Accepted Manuscript

Granite quarry waste as a future eco-efficient supplementary cementitious

material (SCM): scientific and technical considerations

G. Medina, I.F. Sáez del Bosque, M. Frías, M.I. Sánchez de Rojas, C. Medina

PII: S0959-6526(17)30252-4

DOI: 10.1016/j.jclepro.2017.02.048

Reference: JCLP 8974

To appear in: Journal of Cleaner Production

Received Date: 19 November 2016

Revised Date: 06 February 2017

Accepted Date: 06 February 2017

Please cite this article as: G. Medina, I.F. Sáez del Bosque, M. Frías, M.I. Sánchez de Rojas, C.
Medina, Granite quarry waste as a future eco-efficient supplementary cementitious material (SCM):
scientific and technical considerations, Journal of Cleaner Production (2017), doi: 10.1016/j.jclepro.
2017.02.048

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 ACCEPTED MANUSCRIPT

HIGHLIGHTS

 The granite sludge has been used as SCM in the design of the new blended cements.

 The mortars designed compliant with the requirements laid down in European standard.

 The amount of the portlandite is slightly less in the new blended cements.

 The new SCM induces no changes in C-S-H gel product morphology.

 Low concentrations of the waste can be regarded as feasible new SCM.

 ACCEPTED MANUSCRIPT

Granite quarry waste as a future eco-efficient supplementary cementitious

material (SCM): scientific and technical considerations

G. Medina1, I.F. Sáez del Bosque2, M. Frías3, M.I. Sánchez de Rojas3, C. Medina3*

1. Departamento Ingenierías Mecánica, Informática y Aeroespacial, Escuela de Ingenierías Industrial e

Informática, Universidad de León, Campus de Vegazana, s/n, 24071 – León, Spain

2. Departamento de Construcción, Escuela Politécnica de Cáceres – Grado de Ingeniería Civil,

Universidad de Extremadura, Unidad Asociada UEX-CSIC, 10071 - Cáceres, Spain

3. Departamento de Cementos y Reciclado de Materiales, Instituto de Ciencias de la Construcción

Eduardo Torroja, Consejo Superior de Investigaciones Científicas (CSIC), 28033 - Madrid, Spain

*Corresponding author: cmedinam@unex.es / cemedmart@yahoo.es

Abstract

The vast volumes of waste generated to quarry ornamental granite constitute both an

environmental and a public health hazard.

This study assesses the viability of designing new blended cements in which 10 % or 20 % of the

clinker is replaced with granite sludge by analysing the effect of its inclusion on the chemical,

rheological, mechanical and microstructural properties of the end product. The later age change

in the pore structure of the new mortars induced by the slow pozzolanic kinetics of this

supplementary cementitious material (SCM) translates into a narrow difference in the mechanical

performance between these and conventional mortars. Despite that difference, the new cements

are apt for use in construction, inasmuch as they are compliant with the requirements laid down

for Type II/A and IV/A cements in European standard EN 197-1.

Keywords: granite sludge; supplementary cementitious materials; mechanical behaviour;

microstructure

1. Introduction

The non-energy extractive (NEE) industry furnishes many basic raw materials for European

manufacturing and construction and is vital for European Union (EU) economic competitiveness.

The European construction mineral (essentially aggregate and natural crushed stone) sub-sector

quarries around 109 t/y of stone (European Comission, 2011). Ornamental stone (granite, marble,

slate and similar) was the material most widely used in construction up to the twentieth century,

after which its application in major structures was largely replaced by cement and concrete

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(Mustafa et al., 2016). At this time, the use of ornamental stone such as granite and marble is

confined to floors, pavements, breakwaters, retaining walls, cladding, funeral monuments and

statues. That notwithstanding, worldwide output of ornamental stone amounted to 125 Mt in 2012

(Rana et al., 2016).

Global granite production in 2014, in turn, amounted to 309 Mm2-349 Mm2 (World Natural Stone

Association, 2014). Spain, with 6 Mm2 quarried primarily in Galicia, Madrid and Extremadura

(Centre for Public Works Studies and Experimentation, 2015), was the sixth largest producer

(World Natural Stone Association, 2014).

The inert waste generated by the stone industry (granite, marble…) accounts for approximately

58 % of the total quarry and plant output (Rana et al., 2016). Depending on particle size, this

waste is divided into two major groups: a) solid waste generated during cutting operations; and

b) sludge, comprising splitter cooling water and the particles originated in rock processing (Rana

et al., 2016). This inert granite quarry waste is classified on the European List of Waste under

code 01 04 13, “wastes from stone cutting and sawing other than those mentioned in 01 04 07”

(European Comission, 2000). It has a heavy environmental impact due to its adverse effect on

soil permeability, for it hinders water seepage to the lower layers, which in turn affects aquifer

recovery and plant life. It also constitutes a risk to human health due to the small percentage of

crystalline silica in the fines which, if inhaled, may cause lung disease of varying severity (Singh

et al., 2016).

