefit of society as a whole and business in particular. These factors should include, for

example, the life cycle analysis of products or services, thus integrating into these processes the management

of residues and by-products. Engineering and environmental studies can facilitate this management,

particularly in civil engineering [1-2]. Moreover, the building materials sector is responsible for 9.5 % of the

total anthropogenic emissions of carbon dioxide in Europe. About 80% of this amount comes from cement

production, then it seems that reducing the amount of cement in concretes and mortars has become a priority

[3]. One way for cement and concrete industries to do so is the substitution of clinker with mineral additions.

In recent years, many studies have focused on the ordinary Portland cement supplementation by industrial

by-products [4].

The use of industrial waste and reducing the demand for natural resources (such as limestone and iron

ore) are beneficial. It is also important to note that the concrete with supplementary cementitious materials

(SCMs) generally have a lifespan longer than conventional concrete [5].

The most aggressive environments for concrete are saline and sulfate environments, these represent a

major hazard by virtue of chemical attack on the concrete. A survey by the OECD (Organization for

Economic Cooperation and Development) conducted in 1989 indicates that the sulfate attack is the second

leading global cause of damage; this type of attack being detected on 800 000 structures.

Given the denser structure of high-performance concretes (HPC), these materials exhibit a better

behaviour towards aggression mechanisms. Most degradation processes are caused by the penetration of

aggressive substances, such as chlorides, carbon dioxide, acids and sulfates. If this penetration is impeded, as

in the case of HPC, the degradation processes will not manifest itself until much later in the service life.

Corresponding author. Tel +21324913866, Fax +21324913866 E-mail address: chaidr@yahoo.fr

2015 5th International Conference on Environment Science and Engineering

Volume 83 of IPCBEE (2015)

DOI: 10.7763/IPCBEE. 2015. V83. 6

33

By using various experimental techniques, special care is given to the behaviour of the finely ground

marble powder together with Portland cement containing limestone addition. The use of Marble powder as a

SCM has already been studied in the recent literature, especially for SCC mix design [6-7-8]. However, none

of this study focuses on the durability behaviour containing marble powder. Depending on the nature of

SCMs considered, their different behaviour may influence the design of the concrete mixes with an impact

on their durability. This study confirmed the improvement of physico-chemical properties of concrete with

marble powder, which presents a strong argument for its use as a concrete addition.

2. Materials Used

2.1. Cement

The Portland cement has a Blaine Specific Surface (BSS) of 3830 cm2/g. It is a CEM II / A 42.5 clinker

with addition of 10% limestone. The cement is marketed by Egyptian Orascom Group (Algerian Cement

Company). The X-ray diffraction analysis of the anhydrous cement is shown on Fig. 1.

The XRD pattern shows the presence of different crystalline phases: the four essential minerals (C3S,

βC2S, C3A and C4AF) which are responsible for setting and hardening; gypsum, (CaSO4.2H2O) regulate

setting time; and limestone filler addition.

Fig. 1: XRD pattern of CEM II / A 42,5 (λkα Cu).

2.2. Marble powder (PM)

The marble power used is a waste product from marble masonry. The micro analysis performed over a

wide range of points shows identical chemical compositions (Fig. 2).

Fig. 2: Micro analyse EDS of the marble powder.

The Particle Size Distribution (PSD) was measured in ethanol using a laser granulometer CILAS 1180;

the results are shown in Fig. 3. The marble powder has a Blaine specific surface of 12 000 cm2 / g. The key

point that emerges from the results, summarized by granulometric fineness, is that the powder is well graded.

50% of the marble powder particles are finer than 4 microns and 77% are finer than 10 microns.

C calcite

G gypsum ▲ C3S

► βC2S

◄ C4AF

♠ C3A

Position [°2Theta]

Counts

225

100

25

0

10 20

40 50

Element %Mass %Atomic

C K 17.44 27.42

O K 47.20 55.73

Mg K 0.31 0.24

Al K 0.16 0.11

Si K 0.26 0.18

Ca K 34.64 16.32

Totals 100.00

34

Approximately 95% of particles are finer 20 microns. Based on the coefficient of uniformity (Cu), the

powdered marble has a tight distribution.

Fig. 3: Granulometric curve for marble powder.

2.3. Aggregates

An optimized concrete mix design necessarily involves the determination of optimum mass ratios of

various aggregates. The coarse aggregate are crushed gravel from the Jaubert quarry (Algeria), and is mainly

limestone.

In this study, after preliminary tests on both the rheology of concrete mixtures at fresh state and the

mechanical behaviour at hardened state, the granular classes 3/8 and 8/15 were chosen.

The sand consists of a mix containing 76% of Akbou Sand and 24% of Boussaâda Sand (Algeria), the

final fineness modulus after homogenization is 2.60.

