Volcano-related materials in concretes: a comprehensive ...

REVIEWARTICLE

Volcano-related materials in concretes: a comprehensive review

Gaochuang Cai1,2 & Takafumi Noguchi2 & Hervé Degée1 & Jun Zhao3 & Ryoma Kitagaki2

Received: 4 September 2015 /Accepted: 21 January 2016 /Published online: 11 February 2016# Springer-Verlag Berlin Heidelberg 2016

Abstract Massive volcano-related materials (VRMs) eruptedfrom volcanoes bring the impacts to natural environment andhumanity health worldwide, which include generally volcanicash (VA), volcanic pumice (VP), volcanic tuff (VT), etc.Considering the pozzolanic activities and mechanical charac-ters of these materials, civil engineers propose to use them inlow carbon/cement and environment-friendly concrete indus-tries as supplementary cementitious materials (SCMs) orartificial/natural aggregates. The utilization of VRMs in con-cretes has attracted increasing and pressing attentions fromresearch community. Through a literature review, this paper

presents comprehensively the properties of VRMs and VRMconcretes (VRMCs), including the physical and chemicalproperties of raw VRMs and VRMCs, and the fresh, micro-structural and mechanical properties of VRMCs. Besides,considering environmental impacts and the development oflong-term properties, the durability and stability propertiesof VRMCs also are summarized in this paper. The formerfocuses on the resistance properties of VRMCs when subject-ed to aggressive environmental impacts such as chloride, sul-fate, seawater, and freezing–thawing. The latter mainly in-cludes the fatigue, creep, heat-insulating, and expansion prop-erties of VRMCs. This study will be helpful to promote thesustainability in concrete industries, protect natural environ-ment, and reduce the impacts of volcano disaster. Based onthis review, some main conclusions are discussed and impor-tant recommendations regarding future research on the appli-cation of VRMs in concrete industries are provided.

Keywords Sustainability . Hydration .Microstructures .

Fresh properties .Mechanical properties . Materials .

Durability . Stability

Introduction

Volcano disaster and VRMs

Volcano is a kind of earth crust rupture which is generallyfound where tectonic plates re diverging or converging.Typically, volcano-related materials (VRMs) can be obtainedmainly in three ways: explosive volcanic eruptions (Wilsonand Stewart 2012), phreatomagmatic eruptions (Zimanowski2000), as well as the transports in pyroclastic density currents(Parfitt and Wilson 2008). In addition, the physical propertiesand chemical components of VRMs depend mainly on the

Responsible editor: Philippe Garrigues

Research highlights1. Comparing with existing review papers regarding volcanic ash inconcrete, this paper comprehensively reviews the basic, mechanical,durability, and stability properties of VRMs and VRMCs, not onlyvolcanic ash concrete.2. This paper presents a research summary of VRMs/VRMCs throughcollecting and reviewing massive literatures reported mainly by Englishand Japanese.3. This study is very helpful to reduce the impacts of volcano and manageof the reestablishment post-disaster.4. Some recommendations regarding VRMs in concrete industries areprovided.

* Gaochuang [email protected]

1 CERG, Faculty of Engineering Technology, Hasselt University,H-B106, Campus Diepenbeek, Agoralaan Gebouw H,B-3590 Diepenbeek, Belgium

2 Department of Architecture, Graduate School of Engineering, TheUniversity of Tokyo, Tokyo, Japan

3 School of Mechanics and Engineering Science, ZhengzhouUniversity, Zhengzhou, China

Environ Sci Pollut Res (2016) 23:7220–7243DOI 10.1007/s11356-016-6161-z

http://orcid.org/0000-0003-2847-0699

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eruption style of volcanoes. When fragmentations occur un-derground, magma is teared into some debris through violent-ly expanding bubbles which subsequently are ejected out andcarried to the atmosphere, forming further ash particles orlarge-scale ash falls. Among of these materials, VA causedby explosive volcanic eruptions is the most drastic and exten-sive product/particle. Figure 1 shows the disaster and impactsof volcano eruption, including the formation of magma, VAs,VPs, VTs, and main secondary disasters (acid rain, ash fall),the transportation and accumulation of VRMs and maindamages.

As shown in this figure, the damages caused by VRMs canbe summarized compactly as, damage human life and proper-ties (US Geological survey 2010), interrupt power supplies,make a destruction/interruption to communication systems(e.g., radio, TV, and telephone), pollute water supply systems,and damage effluent treatment systems (especially, waterpump) (Stewart et al. 2006), as well as disrupt of transporta-tion systems (Wilson et al. 2012). Because 9 % of world pop-ulation is estimated to be living within 100 km of a historicallyactive volcano regions, how to reduce the impacts of VRMsand manage them postdisaster are very significant (Horwelland Baxter 2006; Wardman et al. 2012).

Abundant VRMs can be obtained from volcanoes world-wide, especially from the active ones. As presented in Fig. 2,most active volcanoes in the world are located mainly in theconnecting regions between two or more plates, i.e., tectonicplate boundaries, specifically destructive and constructiveboundaries. The figure shows these regions including mainlythe following: Pacific edge, center Atlantic Ocean, SouthernEurope, and the east coast of Africa. These volcanoes aregenerally caused by the hotspots underground under the aboveregions. Besides, the east coast of Africa is not a plate bound-ary; however, this region is a plate ripping itself (African

Plate) in half to create a rift valley lined by volcanoes. Atthe same time, as illustrated in Fig. 2, earthquakes usuallyhappen together with volcano at the above tectonic plateboundaries such as Japan.

Significance of utilization of VRMs

Historically, as the oldest cementitious materials, VRMs wereused in combination with lime for construction purposes inancient Rome, such as the famous Colosseum, which present-ed high strength and durability, even according to currentstandards. In modern construction technology, some naturalpozzolans are also used in various concrete structures. Manyprevious studies (e.g., Osawa 1950; Togo 2003; Khan andSiddique 2011; Parande et al. 2008; Bakharev et al. 2001;Lothenbach et al. 2011; Wang and Baxter 2007; Nazari et al.2010; Naik and Moriconi 2006; Meloso et al. 2009; Kasai1999; Naik 2005; Peris 2007) have found that VRMs can beapplied in concretes and reinforced concrete (RC) structures inplace of part cement or aggregates, which mainly can be at-tributed to their potential hydraulicity (Osawa 1950; Togo2003), economical efficiency (Ueda et al. 2005), and environ-mental friendliness (Iyer and Scott 2001). However, accordingto these studies, the upper limit of these materials in concreteis limited, for example, VA has generally been proposed to beunder 30–40 % (e.g., Ueda et al. 2005; Nagai and Yoshida1934), and the concretes containing VRMs usually exhibitedrelative inferior properties, especially at early stages.

On the other hand, it was well known that a ton of carbondioxide (CO2) will be released into the atmosphere when 1 t ofportland cement (PC) was produced in factory (e.g., Bilodeauand Malhotra 2000), which indicates that the CO2 emissioncontribution of PC production is approximately 5–7 % ofglobal CO2 anthropogenic emission (Meyer 2009;

Where,AA: Human and other life;BB: Buildings and infrastructure;CC: Water supply and waste system; EE: Power system;DD: Transporta�on system; FF: Communica�on system

A: Ash, HCl,H2O, CO2, SO2

D: VA II (small weight), CO2

Lake

Acid rain Ash fallsWind

FF

AA

BB

CC

DDEE

VA I(Middle weight)

VP, VT etc.