Valorisation of this type of waste is a highly topical issue in the present socio-economic

environment. In the transition from today’s linear to a circular economic model, waste is reused

as raw materials for new products, with a view to ensuring intelligent, sustainable and integrated

growth (Ministry of Agriculture, Food and Environmental Affairs, 2015).

For decades, the scientific community has been conducting in-depth research on the viability of

valorising industrial waste such as marble dust (Aruntaş et al., 2010), rice husk or bamboo leaf

ash (Aprianti et al., 2015), sewage sludge ash (Paris et al., 2016) or blast furnace slag as cement

additions (Li et al., 2016a). The findings show that the inclusion of small percentages of such

waste induces no decline in the physical or mechanical performance or durability of new cements.

The effect of using mixed recycled (Medina et al., 2015a) or recycled concrete (Thomas et al.,

2013) aggregate from construction and demolition waste (C&DW) on concrete mechanical

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strength and durability has also been studied. Research has likewise addressed the impact of

C&DW on the microproperties of the aggregate/paste interface transition zone (ITZ) (Medina et

al., 2015b) and the use of stone industry waste (Kumar et al., 2017) as coarse aggregate on new

concrete design.

To date, research on granite industry waste has focused primarily on its use as a component in:

a) fired red clay (with slightly lower performance at a replacement ratio of 50 wt% (Acchar et al.,

2006) and higher at 30 wt% (Acchar et al., 2006)); b) roof tiles (with replacement ratios 10 wt%

yielding higher density and strength and ratios of 11 wt%-30 wt% inducing a slight decline (Torres

et al., 2009)); and c) floor finishes (Ayangade et al., 2004) and floor tile (Hojamberdiev et al.,

2011) at replacement ratios of under 30 wt%. The end product in all cases was standard-

compliant.

Research on the valorisation of these materials as cement constituents is incipient and has been

geared to its applicability as a filler or an addition. Authors such as Elmoaty (Abd Elmoaty, 2013)

and Abukersh and Fairfield (Abukersh and Fairfield, 2011), analysing the feasibility of including

5 % (Abd Elmoaty, 2013) and 30 % (Abukersh and Fairfield, 2011) granite sludge as a cement

replacement in new concrete design, reported that mechanical strength underwent no significant

decline at those replacement ratios. Ramos et al. (Ramos et al., 2013), however, observed that

adding 5 % and 10 % granite sludge to cements with varying particle size distributions adversely

affected the fresh and hardened properties of the product.

In another line of research, Mármol et al. (Marmol et al., 2010) and Ho et al. (Ho et al., 2002)

studied the viability of using granite dust as a filler, the former in masonry mortar and the latter in

self-consolidating concrete. Both teams found that inclusion of the waste impaired rheological and

mechanical behaviour, more intensely at higher replacement ratios, requiring larger amounts of

superplasticiser to offset these effects.

The present gap in scientific knowledge on the reuse of granite sludge as a supplementary

cementitious material to reduce cement clinker content makes this study particularly relevant to

the present state of play. Moreover, research on this waste is of special interest in Spain, given

the country’s position as a worldwide granite production major, a matter addressed in the

country’s national waste management framework plan (PEMAR) for 2016-2022 and the Spanish

Centre for Public Works Studies and Experimentation (CEDEX) specifications sheet entitled

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“‘Ornamental stone cutting and processing sludge” (Centre for Public Works Studies and

Experimentation, 2015). The originality of this research lies in the study of the microstructural

changes taking place to substantiate the mechanical and rheological implications of the intrinsic

properties of the waste analysed, which may make it apt for use in the manufacture of new low

clinker blended cements.

This study aims to assess the effect of the replacement of 10 % and 20 % of portland cement with

granite sludge on the chemical, rheological, mechanical and microstructural properties of new,

sustainable type II/A and IV/A cements.

2. Materials and methods

2.1. Materials

The granite sludge (AF) used (around 500 kg) was collected at ornamental stone spoil heaps in

the Spanish region of Extremadura and carried to the laboratory, where it was dried and

characterised for its chemical, mineralogical and physical properties.

The chemical composition determined with X-ray fluorescence (XRF) is given in Table 1 and the

results of the X-ray diffraction (XRD) studies in Figure 1. Table 1 shows that the granite waste

consisted primarily in silica (SiO2) and alumina (Al2O3), which together accounted for 84.6 wt% of

the total. The content in other oxides such as Fe2O3 and MgO was under 2.6 wt%.

Table 1. Chemical composition of the materials used

The sodium oxide equivalent [(Na2O)eq = 0.658*K2O+Na2O)], in turn, an indication of alkali

content, was 6.3 wt%, higher than the 0.6 % recommended in Spanish structural concrete code

EHE-08 for cements with reactive aggregate located in moist environments. As noted earlier by

Abukers and Fairfield (Abukersh and Fairfield, 2011) in red granite dust, most of the alkalis

present were not available for reaction and were unable to contribute to the decay induced by the

alkali-aggregate reaction.