2.4. Admixtures

In order to ensure required workability, the incorporation of a water-reducing superplasticizer is

necessary. The molecules of superplasticizer are adsorbed on the cement grains surface at the interface with

the mix water. Once adsorbed, the superplasticizer molecules induce a steric effect that increases the distance

between cement particles. As a consequence, the cement grains network is weakened [9-10]. The resulting

dispersion reduces the viscosity and the yield stress of the cement paste and increases workability; the

molecular structure of the polymeric superplasticizer - in the form of long chains - reinforces this effect.

The admixture used is Viscocrete 3045, an unchlorinated water reducer plasticizer, based on modified

polycarboxylates, it provides a good workability for up to 1h 30.

In fluid concrete, Viscocrete 3045 improves stability of the concrete, reduces the risk of aggregates

segregation and makes the mix less sensitive to small variation in water and constituents mass ratio.

Table 1: Composition of the concretes studied

Constituents Composition

CC CMP

Cement kg/m3 400 360

Sand kg/m3 612 612

Aggregate (3/8) kg/m3 108 108

Aggregate

(8/15)

kg/m3 1064 1064

Water l/m3 136 136

Admixture l/m3 7.2 7.2

Marble (MP) kg/m3 - 40

3. Experimental Program

Perc

en

tag

e p

assin

g %

Particle size µm

35

The compositions of concretes with and without powdered marble are used in the experimental program

as reported in Table 1. It should be noted that the levels of marble powder addition (MP) and superplasticizer,

after optimization, are respectively 10% and 2% of the cement mass. For reported tests the following legend

is adopted.

3.1. Types of concrete

CC: Control Concrete

CMP: Concrete with Marble Powder

The physical, mechanical and microstructure of concrete with and without addition of marble powder are

compared. In addition, mineralogical characterization techniques have been carried out which include X-ray

diffraction (XRD), differential thermal analysis and gravimetric analysis (DTA-TGA) and scanning electron

microscopy (SEM) combined with a micro analysis (EDS).

4. Results and Analysis

The aim of this study is to examine the durability of concrete exposed to sulfates; the resistance of

concrete to sulfate attack being an important factor for durability.

The origin of sulfate contamination of concrete is diverse; internal sources namely the material itself

(aggregates containing gypsum or sulphides; gypsum cement used as a retarder ...); external sources of

sulfates from exposure to the ambient environment (sewage, industrial pollution, groundwater and

seawater ...). In these cases the sulfate migrated into the cement matrix by diffusion thus attacking the

integrity of the concrete. The sulfate can alter the concrete in two physico-chemical ways, expansion and / or

loss of binding properties of the CSH.

4.1. Strength

It is noted that the compressive strength of concrete with marble powder addition, with a very tight

particle size distribution (Fig. 4) as used in this study, has a higher strength than the control one for all stages

of maturity. It is concluded that these are high-performance concretes; this property is not altered by the

surrounding environment (Fig. 5). This can be attributed to the fact that the specific surface of marble

powder is higher than the one of cement. Then, marble powder adsorbs more water than cement. As a result,

the ratio of water available for hydration is reduced leading to better mechanical strengths.

0

20

40

60

80

3 7 28 90

Age (days).

Fig. 4: Evolution of compressive strength with relation to age

4.2. Capillary absorption

Capillary absorption of the samples is determined; the results obtained confirm the low capacity of water

absorption for concrete with marble powder addition compared to the control concrete; this is an indication

of an increased compactness of the concrete. This can be attributed to the fineness of the marble powder that

reduces the pore size distribution compared to control concrete. In addition to their high strength the samples

have improved durability. The marble powder addition will retard the penetration of aggressive agents,

including the sulfate ions within the concrete matrix.

CMP

CC

Co

mp

ress

ive

Str

ength

M

Pa

36

0

2

4

6

8

10

12

1h 2h 3h 4h 2j 3j 7j 11j

Square root of time (h).C

ap

illa

ry

ab

sorp

tio

n c

oeff

icie

nt

(%).

CC

CMP

Fig. 5: Evolution of capillary absorption coefficient.

4.3. Measurement of oxygen permeability

This method is applicable to moulded samples and cores that are within the dimensional tolerance limits

imposed by the apparatus. The technique can measure permeability ranging between 10-15 and 10-20 m2

[11].

The test consists of submitting a cylindrical sample to a constant pressure gradient of oxygen. The

permeability thus is determined from the measurement the oxygen flux at a steady flow. This test is

performed on five specimens at three pressures (2, 4 and 6 bar absolute). An average permeability value is

computed. The three samples, from the group of five, that exhibit the permeabilities closest to the average

are considered as the most representative of the material [12].

0,00

0,50

1,00

1,50

2,00

2,50

0,50 0,25 0,17

Reciprocal of the applied pressure (MPa).