MagmaBB Road

Deposi�ons

Main damages

Ash falls

Fig. 1 Volcano eruption and itsdisasters and impacts

Environ Sci Pollut Res (2016) 23:7220–7243 7221

Huntzinger and Eatmon 2009). The impact and pollutioncaused by the massive use of PC in concrete industries will bemore terrible as increasing constructions worldwide. At thesame time, the destruction of earth surface caused by the over-exploitation of natural aggregates implies that the high-volumeutilization of VRMs in concretes is very significant to the earth.Therefore, summarily, the use of VRMs in concretes can reduceeffectively CO2 emissions, improve greenhouse effect, protectnatural environment, as well as propel the developments oflow-carbon society and carbon-neutral building. Besides, theuse of VRMs in concretes can also effectively reduce secondarydisasters caused by volcanoes and guide the reestablishment ofpostdisaster, because free VA and ash fall are harmful to humanand other lives. In addition, because it can encourage adequate-ly and fast ash collection conducted by public or companies, theextensive use of VRMs in concretes is also very significant tothe living and environment post-disaster.

Objectives of this paper

To comprehensively and clearly understand the potential ap-plication of VRMs in civil engineering, this paper tries topresent the properties of VRMs in concretes in more detailed,on the basis of the investigations of previous literature. Thediscussed properties primarily include the physical and chem-ical properties of VRMs or VRMCs, and the durability andstability of VRMCs. Firstly, the main physical and chemicalproperties of raw VRMs or VRMCs are summarized compre-hensively. Subsequently, the fresh properties, microstructural,mechanical, and durability properties of concretes usingVRMs are reviewed and discussed. Further, to investigatethe stability of VRMs in concrete, a short review focusing

on alkali aggregate reactions, heat-insulating property, thermalexpansion performance, and crack resistance of VRMCs isprovided. Besides, regarding the use of VRMs in asphalt con-cretes, the stripping and creep resistance of this concrete willalso be presented in this paper, synoptically. Based on thisresearch, the authors provide some recommendations to guidethe use of VRMs in concrete industries.

Physical and chemical properties of VRMs/VRMCs

Physical properties

Particle size

Based on previous investigations (e.g., Hiroyuki and Koji1981), the output of the eruption of volcano mainly consistsof lava and pyroclastic materials, including volcanic rockmass (d i ame t e r (D ) ≥ 64 mm) , vo l can i c g r ave l(2 mm≤D≤64 mm), and volcanic ash (D≤2 mm), as shownin Table 1. The studies conducted by Wilson and Stewart(2012) and Tomoshisa (1990) presented a similar result. Asshown in Fig. 1, large-size rock fragments usually fall back tothe ground or are pushed out from volcano, and progressivelysmaller and lighter fragments or tuff or pumice are blownfarther from the volcano by wind or heat flow. VA, with thesmallest diameter in VRMs, usually can spread about 50–600 km depending on wind speed and the height/eruptionvolume of volcano. Table 1 lists the moving distance variationof various VRM particles from Mount St. Helens. As shownin this table, small particles can be moved to a location farfrom the eruption point of the volcano and the smallest-size

Fig. 2 Distribution of activevolcano in the world(Greenfield geography Website,http://greenfieldgeography.wikispaces.com)

7222 Environ Sci Pollut Res (2016) 23:7220–7243

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volcanic ashes have been moved to about 600 km away fromeruption point.

Density of VRMs and VACs

The density of individual volcanic particles may vary; forexample, some researchers reported that the ones of pumicesare 700–1200 kg/m3, glass shards are 2350–2450 kg/m3, andcrystals are 2700–3300 kg/m3, and lithic particles vary be-tween 2600 and 3200 kg/m3 (Shipley and Sarna-Wojcicki1982; Siddique 2012), as shown in Table 2 and Fig. 3. Thereport of USGeological Survey shows that water content has asignificant influence on the density of VA itself. In addition,when VRMs are used in concrete, the density of VA concretes(VACs) decreases with VA content (Olawuyi and Olusola2010) and with the increase of VP aggregates (VPAs) as well(Hossain et al. 2011). This was attributed to a lighter finelyground pumice/pumice aggregate when using VPAs to replacegravel ones. For example, when Type D cement and 100 %VPA are applied in concrete, the maximum decrease ratio ofthe density of concrete reaches 42 % comparing with controlconcrete (Hossain et al. 2011).

Particle compositions of VRMs

As shown in Table 2, VRMs typically consisted of lots of tinyparticles composed of varying proportions of volcanic glass(VG), minerals, crystals, pyroxene, and lithics. Volcanic ashmainly consisted of 70–80 % of volcanic glass, 15–20 % offeldspar, about 5 % of pyroxene, and little magnetite and

amorphous clays (Kawano and Tomita 2001). Regarding volca-nic glass, Kawano and Tomita (2001) reported that a diffuse halowith no lattice fringes has been observed in the leached layers ofVG, suggesting a noncrystalline structure, as shown in Fig. 4a.The EDX investigations of the volcanic glass matrix show anobvious Si and Al peak characteristics, and weak Fe, Ca, Na,and K peaks in VGs, as seen in Fig. 4b. On the other hand, aspresented in Fig. 4c, in the leached layer of VG, richer Al and Feand less Si have been confirmed based on a EDX spectrumanalysis, when comparing with that of original VG.

Specific surface area/specific gravity

Specific surface area represents the total surface area of a perunit mass material, which has a significant influence on theadsorption behavior and reaction capacity of materials. Thespecific surface areas of VRMs from different volcanoesusually are various. Delmelle et al. (2005) investigated andcompared the specific surface areas of six VA samples, respec-tively comes from Mexico (EC), Iceland (HE), the USA(MSH), Philippines (PIN), Nicaragua (SC), and Montserrat(SH), as shown in Table 3. The main findings from their re-sults can be drawn as follows:

1. All VA samples have a similar specific surface area ofabout 1–2 m2/g.

2. The presence of clay minerals in VAs may develops alarger specific surface area for this material.

On the other hand, the findings from Horwell et al. (2003)also showed that the special surface areas of the volcanic ashfrom Soufrire Hills varied from 2.8 to 7.5 (m2/g), the largerone of which was found in the mixed leached and weatheredVA samples. However, Ogunbode and Olawuyi (2008) andHassan (2006) reported that the specific gravity of VA is about3.04–3.05, which generally larger than the ones of sand, lat-erite, and ganite, and less than that of portland cement (about3.15) as provided by most researchers (e.g., Neville 2006).Besides, some sandy VAs may have low specific gravity,

Table 1 VRMs’ particles andtransmission characteristic Types Diameter region (μm) Transmission characteristic (Johnston 1997)

VRMs’ diameter (μm) Location from volcano (km)

Volcanic ash 0–2 0.034

0.038

0.047

0.063

0.100

621

414

235

150

54

Volcanic gravel 2–64 4.000 0

Volcanic rock mass 64– – –

Source: Hiroyuki and Koji (1981), Tomoshisa (1990), Johnston (1997), and Siddique (2012)

Table 2 Densities of various volcanic materials

Name Density (kg/m3) Status of VA bulk Region (kg/cm3)

Pumice 700–1200 Dry bulk density 500–1500Glass shards 2350–2450

Srystals 2700–3300 Wet bulk density 1000–2000Lithic particles 2600–3200

Source: Siddique (2012) and US Geological Survey


although they may have higher pozzolanic activity thanothers. For example, some studies presented that the specificgravities of sandy VAs are less than 2.7 and ranged from 2.51to 2.68 (Horiuchi et al. 1992; Demirdag et al. 2008), which aresimilar to sand, laterite, and ganite reported by Ogunbode andOlawuyi (2008).