Further to the mineralogical composition shown in Figure 1, this waste contained quartz, feldspar

(orthoclase and alite), phyllosilicates (muscovite, biotite and chamosite) and hematites.

Figure 1. Mineralogical composition of the materials

CEN-standardised, European standard EN 196-1-compliant (European Committee for

Standardization, 2005a) sand with a particle size range of 2-0.08 mm was used.

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The chemical and mineralogical composition of the CEM I 42.5 R ordinary portland cement (OPC)

supplied by a Spanish manufacturer (Lafarge, Toledo, Spain) used in the study is given in Table 1

and Figure 1, respectively.

The blended cements were prepared in a 1 kg capacity high-speed powder mixer to guarantee

homogeneity on the laboratory scale. The blends were calculated by weight, with AF/OPC ratios

of 0/100, 10/90 and 20/80. These replacement levels were adopted on the grounds of the ratios

allowed for Type II/A (6 %–20 %) and Type IV/A (11 %-35 %) cements in European standard EN

197-1 ( European Committee for Standardization, 2011b).

2.2. Material pore size distribution and fineness

The pore size distribution for granite and cement shown in Figure 2 and Brunauer-Emmett-Teller

(BET) - specific surface values were found by measuring N2 adsorption isotherms on a

Micrometrics ASAP 2000 analyser. Both materials had pore diameters in the 0.7-1.9 nm range

and the granite sludge curves had a small shoulder at 1.6 nm and the cement curve at 2.0 nm.

Figure 2. Pore size distribution for OPC and granite sludge

Given the similarity between the BET specific surface values for the addition (1.35 m2/g) and the

cement (1.37 m2/g), that parameter would not affect the performance of future new blended

cements containing this type of waste.

The BET value for the waste was: a) similar to that of other additions such as fired-clay sanitary

ware waste (1.36 m2/g) and fly ash (1.40 m2/g) (Medina et al., 2016); b) higher than in blast

furnace slag (0.72 – 1.02 m2/g) (Arvaniti et al., 2015); c) slightly lower than in fired-clay roof tile

(3.00 m2/g) and construction and demolition waste (6.58 m2/g) (Medina et al., 2013); and d) much

lower than in silica fume (17.10 - 22.20 m2/g) (Arvaniti et al., 2015) and zeolites (39.90 – 17.50

m2/g) (Özen et al., 2016).

2.3. Standard methods

2.3.1. Pozzolanicity test

Pozzolanic activity was determined with the Frattini test described in European standard EN 196-

5 (European Committee for Standardization, 2011a). Further to that procedure, 20 g of cement

were mixed with 100 ml of distilled, decarbonated water and stored in an air-tight polyethylene

container in an electric oven at 40 C. After 8 and 15 d, 20 ml of the solution were titrated with

0.1 N hydrochloric acid (HCl) and the [OH-] concentration was determined with methyl orange.

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Calcium ion concentration was determined from the titrated samples in which the pH was adjusted

to 12.5  0.2 with a 4 N sodium hydroxide solution. The sample was then titrated against a 0.02

mol/L solution of EDTA. Using calcein as the indicator, the endpoint was the change in colour

from pinkish to violet. The presence of Ca(OH)2 in ordinary portland cement was determined from

the solubility curve resulting from plotting the [OH-] values in mmol/L on the X-axis and [Ca2+],

expressed as the CaO equivalent, in mmol/L on the Y-axis.

2.3.2. Setting

The rheological properties (normal consistency and initial and final setting times) for the new

blended cements were determined using a Vicat needle, as described in European standard EN

196-3 (European Committee for Standardization, 2005b).

2.3.3. Expansion

Cement volume stability in normal consistency cement paste was studied with a Le Chatelier

instrument as specified in standard EN 196-3 (European Committee for Standardization, 2005b).

2.3.4. Mechanical behaviour

The new blended cements bearing 10 wt% and 20 wt% granite sludge were tested for

compressive and flexural strength as per European standard EN 196-1 (European Committee for

Standardization, 2005a). The maximum value was adopted because, given the low pozzolanicity

assumed for the waste, higher rates were deemed more likely to adversely affect end product

performance. To that end, 4x4x16 cm mortar prismatic specimens were prepared with a

sand/cement ratio of 3/1 and a water/cement ratio of 1/2. The specimens were removed from the

moulds after 24 h and cured at 201 C and a relative humidity of 100 % until the test date.

2.4. Characterisation

The chemical composition of the materials and new blended cement compliance with chemical

requirements were determined with X-ray fluorescence. Pressed powder samples were analysed

on a Bruker S8 TIGER XRD spectrometer and the data were processed with SPECTRAplus

software, including the QUANT-EXPRESS standardless analysis package.