Fig. 6: Oxygen permeability of the concretes.

Regardless of pressure, the addition of finely crushed marble powder led to a significant decrease in the

coefficient of permeability to oxygen. For example, at a pressure of 6 bar, Ka is 2.3 10-16

m2 for concrete

control, and 1.3 10-17 m

2 for concrete with marble powder addition (Fig. 6). Those results are consistent with

the capillary absorption coefficient.

4.4. Internal Microstructure

The physico-chemical analysis, by XRD shows that the hydration process corresponding to different

cement paste phases leads to a more or less well crystallized structure. The components identified after three

months conservation in calcium sulfate solution are shown in Fig.s 7 and 8.

For all compositions studied hydration leads to the formation of portlandite CH, calcite CC and a silica-

hydrate CSH gel. The three major diffraction peaks of CSH are not clearly identified, reflecting its low

degree of crystallization. XRD analysis indicates that ettringite C3A.3CaSO4.31H2O is present in the

hardened paste after a period of three months.

Ox

yg

en p

erm

eab

ilit

y (

10

-16 m

2).

CMP

CC

37

Fig. 7: XRD pattern of the hardened CEM II 42.5 cement paste after three months conservation in calcium sulfate

solution.

The results indicate that the sulfate attack, initiated by gypsum, induces a weak precipitation of ettringite;

the most stable environment for this compound being a pH greater than 10.5. In the sample without marble

addition, it appears that the sulfate attack is more pronounced. This reaction occurs in an environment where

ettringite is more stable.

Finally, one can note the significant and growing presence of calcite resulting from the carbonation of

hydrated phases, mainly portlandite, in the samples; also from mineral limestone and marble powder. The

differential thermal analysis is used to verify the XRD observations.

Fig. 8: XRD pattern of hardened CEM II 42.5 cement paste with marble addition after three months conservation in

calcium sulfate solution.

4.5. Thermo-gravimetric Analysis

The thermo-gravimetric analysis (Fig.s 9a and 9b) show essentially three mass losses which respectively

characterize the loss of water molecules of CxSyAtHz and C6AS3H32 without differentiating the portlandite

dehydration and the de-carbonation of CaCO3 (initial and newly formed CaCO3). However, this method does

not detect the presence of monocarboaluminate C4ACH11 or hydrated alumina.

The endothermic effect at temperature of 450-550 °C, expresses the presence of remaining free hydrated

lime crystals [13-14].

The thermo-gravimetric analysis shows the initial loss of free water; for the CEM II paste at a higher

temperature (146 ° C) than from that CEM II with marble powder addition (127 °C). Conversely, the amount

of water released is somewhat higher (24.23%) as opposed to 19.10% for the CEMII plus marble addition;

this is a consequence of the fineness of the marble powder, whose demand for water is higher and in parallel

evaporation temperature is lower.

C Calcite

▲ C3S

► βC2S

◄ C4AF

P Ca(OH)2

E Ettringite

Counts

225

100

25

0 10 20 30 40 60 50

Position [°2Theta]

Counts

225

100

25

0

10 20 30 40 60 50 Position [°2Theta]

C Calcite

▲ C3S

► βC2S

◄ C4AF

P Ca(OH)2

E Ettringite

38

Fig. 9: thermo-gravimetric analysis of CEM II 42.5.

The formation of portlandite in the cement paste with marble addition is lower, due to the partial

replacement of cement with marble powder. Dehydration for the former being 4.28% compared with 3.28%

for latter.

Finally, in the temperature range 740-840 °C progressive de-carbonation of carbonates occurs. In this

case, the endothermic peak for the cement paste with addition is more pronounced; marble powder addition

causes a mass loss of 5.03% as opposed to 2.32% for cement paste without addition.

These results confirm the beneficial effect of finely crushed powder marble filler. The properties of

concrete and cement pastes, in terms of compressive strength, capillary absorption and gas permeability are

improved. The impact of marble powder on microstructures, in terms of densification of matrix and

modification of porosity is very pronounced.

5. Conclusions

The partial replacement of cement by marble powder does not contribute to the formation of a significant

volume of hydrated products capable of reducing porosity, however the compressive strength may be

improved to a greater or lesser extent.

The marble powder can efficiently supplement cement in concrete; this structural contribution manifests

itself by the reduction of porosity and consequently a greater resistance to chemical attack.

The concrete with the addition of marble powder with a specific surface of 12,000 cm2/g offers

interesting advantages over the conventional control concrete: higher strength, improved durability against

physico-chemical absorption; the absorption of capillary water is reduced as is the permeability. This should

lead to improved freeze thaw resistance, although this remains to be verified.

In addition to its obvious ecological impact, re-use of waste marble dust and its integration in concrete

has great advantages in terms of long-term maintenance resulting from the improved durability of structures.

6. References

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