Fineness

Generally, the Blaine fineness of VA mainly depends on theplace of production and ranges from 240 to 285 m2/kg(Hossain and Lachemi 2004b; Hossain 2003; Takemoto andUchikawa 1980) and is less than the values of other pozzola-nic materials of 295±3 m2/kg (Turanli et al. 2004). This hasbeen considered as one of the main reasons related to theunsatisfactory of the early strength of VRMCs. However, theabove Blaine fineness levels still can meet the requirements ofASTM C618 (2001) regards to use of class F FA in concretes.The general Blaine fineness of portland cement is about 300±5 m2/g and a Blaine fineness of 470±15 m2/g can be ob-tained when this cement blended using intergrinding materials

(Turanli et al. 2004). On the other hand, some measures havebeen proposed to improve VRMs’ fineness, such as by grind-ing VRMs to get a finer particle size (Hossain 2003), oradjusting the percentage of sandy VA fractions.

Chemical properties

According to previous studies, some supplementary cementi-tious materials (SCMs) (e.g., silica fume (SF), Metakaoline(MK) slag) have a very important influence on the microstruc-ture of concrete such as pore structure and solution (Shi 2004),which subsequently influence the strength and durability ofconcrete. However, fly ashes (FA) and ground VAs are muchless reactive than silica fume, etc. Therefore, the studies of thechemical properties of VRMs and how to activate them inconcretes are significant to propel its utilization in the future.

Chemical and mineral composition

Based on investigations reported by many researchers, VAprincipally consisted of silica (about 40–60 %) and aluminum

Fig. 3 Scanning electronmicroscope images of volcanicashes

Fig. 4 TEM of VG (a), EDXspectra of matrix of VG matrix(b), and leached layer (c)(Kawano and Tomita 2001)


trioxide (about 15–20%) (e.g., Stewart et al. 2006; Tomoshisa1990; Kawano and Tomita 2001; Hossain and Lachemi2004a, b, 2006a, b; Fukushima and Mastumoto 1942;Tchakoute et al. 2013; Rafiza et al. 2013; Olawuyi et al.2012; Chen and Wang 2009), while the main components ofportland cement are calcium oxide (maximum 70 %) and sil-ica (about 20 %) (Stewart et al. 2006; Tomoshisa 1990), asshown in Tables 4 and 5. VA also may include other compo-sitions like calcium oxide, sodium oxide, and iron oxide, sug-gesting that it can be used as pozzolanic materials in concretesaccording to ASTM C618 (2001). Table 5 shows a

comparison between the chemical composition/physical pa-rameters of VA and other usually used SCMs. Their differ-ences mainly focused on the proportions of SiO2, Al2O3, andCaO. On the other hand, Fig. 5 presents the fact that theobtaining way of VAs makes the materials have different com-positions (Baxter et al. 1999). For example, from this figure,cristobalite, tridymite, and minor quartz are considered as theonly phases and sample A contains relatively more tridymiteand less quartz than sample B.

Absorbing capacity and rate of lime of VA

Lime absorbed in VRMs has a short-stage influence onthe activity of VAs at early stages, which can be explainedby high specific surface area of this material. In otherwords, the reactivity of VAs involves mainly the capacityand rate of lime absorption. Previous studies (e.g.,Turriziani and Corradini 1959; Sersale and Orsini 1969;Costa and Massazza 1974; Massazza and Costa 1977;Barnes and Bensted 2002) found that the main reactionproductions between VA and lime have C-S-H, 4CaO·Al2O3·13H2O and C2ASH8, and their reaction capacityand rate depends significantly on the content of activeSiO2 and Al2O3, especially the former as shown inFig. 6 (Costa and Massazza 1974). Besides, some grind-ing crystalline minerals also can enhance the capacity oflime absorption of VA, due to their large specific surfacearea, e.g., feldspar (Ludwig and Schwiete 1962).Summarily, the contents of SiO2 and Al2O3 in VRMs(Barnes and Bensted 2002), specific surface area, water/binder ratio (Massazza and Costa 1977), and curing

Table 3 Experimental results of VAs as derived from nitrogen andwater vapor adsorption isotherms

EC HE MSH PIN SC SH

Nitrogen

Vm (cm3/g) 0.35 0.26 0.37 0.48 2.2 0.47

C 62 50 69 43 112 94

as (m2/g) 1.5 1.1 1.6 2.1 9.7 2.0

Vp, 0.95 (mm3/g) 4.4 3.3 4.1 4.9 19.0 4.7

Water vapor

Vm (cm3/g) 1.29 1.31 2.1 1.86 4.93 1.38

C 43 72 20 20 35 31

asσ = 10.6 (m2/g) 3.7 3.7 6.0 5.3 14.0 3.9

asσ = 14.8 (m2/g) 5.1 5.2 8.3 7.4 19.6 5.5

Vp, 0.95 (mm3/g) 13.0 14.0 10.9 5.5 20.6 8.7

Source: Delmelle et al. (2005)

as specific surface area, C BET constant, Vm volume necessary to coverthe surface of the ash with a complete monolayer of gas molecules, Vp

geometric pore volume

Table 4 Comparison between various volcanic ashes from different sources

Countries Papua NewGuinea

Turkey Japan Japan USA French Greece Italy Germany USA Japan Max. Min.

Type or name Basalt Rhyolite Auvergne Santorin soil Bacoli Tuff Kieselguhr Carclazyte

Silica SiO2 59.30 61.48 60.40 47.10 65.74 46.60 67.98 53.08 52.12 85.97 87.57 87.6 46.6

Alumina Al2O3 17.50 18.20 15.60 18.60 15.89 17.60 19.61 18.20 18.29 2.3 2.44 19.6 2.3

Iron oxide Fe2O3 7.00 3.78 7.31 6.60 2.54 11.80 4.34 4.29 4.5 1.84 0.41 11.8 0.4

Calcium oxide CaO 6.10 4.62 6.32 12.20 3.35 9.84 1.25 9.05 1.5 9 0.19 12.2 0.2

Magnesia MgO 2.60 2.92 3.13 5.30 1.23 5.58 – 1.23 1 0.61 0.23 5.6 0.2

Sodium oxide Na2O 3.80 3.90 4.82 – 4.97 3.14 – 3.88 6.5 0.21 0.11 6.5 0.1

Sulfur trioxide SO3 0.70 0.10 – – – 0.02 0.65 – 0.7 0.0

Loss on ignition 1.00 2.70 0.07 – 3.43 0.24 – – 11.1 4.09 11.1 0.1

Total SiO2 +Al2O3 76.8 79.7 76.0 65.7 81.6 64.2 87.6 71.3 70.4 88.3 90.0 90.0 64.2

Insoluble residue – 92.20 – –

Blain Fineness (m2/kg) 285.0 – – –

Bulk density (kg/m3) 2450 – – 1394

Specific gravity – – 2.63 3.04

Reference (Hossain 2003, 2005a; Turanli et al. 2004; Fukushima andMastumoto 1942; Mielenz et al. 1950; Forest and Demoulian 1963; Battaglinoand Schippa 1968)


temperature (Takemoto and Uchikawa 1980) have signif-icant influences on the rate of absorbing lime of VAs.