The mineralogical composition of the materials and new mortars were found on a CuKα (λ=1.54

Å) Bruker D8 Advance diffractometer (Lynxeye detector, 3 mm antiscatter slit, (0.5 %) Ni K-beta

filter,2θ angles, 5º-60º.

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Mortar pore size distribution was quantified as per ASTM standard D 4404 [36] on a Micromeritics

Autopore IV 9500 mercury porosimeter (scalem 0.006 to 175 m, pressure, 33 000 psi (227.5

MPa).

The DTA and TG analyses were conducted in a dynamic N2 atmosphere on a TA Instruments

SDTQ600 thermal analyser (T=20 ºC-1000 °C at 10 °C/min).

For scanning electron microscopic (SEM) analysis, the samples were secured to a metallic holder

with a two-sided graphic adhesive after carbon coating the surface to ensure conductivity and

detection of all the signals sought.

3. Results and discussion

3.1. Pozzolanicity test

The Frattini test findings (Figure 3) showed that the 8 day additioned materials stood slightly

above the CaO solubility curve and slightly to the left of the reference cement (OPC). That shift

went hand-in-hand with the release of a higher concentration of Ca2+ by the former during cement

hydration.

Figure 3. Frattini diagram for assessing pozzolanicity

The value for the 15 day cement with 10 % sludge (90OPC+10AF) was located above the CaO

solubility curve, and the material with 20 % sludge (80OPC+20AF) below it (Figure 3). Less Ca2+

was released by the 15 day 90OPC+10AF than by the analogous 8 day material. The 15 day

80OPC+20AF cement was positioned underneath the CaO solubility curve, an indication that Ca2+

release during hydration was less intense. Consequently, further to existing European standard

EN 197-1 (European Committee for Standardization, 2011b), the cement with 20 % granite sludge

(80OPC+20AF) would be classified as pozzolanic (class IV).

That behaviour was directly related to granite sludge pozzolanicity patterns, for this material has

been previously reported to exhibit low early age reactivity, with approximately 20 % lime fixation

after 7 d, 29 % after 14 d and 39 % after 28 d (Medina et al., 2017). Juenger and Siddique

(Juenger and Siddique, 2015) observed that this type of low early age activity additions initially

acted as fillers, providing nucleation sites and raising the space available for hydration product

precipitation. At later ages, this filler effect was superseded by the pozzolanic effect, with a

reduction in the portlandite content and consequently of the Ca2+ released.

3.2. Chemical requirements and the new cements

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According to the comparison in Table 2, the new cements had a lower SO3 and Cl- content than

the ceilings laid down in European standard EN 197-1 (European Committee for Standardization,

2011b) for type II/A and IV/A cements and complied with the chemical requirements for type II/A

cements with additions of 6 wt%-20 wt%.

Table 2. Chemical characteristics of blended cements

In addition, the cement bearing 20 wt% of granite sludge (80OPC+20AF) met the pozzolanicity

requirement for type IV/A cements with 11 wt%-35 wt% additions (see point 3.1).

3.3. Setting test

According to the rheological findings given in Table 3, the inclusion of 10 wt% or 20 wt% granite

sludge accelerated hydration, which translated into 30 % earlier initial and final setting times in

90OPC+10AF and 15 % earlier times in 80OPC+20AF than in the reference cement. That

reduction was attributable primarily to the initial filler effect induced by the sludge, which favoured

aluminate phase (C3A and C4AF) and alite (C3S) hydration (Frias et al., 2014). Cement particle

hydration was also accelerated by the alkaline oxides in the industrial waste, for Na+ and K+ are

known to expedite tricalcium aluminate (C3A) hydration (Li et al., 2016b, Jawed and Skalny, 1978,

Jiang et al., 1999).

Table 3. Blended and reference cement rheology and volume stability

The data in Table 3 also show that acceleration was not linearly related to the sludge replacement

ratio, inasmuch as the oxides present in the composition of the waste affect cement rheology in

opposite ways: Na2O and K2O (and others to a lesser extent) are accelerators and TiO2 a

retardant (Medina et al., 2013) . Despite the high Na2O and K2O content in the material, however,

only a small percentage was actually available to accelerate hydration. Under such

circumstances, acceleration could well be mitigated by the retardant (TiO2), particularly at the

earliest age (2 d) (Kakali et al., 1998).

Despite the acceleration induced by this type of pozzolans, the materials were EN 197-1-

compliant (European Committee for Standardization, 2011b) in terms of initial setting times for

strength class 42.5 MPa.

The pattern observed was consistent with findings reported by Elmoaty (Abd Elmoaty, 2013), who

manufactured concrete with 5 wt%-15 wt% granite dust.

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Table 3 also shows that the water demand for a normal Vicat test consistency of 342 mm rose

linearly with the replacement ratio (yWC = 0.35x+156; R2=1) relative to OPC, and more specifically

by 2.2 % in the 10 wt% additioned cement and 4.5 % in the 20 wt% material.

Water demand depends on the amount of water needed to fill the inter-particle space (free water)

and the water physically adsorbed onto inner and outer pore walls (Ferreiro et al., 2013). The

inclusion of granite sludge raised water demand because the rough borders (Medina et al., 2017)

of its particles called for more free water to fill the inter-particle space (Rajamma et al., 2015).

Sludge specific surface obviously had no effect on water demand in this case, given its similarity

with the value found for OPC.

The consistency values found for cement mortars with a water/cement ratio of 0.5 (see Table 3)

revealed that consistency in the cement with 10 wt% granite sludge was 7 % lower than in the

reference, and in the 20 wt% material, 8 % lower. Those findings were directly related to the

higher water demand in the new cement pastes discussed above. The same tendency was

observed by Ramos et al. (Ramos et al., 2013) in mortars designed with granite waste.

Lastly, a linear relationship between replacement ratio (x) and mortar consistency (y) was found

to fit the following equation: y = -0.76x+170.04. The correlation coefficient (R2) was 0.90.

3.4. Volume stability

The volume stability values (mean of three measurements with a precision of 0.5 mm) given in

Table 3 showed that this type of waste had no expansive effect on cement paste and that the new

blended cements (90OPC+10AF/ 80OPC+20AF) were EN 197-1-compliant (European

Committee for Standardization, 2011b) in this respect.

3.5. Mechanical behaviour

Further to Figure 4, all the cements studied exhibited 2 day compressive strengths of over 10 MPa

(42.5 N) or 20 MPa (42.5 R) and 28 day strengths greater than or equal to 42.5 MPa (42.5N/

42.5R). In other words, they met all the mechanical requirements set out in existing standard EN

197-1 (European Committee for Standardization, 2011b) for strength class 42.5 MPa cements.

Figure 4. Mortar compressive strength by age

The data in Figure 4 also show that including granite sludge in the cement did not alter the log

relationship between compressive strength and curing time, with a correlation coefficient (R2) of

over 0.90 irrespective of mortar typology.

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Granite waste induced a decline in strength, which steepened with rising replacement ratio: the

28 day material with 10 wt% waste exhibited 11.6 % lower strength and the cement with 20 wt%

sludge 23.7 % lower strength than OPC. That pattern of declining strength was consistent with

observations reported by Ramos et al. (Ramos et al., 2013) and Mármol et al. (Marmol et al.,

2010), who respectively observed strength loss of approximately 20 % for replacement ratios of

10 wt% in conventional mortars and 23 % for replacement ratios of 20 wt% in masonry mortars.

The flexural strength pattern shown inFigure 5 was reminiscent of the trend in compressive

strength, with 28 day values 10.1 % lower than the reference in the blends with a 10 wt% addition

and 17.4 % in the material with a replacement ratio of 20 wt%.

Figure 5. Mortar flexural strength

The contribution made by the addition to compressive strength (P) given in Table 4 was

determined using the methodology deployed by previous authors to assess the contribution of

recycled aggregate in concrete (Medina et al., 2012a). The symbol q denotes the percentage of

conventional cement (OPC), and Rb and Rr, the proportion of strength accounted for by OPC and

the granite sludge, respectively.

Further to the data in the table, the contribution (P) of granite sludge rose with age, whereby

365 day strength was just 4.3 % lower in the 10 wt% blended cement than in OPC and 12.57 %

lower in the material with the 20 wt% addition.

Table 4. Mortar compressive strength at 2, 7, 28, 90, 180 and 365 d

This narrowing of the difference in mechanical strength with time was closely related to the

pozzolanic activity of the granite waste, which induced a change in pore structure and portlandite

content in the new mortars (see Tables 5 and 6 and Figure 6).

3.6. Total porosity and pore size distribution

As Table 5 shows, total porosity was slightly greater in the new mortars: 9.2 % higher than OPC

in the 2 day cement bearing a 20 wt% addition and 8.6 % greater in the 365 day blended cement,

likewise with a 20 wt% replacement ratio.

Table 5. Two and 365 day mortars: total porosity and mean pore diameter

The mean pore diameter values also listed in Table 5 show that pore system refinement was

attendant upon cement hydration, with declines after 365 d of 30.5 %, 34.9 % and 37.1 % for

replacement ratios of 0 wt%, 10 wt% and 20 wt%, respectively. That greater refinement in mortars

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bearing granite waste was attributable primarily to the pozzolanicity of this new addition.

Refinement was visible as well in the shift to smaller diameters in the pore size distribution curves

plotted in Figure 6.

Figure 6. Two and 365 day mortars: pore size distribution

The 2 day mortars bearing granite waste had a higher volume of macropores (Φ > 0.05 µm) than

the conventional material (Figure 6), although the proportion declined at later ages. Such a

decline in the fraction of macropores went hand-in-hand with a rise in mesopore and capillary

pore volumes (0.05 < Φ < 0.002 µm), particularly in the mortars containing granite waste. This

behaviour was also intrinsically related to pozzolanic activity in later age granite sludge, which

contributed to the formation of the C-S-H gel that filled the pores in the later age mortars (Hewlett,

1998).