Water demands of paste and concrete containing VRMs

In portland cement system, the values of water-to-cement ratiofor obtaining a normal consistency of concrete are similaralmost. However, the microporous and angular structure ofmaterial itself has resulted in that most added naturalpozzolanic materials usually increase the water demand ofconcrete mixes to obtain a similar consistency as PC. Turanliet al. (2004) presented that for getting a normal consistency,the water/binder (W/B) ratios of VA-PC system vary from0.29 to 0.36, while the ratios range from 0.22 to 0.24 inportland system corresponding to same consistencyrequirements.

On the other hand, Kaku and Hori (1989) showed the unitwater demand of concrete should be controlled more than

260 kg/m if VA was used to replace 30–50 % of fine aggre-gates in concrete without any admixtures, when a workableslump is expected. They also reported that concrete needsmore water when VA has a higher ratio of large/small aggre-gates, in order to reach the same required slump level.

Hydration products

When VA partly replaces PC in concrete, though the mainhydration products of the system are similar to the ones inPC concrete, they have different percentage distribution,which mainly focusing on the volume of C-S-H andCa(OH)2. These main products have ettringite (E),tobermorite (T), tetracalcium aluminate hydrate (TAH),Ca(OH)2, and dissociative CaO (Barnes and Bensted 2002).Generally, TAH can be reacted with carbon dioxide andCa(OH)2 to transfer into calcite. Besides, Sestini andSantarelli (1936) indicated that in a VA-PC system, addedVAwill absorbmore lime to change the volume of dissociativeCaO in concrete.

Hydration heat in VRMs-PC system

Hydration heat is one of the significant evaluation factors ofcement when concrete is cured (ACI225 1985) and usuallyinfluences the durability of concrete at later stages, especiallyfor concretes constructed in summer and mass concrete. Indifferent cement hydration systems, hydration heat and itsevolution rate are different as curing time. On the basis ofprevious investigations of VRMCs, one of the main reasonswhy VA has been successfully used in concrete/cement indus-tries is VA reduces effectively the level of hydration heat, notonly its total heat level, but also releasing rate (Barnes andBensted 2002; Hossain 2003). Research (Massazza and

Table 5 Comparison of oxidecomposition of cementitousmaterials

CMs PC type I FA ASTM (class F) VC SF MK SL

Silica SiO2 17–25 – 59.30 92.10 53.20 35.04

Alumina Al2O3 3–8 – 17.50 0.50 43.90 13.91

iron oxide Fe2O3 0.5–6.0 – 7.00 1.40 0.38 0.29

Calcium oxide CaO 60-67 – 6.10 0.50 0.02 39.43

Magnesia MgO 0.1–4.0 ≤5 2.60 0.30 0.05 6.13

Sodium oxide Na2O 0.3–1.3 – 3.80 0.30 0.17 0.34

Potassium oxide K2O 0.5–1.3 – 2.25 0.70 0.10 0.39

Sufur trioxide SO3 1–3 ≤5 0.70 2.43

Loss on ignition 1.22 ≤6 1.00 2.80 0.51 1.45

SiO2 +Al2O3 + Fe2O3 20.5-39 ≥70 83.80 94.00 97.48 49.24

Blain Fineness (m2/kg) 320.0 – 285.0 – – 460.00

Bulk density (kg/m3) 3150 – 2450 – – –

Specific gravity 3.5 – 3.04 2.22 2.62 –

Source: Hossain (2004a, b), Khan and Siddique (2011), Parande et al. (2008), Bakharev et al. (2001)

PC Portland cement, FA fly ash, VA volcanic ash, SF silica fume, SL slag, MK metakaolin

Cristobalite (C)

Tridymite (T)

Quartz (Q)

Fig. 5 Powder XRD patterns of the residues from the talvitie analysis ofVA from different ways: a collapse generated pyroclastic flows and bvulcanian explosions (Baxter et al. 1999).


Costa 1979) also shown that when VA replaced 50 % of ce-ment in concrete, the hydration heats of the systems decreased25, 32, and 33 % at the 7th, 28th, and 90th day, respectively,when compared with corresponding control concrete. It indi-cates the curing time of concrete affects the development ofhydration heat of VA-PC system, as shown in Fig. 7. Besides,the type of SCMs influences the releasing rate of the hydrationheat of concrete and the heat releasing peaks of the systemswere observed at curing time of 7–15 h, as shown in Fig. 8(Takemoto and Uchikawa 1980).

Microstructural characteristics of hardened VA-cement paste

The microstructure characteristics of hardened cement paste/concrete determine the development of strength and durabilityof concrete, such as pore structure. Research (Barnes and

Bensted 2002) indicates that there are three main characteris-tics in hardened VA cement pastes:

1. Less crystalline product such as Ca(OH)2, which affectsthe strength of concrete.

2. Obvious package layer of unreacted VA, which presentsthe low reactivity of VAs.

3. A similar basic paste body as the one of PC system can befound, which can meet basic strength requirement. Thisphenomenon is more obvious when the volume of VAincreases.

In the aspects of porosity and pore diameter distribution,there are no obvious differences between the PC system withand without VRMs, except for that VC-cement system hasmore small-diameter pores and higher porosity (e.g.,Takemoto and Uchikawa 1980; Massazza 1993), especiallyat initial stages, and the porosity of concrete will be improvedwith the further hydration in the system.

pH value of the pore solution of VRMCs

pH is a critical factor of the chemistry of concrete, whose inPC concrete approaches 11, which meaning PC concrete is

Pozz.n.1 2 3 4 5 6Hydra�on under shaking;Sta�c hydra�on;

20 40 60 80 100

S.S. m2/g0

1

0

20

3

0

40

50

60

90days

180days

60days

g Ca

(OH)

2/10

0g P

ozzo

lana

70

0

10

2

0

30

40

50

6

0

70

8

0

0 10 20 30 40 50 60 70 80 90

Com

bine

d lim

e (%

)

Al2O3+SiO2 (%)

a bFig. 6 Combined lime versusspecific surface (S.S.) area (a) andvolume of active SiO2 +Al2O3

(b) (Costa and Massazza 1974)

Fig. 7 Hydration heat versus pozzolana content in concrete (Takemotoand Uchikawa 1980)

Fig. 8 Evolution rates of hydration heat of PC systems using differentnatural pozzolanas (V/G/F/M/R-PC) and one fly ash (T-PC) (Takemotoand Uchikawa 1980)


very alkaline. The protection of steel bar in concrete is benefit-ed by the high PH environment of concrete or pore solution.The addition of VAwill affect the PH value of the internal poresolution of PC concretes. The alkali content of VA and origi-nal PC (Barnes and Bensted 2002) or Ca+ concentration(Larbi et al. 1990) will determine the affecting degree of VAin PC system. For instance, Glasser and Marr (1984) pointedout that the pH value of VA-PC concrete increased comparingwith the one of PC system when ordinary PC containing mod-erate alkali, as shown in Table 6. On the other hand, based onthe research (Barnes and Bensted 2002), the pH levels of poresolution reduced 0.1 degree when VA replaced 30 % of ce-ment in concrete, because of the decease of the alkali concen-tration of productions (OH−). The influence can be attributedto the chemical similarity of VA as ganister sand, which hassolid-hydration products that will absorb alkali from pore so-lutions (Page and Vennesland 1983).