3.7. TGA and XRD characterisation

Further to the thermogravimetric findings for the 365 day mortars given in Table 6, total loss on

ignition (at 1000 C) was smaller in the mortars containing granite waste. The amount of C-S-H

gel forming in mortars can be associated with the amount of water bound to the gel, a parameter

obtained with TG as the total loss on ignition less the loss due to portlandite, ettringite and

carbonate decomposition (Gallucci et al., 2013). Ettringite decomposes in the 90 C-130 C

range (Knapen et al., 2009, Cassagnabère et al., 2009), whilst C-S-H gel begins to release water

at 110 C (Knapen et al., 2009). Moreover, as the loss attributable to ettringite is negligible, it may

be disregarded in the calculations to determine C-S-H gel formation, which can be simplified to

be the difference between total mass loss and the loss attributable to portlandite and carbonates.

The unreacted mineralogical phases present in granite waste, in turn, have no effect on mass

loss, for orthoclase, albite, biotite and hematite do not decompose between 25 C and 1000 C.

Kaolinite was likewise disregarded in the calculations, for no mass loss was observed on the DTG

curve at around 560 C, the temperature at which that mineral releases its chemically combined

water (see the example in Figure 7).

Figure 7. Differential thermal analysis (solid line), thermigravimetric analysis (dotted line) and

differential thermogravimetric analysis (dashes) for: a) 90OPC+10AF; b) 80OPC+20 AF and c)

OPC mortars

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Likewise pursuant to the data in Table 6, less C-S-H gel was observed in the mortars containing

the new addition than in OPC. More specifically, the 10 wt% blend exhibited 6.2 % less gel and

the 20 wt% material 12.3 % less. The explanation for those smaller C-S-H gel volumes lies in the

slow pozzolanic activity characterising this addition, due to which the pozzolanic reaction

(addition + Ca(OH)2 ⟶ C-S-H gel) would not suffice to offset the higher initial, gel-forming alite

and belite content in the unadditioned cement mortar. As the difference was smaller than the

10 wt% and 20 wt% cement replacement ratios, however, some C-S-H gel was obviously

generated by the pozzolanic reaction. These data are consistent with the loss of mechanical

strength and the change in pore size distribution observed in the additioned mortars.

Table 6. Portlandite and total mass loss in 365 day mortars

In addition, the total portlandite (Ca(OH)2) content was obtained from the thermogravimetric curve

as the sum of the mass loss due to portlandite decomposition at 400 C-480 ºC and the loss at

480 C-715 ºC, attributable to carbonate decomposition (regarding the latter to be the result of

portlandite carbonation after contact with atmospheric CO2). This value was observed to decline

as the percentage of the new addition rose: compared to the reference mortar, portlandite content

was 15.8 % lower in the material containing 10 wt% waste, and 24.0 % lower in the mortar made

with 20 wt% blended cement. The decline was greater than the cement replacement ratio, i.e.

greater than the decline in silicate concentration that determines portlandite formation as a

secondary product, further to the following reactions:

C3S (alite) + H2O  C-S-H gel + Ca(OH)2 and C2S (belite) + H2O  C-S-H gel + Ca(OH)2.

This greater portlandite consumption stands as proof of the (admittedly slight) pozzolanic activity

of this waste at later ages, reinforcing the findings in this respect in connection with C-S-H gel

formation, calculated as total loss less the loss attributable to portlandite and carbonates.

This effect on portlandite content was not observed by Elmoaty (Abd Elmoaty, 2013), who

reported no significant change in portlandite content in mortars containing 7.5 wt% or 15 wt% of

granite dust.

The XRD traces for the 365 day mortars reproduced in Figure 8 show that the main mineralogical

phases identified included: a) portlandite, calcite and ettringite, products of cement hydration; b)

muscovite, orthoclase and albite, present in the granite waste (Figure 1); and c) quartz, present

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in both the standardised sand used to prepare the mortars and in the addition. Due to the scantly

crystalline nature of C-S-H gels, they could not be identified with this technique.

Figure 8. XRD patterns for 365 day mortars

The figure also shows that the addition induced no mineralogical changes in the cement hydration

products. A qualitative review of the pattern revealed that the diffraction lines for portlandite were

less intense in the waste-bearing than in the reference mortar, a finding consistent with the

thermogravimetric results (Table 6).

3.8. Microstructure

The micrographs of the 365 day mortars in Figure 9 show that the partial replacement of cement

with granite sludge had no adverse effect on matrix uniformity. All the samples contained C-S-H

gel, portlandite, ettringite and sand. The new mortars (90OPC+10AF and 80OPC+20AF) were

also observed to contain small amounts of the unreacted addition due to the slow pozzolanic

reaction that characterises this sludge. The pozzolanic reaction mechanism favours the hydroxide

ion (OH-) attack, which breaks the Si-O and Al-O bonds in the granite sludge. It also prompts the

reaction between silicon and aluminium anions and calcium cations to form the C-S-H gels that

adsorb on to waste particle surfaces (AFI) (Hewlett, 1998).

Figure 9. SEM micrographs of 365 day mortars (x40 000): a) OPC; b) 90OPC+10AF;

c) 80OPC+20AF

Figure 10 depicts the calcium silicate hydrates (C-S-H gels) that form a strong, dense, compact,

continuous matrix. All these C-S-H gels exhibit a fibrous structure, forming a Diamond (Diamond,

1976) scale type I gel. This morphology was observed in mature OPC pastes by Fonseca and

Jennings (Fonseca and Jennings, 2010), who noted that gel morphology was impacted more by

drying conditions than by paste age.

Figure 10. SEM micrographs of C-S-H gel (x40 000): a) OPC; b) 90OPC+10AF;

c) 80OPC+20AF

The calcium-silicon (C/S) ratio for the C-S-H gels was 2.0 for the OPC reference mortar and 1.9

for the two granite sludge mortars (90OPC+10AF and 80OPC+20AF). That difference was not

found to be significant and both values were observed to lie within the normal range (1.2-2.3)

(Hewlett, 1998).

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The micrographs in Figure 11 illustrate typical portlandite (CH) and ettringite (Et) morphology, the

former characterised by an elongated, hexagonal crystal with well-defined edges and the latter

by needle-like crystals (Medina et al., 2012b).

Figure 11. SEM micrographs of hydration products: a) portlandite (x2000); b) ettringite (x20 000)

Respect to the ettringite was less abundant than the other hydration products (C-S-H gels and

CH) in all the mortars. The former was observed only locally and in small quantities, primarily

inside pores which, together with cracks, are the sites where conditions (pressure and the

presence of a number of necessary ions, Al(OH)4- in particular) favour its formation (Taylor et al.,

2001).

Lastly, the scanning electron microscope findings showed no morphological change in the

hydrated phases: the main differences observed were a minor decline in the C/S ratio in the gels

and the presence of small amounts of addition in the matrix.

4. Conclusions

A number of conclusions may be drawn from the findings discussed above.

- Inasmuch as they lie underneath the CaO solubility curve after 15 d, the new binders

containing 20 wt% granite waste can be classed as pozzolanic, type IV/A cements (11 %-

35 %).

- Cements containing 10 wt% or 20 wt% AF meet the chemical requirements (chloride  0.1

wt% and sulfate content  4.0wt%) laid down in European standard EN 197-1.

- Adding AF to cement pastes shortens initial setting times relative to the time observed for

OPC: by 28 % when the replacement ratio is 10 wt% and by 19 % when it is 20 wt%, although

the new cement pastes are EN 197-1-compliant with respect to initial setting time (> 60 min).

- The inclusion of AF raises water demand compared to OPC, although by less than 4.5 % at

20 wt% replacement.

- These new blended cements meet the volume stability requirements (< 10 mm) set out in

European standard EN 197-1.

- Strength is lower in sludge-containing than conventional mortar and declines with rising

replacement ratios. This difference in strength is partially offset by the pozzolanic reaction

typical of this addition, although given the slow kinetics involved, the effect is somewhat

retarded. Despite that decline in strength, the mortars designed in this study are compliant

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with the requirements laid down in European standard EN 197-1 for class 42.5 MPa cements

(> 10 MPa and > 42.5 MPa at 2 and 28 d, respectively).

- Total porosity and mean pore diameter decline more steeply between 2 and 365 d in the

mortars bearing the addition than in the conventional OPC material. Although low, pozzolanic

reactivity leads as well to a slightly lower portlandite content than in conventional mortars.

- The new addition (AF) induces no changes in hydration product (C-S-H gel, portlandite,

ettringite) morphology or any significant effect on the C/S ratio of the C-S-H gels formed.

The overall conclusion is that granite cutting waste can be used in the design of new low clinker-

content II/A and IV/A cements, a practice that would lower: raw material (limestone) extraction

and the risk to human health posed by small granite particles suspended in the air.

Acknowledgements

This study was funded by the Spanish Ministry of Science and Innovation under projects BIA

2013-48876-C3-1-R, BIA 2013-48876-C3-2-R and BIA2016-76643-C3-1-R, as well as by the

Government of Extremadura and the European Regional Development Fund (ERDF) under grant

GR 15064 awarded to the MATERIA research group.