Utilization of VRMs in concretes

Aggregates in concrete

As described in several studies (e.g., Demirdag et al. 2008;Rafiza et al. 2013; Hosokawa 2014; Kuroiwa 1976; Demirdagand Dunduz 2008), VRMs can be used in concrete asfine/coarse aggregates or artificial geopolymer aggregates, asshown in Fig. 9. Hosokawa (2014) also considered that thefineness of some natural VAs can directly satisfy the

requirement of fine aggregates in Japanese code. The utiliza-tion of VA in concretes protects environment and reduceseffectively construction costs, especially in the places wherenatural fine aggregate can’t be obtained easily. Besides, thestudies (Naji and Asi 2008; Rafiza et al. 2013) have provenexperimentally that the replacement of aggregates by granularvolcanic ash is technically feasible, even using 100 % VAartificial aggregates (Hossain 2004a), which can make con-crete to obtain an approximately 50–60 % of the compressivestrength of control concrete. In addition, using volcanic pum-ice aggregates (VPAs), a structural lightweight concrete canbe made meeting the requirements of ASTM C330 (2014).

Pavement concrete and lightweight concrete

Asphalt concrete (AC) Naji and Asi (2008) showed that it istechnically feasible using granular volcanic ash aggregates toreplace partly conventional aggregates in asphalt concrete.Based on their research, if the replacement ratio of VA aggregatein concrete is controlled less than 10 %, the asphalt concrete canexhibit well creep resistance, resilient modulus, and fatigue be-haviors. These are very significant to pavement concrete.

Lightweight concrete (LWC) The large self-weight of con-crete is a nonignorable problem of RC structures, especially inhigh-rise buildings. Massive studies worldwide have proved theadvantages of LWC, such as reducing the self-weight concretemembers by 30–50 % (Demirdag and Gunduz 2008), obtaininga satisfactory workability, better shrinkage resistance, higher

Table 6 pH values of various SCMs-PC systems (w/c = 0.6, curing time/temperature = 90 days/18 °C)

PC characteristic Alkalinity Cements

PC 15 % SF+ 85 % PC 15 % SL+85 % PC 15 % VC+85 % PC

Ordinary PC system pH 13.43 – 13.54 13.61

Na2Oeq 0.50 – 0.54 0.78

High alkalis PC system pH 13.77 13.48 13.68 13.77

Na2Oeq 0.95 0.94 0.93 1.16

Source: Glasser and Marr (1984) and Barnes and Bensted (2002)

PC portland cement, FA fly ash, VA volcanic ash, SF silica fume, SL slag, MK metakaolin

Fig. 9 VRMs as fine and coarseaggregates in concrete (Demirdaget al. 2008; Demirdag andGunduz 2008; Rafiza et al. 2013)


tensile strength (Hossain 2004a), etc. Researchers (Hossain2004a; Hossain and Lachemi 2007a; Demirdag and Gunduz2008) implied that acceptable LWCs can be made by usingmoderately VAs or VPs as cement replacement material orcoarse aggregate in lightweight concrete.

Building/concrete products

Masonry blocks According to the research findings fromDemirdag et al. (2008), VA aggregates can be used to makeLWCmasonry blocks, which can have a compressive strengthof about 2.8MPa when by utilizing 60% fine and 40% coarseVA aggregates, which can meet the requirements of LWCaccording to BS EN 771–3 (2004).

Prepacked LWC products Using VA and some foaming,thickener and dispersing agents, prepacked LWC productscan be made which having lower drying shrinkage rates thanplain concrete (Kuroiwa 1976).

ALC building materials Because VA particles can reactwith lime and show certain expansion performance ofpresent gelatinization under 100 °C (Kuroiwa 1976), theycan be applied to create some light weight building mate-rials. With this view and using autoclave curing method,autoclaved lightweight aerated concrete (ALC) buildingmaterials can be manufactured.

Ocean/port engineering

In Japan, OTARU port (Hokkaido, Japan) (see Fig. 10) built in1897 usually has been referred as a famous example of utili-zation of VA in concrete, which used VA to replace 80 % ofcement and had a rough water/cement ratio of 0.38–0.44(Yamashita and Fukute 1992). The use of the method can beattributed to that some practical structures had verified theeffectiveness of VA in concretes subjected to seawater attacks,as presented in the table in Fig. 10 (Yamashita and Fukute1992). In addition, in 1987, a high durability concrete hadbeen reported in Japan after subjected to 60 years of seawaterattacks, which was made using VA as an admixture and

containing a blast furnace slag cement as cementitious mate-rials (slag≥70 %) (Kazuto et al. 1990).

Environment-friendly concrete

Generally, as one production of important human activities,concrete should be an environmental-friendly and durable ma-terial. However, many concrete structures may begin to deteri-orate after 20 to 30 years or much less, even though they weredesigned with a service life of 50 years (Mehta 1997). Usingby-products such as VRMs, to develop cheaper andenvironmental-friendly VRMCs with acceptable strengths anddurability characteristics will be helpful to the sustainability inconcrete and the rehabilitation in volcanic disaster regions (e.g.,Hossain 2003, 2004a; Naik et al. 2003; Hossain and Lachemi2007a). In additional, VAC can find its place as a soil stabiliza-tion material to prevent soil erosion (Rifa’i et al. 2013).

Main basic properties of VRMCs

Fresh properties

Workability

As one of the main physical parameters of fresh concrete, theworkability of concrete influences the development of thestrength and durability of concrete. Usually, the factors affect-ing concrete workability include W/B ratio, cement content,aggregate properties, curing temperature, etc. According toprevious reports (Hossain 2003, 2006), when added VA wascontrolled under 40% of cement in concrete, the slump valuesof VRMCs generally increase with VA content. TheseVRMCs have been found to present a satisfactory workabilitywith no segregation and excessive bleeding. Besides, inVRMC system, the change from ASTM type I to type Vseems to have no influence on the fresh properties of concretemixture, reported by Hossain and Lachemi (2006a).

On the other hand, in self-compacting concrete (SCC) sys-tems, in order to satisfactory fresh properties and obtain goodworkability, W/B ratio and VA content should be optimized

Concrete block using VA

Otaru Sasebo* Aomori Funagawa Yokkashi Murotsu

Cement 1 1 1 1 0.65 0.7

VA 0.8 0.38 0.6 0.6 0.35 0.3

Sand 3.2 ― 4 3.2 2 3

Gravel 6.4 ― 8 8 5 6

Mix

(volume

ratio)

Ports

* is weight ratio;

Fig. 10 Utilization of VA inOTARU port in 1897 and someconcrete structures (Fujita 1960)


carefully (Hossain and Lechemi 2009). Because of the lowerdensity of light aggregates, LWCs usually have lower slumpwhen compared with PC concrete (PCC). Little added VA canmake the slump of light weight SCCs (LWSCCs) to increasewith the volume of VA and to obtain better workability whichmeets EFNARC classifications (Hossain 2014).

Air content

Though the increase of air content generally lead to an in-crease in workability, it will result in the decreases of strengthand durability of concretes. As described bymany researchers,the air content of VRMCs increased with VA/VP content(Hossain and Ahmed 2010; Ramezanianpour et al. 2012;Hossain 2014), which is due to the addition of these compar-atively coarser VRMs (Hossain and Lachemi 2006b). In ad-dition, previous studies have indicated that the air content ofhigh-performance VACs (HPVACs) increased generally withthe increase of VA content, ranged from 2.6 to 3.2 % (Hossainand Lachemi 2006b; Tchakoute et al. 2013), which are similarto the ones of no air-entrained PCCs.

Setting time

The setting time of concrete is important for practical engineer-ing because it affects the time available for the transportation,placing, and compaction of concrete. Usually, the increase inVA content will increase the initial and final setting times ofconcrete both (Ogunbode and Olawuyi 2008; Hossain 2004a;Tchakoute et al. 2013; Hossain 2014; Hossain and Lachemi2009). This can be explained by the following:

1. The hydration process of VRM-PC system got slow downwhen VRMs were added, because the addition of VRMsreduces the content of effective cementitious materials inconcrete and decreases the total surface area of hydrationcementitous materials at early stages (Hossain 2003;Hossain and Lachemi 2009);

2. VRMs have low specific surface area and low content offree CaO (Tchakoute et al. 2013). For example, the initialsetting times of concrete are from 3.15 to 3.60 h and theirfinal setting times ranged from 5.15 to 5.80 h, when con-cretes use a blended ASTM type I cement using 0 to 25%volcanic pumice powder (VPP) (Hossain 2004a).

3. The type of VRMs also can affect the setting times of con-crete. Hossain (2003) indicated that the initial and final set-ting times of concrete both increased by 90 and 58 % whenVA content in concrete are 0 and 50 %, respectively, whilethe ones are 94 and 59.2 % when 0 and 50 % VPPs wereused in concretes, respectively. On the other hand, Turanliet al. (2004) reported when volcanic tuff was used as blend-ed cementitious material in concrete, the initial and finalsetting times of concrete both decreased as its content,

which is similar to the findings of Targan et al. (2003)who explained this as that a greater interparticles contactcan be obtained when more large surface area natural poz-zolans was added in concrete. In the case of SCCs, somesimilar observations can be confirmed in their initial andfinal setting times, i.e., the using of VA can increased boththe two setting times (Hossain and Lachemi 2009).

Internal structural properties

Microstructures of VRMCs

Generally, fine reactive particles can contribute to a more ho-mogeneous and compact internal structure for concrete (e.g.,porosity and compactness), similar to the influences of SCMson hardened PC pastes. Bărbuţă and Toma (2014) reportedthat the presence of VTs has a beneficial influence on themicrostructure of concrete. In a VA-LWC system (VALWC),a lower porosity and smaller average pore diameter can beobserved than the ones in control PCCs, especially at laterstages, which can be explained by the pozzolanic behaviorof VA at later stages, as shown in Fig. 11 and Table 7(Hossain and Ahmed 2010).

In addition, hydration or curing temperature has an influ-ence on the pore structure development of VRMCs. The re-search (Escalante-Garcıa and Sharp 2001) showed that an in-crease of porosity was found when the hydration temperaturesincreased from 10 to 60 °C in the blended cement pastes usingVRMs, as shown in Fig. 12.

Density of VRMCs

Generally, the increase of VRMs’ has a negative effect on thedevelopment of density of concretes (Hossain 2004a; Hossainand Lachemi 2006b, 2007a, b; Bărbuţă and Toma 2014), i.e.,the density of concrete decreases when VRMs’ content in-creases. This usually can be explained by the lighter mass ofVRM aggregates. However, the above researchers also report-ed that the reduction of density in these concretes is not sig-nificant. For example, using 0–40 % of VA content, the den-sity of VACs ranged between 2350 and 2400 kg/m3 at 28 days,which means the decrease ratio is only 1.5–1.9 %, similar tothe one is 3.25 % in HPVACs using 0–20 % VA (Hossain andLachemi 2007b). The above reported densities satisfy the re-quirements in CSA Standard (2004) for semi-lightweightstructural concrete, even the ones of concretes using 100 %VPA according to ASTM C 330 (Hossain 2004a).

Microhardness and interfacial transition zone

In order to evaluate the influence of additional materials on thefeature of interfacial transition zone (ITZ) of concrete, analyze


the microstructural characteristics of hardened cement pasteand ITZ, as a powerful method, a microhardness testing usu-ally was implemented. The two properties affect significantlythe strength and durability of concrete. Figure 13 shows theresult of microhardness of ITZ in VALWC mixtures, present-ed by Hossain and Ahmed (2010). The infill effectiveness ofsmall-diameter VRMs usually can be helpful to improve themicrohardness of concrete/paste near to aggregates. Igarashiet al. (1996) explained that this is a result that stiff inclusionsrestrain the flow of material under the indentation. For ITZcharacters, as shown in Fig. 13, previous studies (Hossain andLachemi 2007b; Hossain and Ahmed 2010) shown that con-cretes with VA showed better ITZ when compared to PCCs;

however, it is not significant when VA content from 0 to 20%.Due to the effect of absorbed pore water of lightweight aggre-gate, in LWCs, the paste-aggregate transition zone was im-proved when VRMs increase, especially at latter stages, re-ported from Hossain and Ahmed (2010).

Initial surface absorption

Pozzolanic materials can effectively reduce the initial surfaceabsorption (ISA) of concrete, such as silica fume (Chan and Ji1999). Even though a few studies focusing on the ISAs ofVRMCs, VA/VRMs’ powder also can realize this improve-ment, theoretically. On the other hand, research (Hossain

Fig. 11 Cumulative pore volumeof VRMCs and PCCs (Hossainand Ahmed 2010)

Table 7 Porosity and average diameter of porosity of VRMCs

Mix W/B Binder Aggregate (kg/m3), coarse fine Microstructures Note

Cement VA VPA For GA and type Iportland cement GA

Sand Porosity (% v/v) Average porediameter (μm)

A-100-C 0.45 462 0 368 0 714 8.91 0.033 Volcanic pumice aggregateas replacementA-75-C 0.45 462 0 276 247 714 9.09 0.0332

A-50-C 0.45 462 0 184 494 714 9.21 0.0336

A-0-C 0.45 462 0 0 988 714 9.4 0.0344

B-100-C 0.45 406 0 436 0 640 9.98 0.0371

B-75-C 0.45 406 0 327 293 640 10.09 0.0381

B-50-C 0.45 406 0 218 586 640 10.21 0.0392

B-0-C 0.45 406 0 0 1172 640 10.58 0.0415

A-100-PVAC 0.45 370 92 368 0 692 6.18 0.0314 PVAC was used in place ofportland cementA-75-PVAC 0.45 370 92 276 247 692 6.21 0.0318

A-50-PVAC 0.45 370 92 184 494 692 6.25 0.0319

A-0-PVAC 0.45 370 92 0 988 692 6.33 0.0324

B-100-PVAC 0.45 325 81 436 0 621 6.8 0.0352

B-75-PVAC 0.45 325 81 327 293 621 6.85 0.0361

B-50-PVAC 0.45 325 81 218 586 621 6.91 0.0378

B-0-PVAC W/B 325 81 0 1172 621 7.02 0.0396

Source: Hossain and Ahmed (2010). Series C: (0, 25, 50, and 100 %) gravel aggregate (GA) and PC were replaced by VPAs; series PVAC: similar toseries C, but using VA to replace PC in concretes


2004a) showed that a significant difference in absorption ca-pacity has been confirmed between VPA concrete (VPAC)and conventional concrete at first 2 h. Due to VPAs have ahigh porosity and absorption capacity, VPACs showed ahigher ISA value than control concrete and their ISA levelsincrease as the percentage of VPAs. The highest increase ratiowas reported to be 35%when concrete used VPAs to replaces100 % of aggregates, which is similar to the situations oflightweight concrete.