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List of abbreviations

- SCM: supplementary cementitious materials

- NEE: non-energy extractive

- PEMAR: national waste management framework plan

- CEDEX: Centre for Public Works Studies and Experimentation

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- AF: granite sludge

- OPC: ordinary portland cement

- BET: Brunauer Emmett Teller

- XRF: X-ray fluorescence

- XRD: X-ray diffraction

- SEM: scanning electron microscopic

- DTA: differential thermal analysis

- DTG: differential thermogravimetric analysis

- TGA: thermogravimetric analysis

- EHE-08: Spanish structural concrete code

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Figure 1. Mineralogical composition of the materials

Figure 2. Pore size distribution for OPC and granite sludge

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Figure 3. Frattini diagram for assessing pozzolanicity

Figure 4. Mortar compressive strength by age

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Figure 5. Mortar flexural strength by age

Figure 6. Two and 365 day mortars: pore size distribution

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Figure 7. Differential thermal analysis (solid line), thermogravimetric analysis (dotted line) and

differential thermogravimetric analysis (dashes) for: a) 90OPC+10AF; b) 80OPC+20 AF and c)

OPC mortars

Figure 8. XRD patterns for 365 day mortars

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Figure 9. SEM micrographs of 365 day mortars (x3000): a) OPC; b) 90OPC+10AF;

c) 80OPC+20AF

Figure 10. SEM micrographs of C-S-H gel (x40 000): a) OPC; b) 90OPC+10AF;
c) 80OPC+20AF

Figure 11. SEM micrographs of hydration products: a) portlandite (x2000); and b)

ettringite (x20 000)
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Table 1. Chemical composition of the materials used

Oxide (wt%)
Material
SiO2 Al2O3 Fe2O3 MnO MgO CaO Na2O SO3 K 2O TiO2 P2O5 LOI Cl (ppm)
Granite sludge
69.60 14.99 2.52 0.04 1.60 2.36 3.59 0.00 4.04 0.51 0.17 0.52 284.00
(AF)
Cement (OPC) 20.26 4.61 2.44 0.03 3.35 59.37 0.84 4.14 1.41 0.14 0.22 3.04 135

Table 2. Chemical characteristics of blended cements

Chemical constituent (wt%)

Blended cement Pozzolanicity
SO3 Cl
Standard requirement for cement type II/A -
< 4.00 < 0.10
Standard requirement for cement type IV/A Positive (Frattini)
90OPC+10AF 3.73 0.01 -
80OPC+20AF 3.31 0.02 Positive (Frattini)

Table 3. Blended and reference cement rheology and volume stability

Standard requirement
Property OPC 90OPC+10AF 80OPC+20AF
(EN 197-1)
Setting time (min) Initial 210 150 170 > 60 min
(+ 10 min) Final 300 255 260 -
Water content (g) 156.00 159.50 163.00 -
Consistency (mm) 171.50 159.50 156.25 -
Volume stability (mm) 1 1 1 < 10 mm
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Table 4. Mortar compressive strength at 2, 7, 28, 90, 180 and 365 d

Age (days) Mortar q Rb Rr P

OPC 100 0.42 0.00 0.00
2 90OPC+10AF 90 0.41 -0.01 -2.60
80OPC+20AF 80 0.39 -0.03 -8.36
OPC 100 0.56 0.00 0.00
7 90OPC+10AF 90 0.54 -0.01 -2.28
80OPC+20AF 80 0.52 -0.03 -6.67
OPC 100 0.66 0.00 0.00
28 90OPC+10AF 90 0.65 -0.01 -1.76
80OPC+20AF 80 0.63 -0.03 -4.81
OPC 100 0.71 0.00 0.00
90 90OPC+10AF 90 0.71 0.00 -0.04
80OPC+20AF 80 0.70 -0.01 -1.86
OPC 100 0.74 0.00 0.00
180 90OPC+10AF 90 0.75 0.01 1.63
80OPC+20AF 80 0.75 0.01 1.08
OPC 100 0.75 0.00 0.00
365 90OPC+10AF 90 0.79 0.05 5.96
80OPC+20AF 80 0.82 0.07 8.50
Rb = fck/q / Rr = Rb – Rb(OPC) / P = 100*(Rr/Rb)

Table 5. Two and 365 d mortars: total porosity and mean pore diameter

Total porosity Mean pore diameter

Mortar
2d 365 d 2d 365 d
OPC 13.07 11.71 0.0948 0.0649
90OPC+10AF 14.79 12.14 0.0965 0.0628
80OPC+20AF 14.27 12.72 0.1043 0.0656

Table 6. Portlandite and total mass loss in 365 d mortars

Mix
Parameter
OPC 90OPC+10AF 80OPC+20AF
Pp = Weight loss due to Ca(OH)2 decomposition (wt%) 1.87 1.50 1.44
PC = Weight loss due to CaCO3 decomposition (wt%) 1.55 1.38 1.16
Pp+PC = Weight loss due to (Ca(OH)2+ CaCO3) decomposition
3.42 2.88 2.60
(wt%)
PT = Total weight loss at 1000 ºC (wt%) 9.00 8.11 7.49
PC-S-H gel = PT – (Pp+PC) = Weight loss due to the release of
5.58 5.23 4.99
bound water during C-S-H gel decomposition (wt%)