Mechanical properties of VRMCs

Compressive strength

The strength development of concrete using blended cement isaffected not only by W/B ratio, the pozzolanic activity ofSCMs and cement composition, but also by the particle sizedistribution of cementitious materials. Massive studies shownthat the use of VRMs for replacing partly cement, fine and

coarse aggregates will generally reduce the compressivestrength of concrete (e.g., Kaku et al. 1988; Kaku and Hori1989; Turanli et al. 2004; Hossain and Lachemi 2007a, b,2009; Olawuyi et al. 2012; Hossain and Ahmed 2010), whilethis strength can be improved as the increase of curing ages.The researchers considered that the following can explain thiseffect of VRMs on concretes, i.e., as VRMs increases:

1. The total aggregate/cement ratio increases (Hossain andLachemi 2007b).

2. The strength of aggregates decreases (Hossain andLachemi 2007a).

3. The internal phase content such as amorphous decreases(Tchakoute et al. 2012).

However, these VAC/VPACs still can provide acceptablestrength levels. For example, a compressive strength in excessof 15 MPa at 28 days can be obtained when using less than40 % VA in concrete (Hossain and Lachemi 2006b). In

Fig. 12 BEI micrographs of VAcement paste (1 year) at differenttemperatures (Escalante-Garcıaand Sharp 2001)

Fig. 13 ITZ microhardness ofVRMCs with different totalaggregate-binder ratio by mass(the control mixes of series A is3.7, series B is 4.5) (Hossain andAhmed 2010)


addition, HPVACs can have a 28-day compressive strength inexcess of 60 MPa when the added percentage of VA in con-crete was controlled fewer than 20 % of cement (Hossain andLachemi 2007b). Hossain (2004a) also reported that the com-pressive strengths of VPCs with 100 % VPAs are approxi-mately 40–45 % of the ones of control concrete.

Based on the above studies, to improve the early strength ofVRMCs, some feasible improvement methods were collectedand suggested, as follows:

1. Using a curing temperature ranges from 25 to 200 °C(Hossain 2006).

2. Using Metakaolin in VA-based geopolymer concrete andusing fused-VA/Metakolin as a ratio of 40/60 (Kouamoet al. 2013).

3. Adding moderate lime (Shi 2001; Chen and Wang 2009);for example, using a lime-volcanic ash mixture or a ce-ment lime-volcanic ash mixture.

4. Using VT as a filler in polymer concretes (Bărbuţă andToma 2014).

5. Using a modified mixture, e.g., 20 % laterite/CaO+80%VA (Ogunbode and Olawuyi 2008).

Tensile strength

A low tensile strength will make concrete to be subjectedto a danger of shrinking cracks affecting significantly itsdurability. Due to concrete members are under differentloads, the tensile strength of concrete mainly can be divid-ed into two kinds, i.e., splitting and flexural tensilestrengths. Comparing with the effect of VRMs on the com-pressive strength of concrete, generally, VRMs have a pos-itive influence on the tensile strength of concrete. For ex-ample, the splitting strengths of VACs ranged from 0.49 to0.77 MPa, which generally meets the splitting strength re-quirement of 0.6–0.8 MPa in expressways or first-classhighways at 180-day age (Chen and Wang 2009).Besides, Ramezanianpour et al. (2012) indicated that theconcretes containing VRMs can obtain a better tensilestrength than the ones using identical modified PC, whichcan be attributed on the recrystallization of CaO3. On theother hand, in concretes using VTs, the addition of VTimproves the tensile strength of concrete as shown inFig. 14. At the same time, they pointed out when epoxyresin was added into VRMCs, the governing factor to flex-ural tensile strength of concretes seems to be VT content,not is epoxy resin percentage, which is different with PCsystem. In LWC system, due to using comparatively weak-er VPAs, Hossain and Lachemi (2007a) showed that thesplitting tensile strength of concretes with 100 % VPAsranged from 3.7 to 3.4 MPa, corresponding to the valuesof 2.6 to 2.2 MPa in control concrete.

Elasticity modulus

The main affecting factors of the elasticity modulus (E) ofconcrete include concrete compressive strength, the stiffnessof coarse aggregate and ITZ characteristics. The elasticitymodulus of concrete usually increases with compressivestrength as presented in the empirical equations proposed byvarious codes. Regarding to the effect of VRMs on the elas-ticity modulus of concrete, main findings can be summarizedas follows:

1. The elasticity modulus of VRMCs decreases with the in-crease of VPA or VA content. When 0–20 % of PC wasreplaced by VA, the maximum decrease level of elasticitymodulus of VACs reached about 44 % as shown inTable 8.

2. When 100% of coarse aggregates was replaced VPAs, the28-day elastic modulus of concretes decreased 43% of theone of control concrete, from 17.7 GPa. The lowest deg-radation level has been confirmed when both coarse andfine aggregates were replaced by VPAs (Hossain andLachemi 2007a).

3. In polymer concretes, increasing VT has resulted in asteep decrease in the elasticity modulus of concrete(Bărbuţă and Toma 2014), which can be improved whenusing appropriate resin.

Resilient modulus of asphalt concrete using VRMs

Resilient modulus (MR) is a very important evaluation factorfor asphalt concretes in pavement engineering. According tothe test method of ASTM D-4123 (1995), a resilient modulustest is applied to evaluate the performance and quality of hotmix asphalt (HMA). Generally, concrete compressive strengthand compactness will affect resilient modulus of asphalt con-crete. As shown in Fig. 15, when VA content was controlledup to 20 %, Naji and Asi (2008) considered the addition ofgranular volcanic ash aggregates has resulted in an increasedin the resilient modulus of the asphalt concretes. This possiblycan be attributed to the rough surface texture of granular VAparticles improving the interlocking of aggregates when theiraddition volume is low. However, the resilient modulus ofconcrete decreased as Vas when their contents are in excessof 20 %, because the low strength of granular VA particlesprovides more obvious effects than the one caused by theirrough surface texture (Naji and Asi 2008).

Fatigue behavior of VRMCs

Investigation of fatigue behavior of concrete is applied toassess the capacity of this material to resist the impacts ofrepeated loads including tensile, compressive, and flexural


loads. The research focusing on the fatigue behavior ofVRMCs is limited, which will propel the utilization ofVRMs in pavement and deck eng inee r ing . Bycomparative test and analyses, Chen and Wang (2009)indicated that cement-lime-volcanic ash mixture has a bet-ter performance of flexibility and fatigue resistance thanconventional concrete. The mixtures using VA also pre-sented superior properties under higher stress intensitywhen compared with normal concrete, especially at theletter stages. Up to now, however, there are not furtherstudies focusing on the explanation of the resistance me-chanics of VRMCs.

Durability properties of VRMCs

Based on the above reviews, the fresh and hardened propertiesof various VRMCs demonstrated that the materials can beused to develop a concrete for RC structures with acceptableproperties, just with appropriate initial concern and curing.However, under environmental impacts, the durability of con-crete also is very important assessing index to predict the lifeof concrete and manage concrete structure. This section em-phasizes the durability properties of VRMCs which affectingsignificantly their application in concrete industries and pro-vides a comprehensive summary.

Table 8 The strength and modulus of elasticity of VACs or VPACs

Mix W/B Binder Fine/coarse aggregate(kg/m3)

28 days Note

Cement VA VPA GA Sand Density (kg/m3) Compressive strength Elasticity (GPa)

A-100-C 0.45 462 0 368 0 714 1910 27 10.5 volcanic pumice aggregateas replacement for GAand Type I portlandcement

A-75-C 462 0 276 247 714 1996 31 12.1

A-50-C 462 0 184 494 714 2160 35 14.3

A-0-C 462 0 0 988 714 2520 40 18.2

B-100-C 406 0 436 0 640 1861 23 10.1

B-75-C 406 0 327 293 640 1975 27 12.2

B-50-C 406 0 218 586 640 2149 32 14.2

B-0-C 406 0 0 1172 640 2480 36 17.7

A-100-PVAC 0.45 370 92 368 0 692 1849 23 10.3 PVAC was used in place ofportland cementA-75-PVAC 370 92 276 247 692 1936 27 11.9

A-50-PVAC 370 92 184 494 692 2095 30 14

A-0-PVAC 370 92 0 988 692 2444 35 17.8

B-100-PVAC 325 81 436 0 621 1824 21 9.6

B-75-PVAC 325 81 327 293 621 1936 23 11.8

B-50-PVAC 325 81 218 586 621 2106 28 13.8

B-0-PVAC 325 81 0 1172 621 2430 32 17.1

Source: Hossain and Ahmed (2010). Series C: (0, 25, 50, and 100 %) gravel aggregate (GA) and PC were replaced by VPAs; series PVAC: similar toseries C, but using VA just to replace PC in concrete

Fig. 14 Splitting (a) and flexural(b) tensile strength of polymerconcrete (Bărbuţă and Toma2014)


Water permeability

Water permeability (WP) is the ability of materials to allowwater to pass through them. TheWP of concrete is significant-ly involving to the porosity, the shape, and connectednessdegree of pore in this material (Hossain 2004a). Based onthe reports from Hossain and Lachemi (2006b), the WP ofVRMCs generally increases with the increase of VA and thereis a drop in WP caused by a further curing time in theseVRMCs (see Fig. 16), which is similar to the fly ash-cementsystem reported by Davis (1954) and Manmohan and Mehta(1981). On the other hand, in the concretes using the compos-ite cement containing VA and limestone with/without air-entraining agent, the water penetration depths of the two con-cretes both increase when comparing with the control concretespecimen, and the drops in water permeability as curing timealso were found in all tested concretes (Ramezanianpour et al.2012).

In a LWC system, Hossain and Ahmed (2010) reported thatthe water permeability capacities of LWC mixtures with VPAwere lower than the ones of control concretes. The authorsexplained that the development of superior contact zone be-tween aggregate and matrix phase can contribute to ITZ mi-crohardness at the surface of aggregate. In addition, the waterpermeability of VPACs was reported to increase in three timeswhen VPA replacement content increased from 0 to 100 %(Hossain 2004a), which presents high moisture movementand corrosion rate of the concretes. He considered that this

changing was from the added comparatively porous VPAs.The high permeability of VRMCs suggests that some specialconcerns should be considered to prevent the potential corro-sion of reinforcements in the concrete.

Chloride resistance

The chloride ion erosion of concrete is most main factorresulting in the corrosion of steel rebar in concrete structures,which destroy the passivation layer of rebars. The chlorideresistance of concrete mainly is affected by porosity,strength, and W/B ratio. Generally, it is unified knowledgethat moderate VA is beneficial to the improvement of theporosity and microstructure of concrete, because of mainlythe infill effectiveness and pozzolanic reactivity of VA. Theymake concrete can provide a more effective resistance of chlo-ride ions and others. For example, Hossain and Lachemi(2009) reported the chloride penetration depth of VACs de-creased with VA content when concretes use the W/B ratio ofup to 0.4, especially at low W/B ratio. Considering the effectof curing time on the permeability of concrete containingVRMs, the adding of VA also can make concrete to be denseras curing age increases, which is good for the long-term cor-rosion resistance of VRMCs. In addition, Hossain andLachemi (2006a) considered the more effective resistance ofchloride ion of VRMCs can be attributed to the fact that VPconsumes calcium hydroxide resulting from hydration ofcement.

In a PC-VA mortars system, similar experimental resultsverified the long-term beneficial effect of VRMs on chloridediffusivity, as shown in Fig. 17 (Hossain and Lachemi 2004a).In VA-SCC system, the resistance to chloride ion penetrationof VA-SCCs is very high as per ASTM 1202 (2012) andincreases with the increase of VA content. The rapid chloridepenetration (RCP) of all tested VA-SCC mixes can be con-trolled between 900 and 1540 C, while the values of normalSCC mixes ranged from 1100 to 1405 C (Hossain andLachemi 2009). Besides, when concretes are in chloride ion-rich environment, Hossain (2005a) reported the concrete

Fig. 16 Effect of VRMs’ contenton water permeability of VRMCs(Hossain and Lachemi 2006b;Hossain 2004a)

Fig. 15 Effect of VA content on resilient modulus (Naji and Asi 2008)


mixes using VA and VPP both presented a high weight losscomparing with control concretes. The author considered thismay be explained by too high alkali brought by VA and VPP,which may lead to a deadly effect to concrete.

Sulfate resistance

The ratio of mass loss of concrete is an important assessingindex to evaluate the capacity of sulfate resistance of concrete.As described previously, because of the refinement of poresand the decrease of total pore volume, the addition of VA andVP can enhance the capacity of concretes to resist chloride ionpenetration. However, the deterioration induced by sulfate en-vironment is different with that induced by chloride ions(Hossain and Lachemi 2006a). Up to now, just a few studiesfocus on the durability of the concretes using VA/VP exposed insulfate environment. Hossain and Lachemi (2006a) investigatedexperimentally the sulfate resistance of VACs/VPACs using twodifferent PCs and compared the concretes using blendedcements containing VRMs with different W/B, as shown inFig.18. The main findings can be summarized as follows:

1. W/B ratio is a significant factor affecting the sulfate resis-tance of VRMCs. A smaller W/B ratio has resulted in alower weight loss in the concretes.

2. Under same situation, the ratios of weight loss of con-cretes using type I +VA/VP and type V+VA/VP arehigher than the one of plain concrete, especially afterabout 18 months. The use of type V PC in VRMCs isbeneficial to the resistance to sulfate of concrete.

3. No obvious difference has been found between the con-cretes using VA and VP.

The phenomenon can attributed to porous and lacunosismagnesium silicate hydrate gels obtained from the reactionof calcium silicate hydrate with magnesium ion when VAand VP were added. The lower C3A content of type V cementmade the VACs/VPACs to present lower deterioration com-paring with the ones using type I PC (Fig. 18).

Salt scaling resistance

The main parameters affecting the scaling resistance of con-cretes include the air content, surface strength of concrete, etc.Due to the W/B ratio of concrete increases or aggregatestrength decreases in VACs/VPACs, and considering gluespall mechanism, generally, the salt scaling resistance capacityof VRMCs is lower than that of PC concrete. Research results(Ramezanianpour et al. 2012) indicated two important find-ings regarding the salt scaling resistance of VRMCs,

1. When without entrained air agents, the resistance of theconcretes using PC is better than the ones using compositecement containingVRMs. Because in these concretes, air-entraining content is the most important parameter affect-ing the scaling resistance of concrete.

2. When with entrained air agents, the mixtures containingVRMs has better salt scaling resistance, due to they havebetter tensile and surface strength and abrasion resistanceunder the consideration of glue-spall theory.

On the other hand, in SCC systems, Hossain and Lachemi(2009) indicated that the surface scaling resistance ratings ofVA-SCC mixtures ranged from 4 to 5 according to ASTMC672 (2003) and was poor, especially in SCCs mixed withmore than 20 % VA, which is mainly due to the nonairentrained nature of concrete mixtures. However, due to thepresence of a balanced air void system, lightweight SCC usingVA/VPPs showed a satisfactory salt scaling resistance with aratings of 3 (Hossain 2014). Researchers considered that itmight be rigorous using ASTM C672 to evaluate salt scalingresistance of the concretes using SCMs or VRMs (e.g.,Thomas 1997).

Seawater attacks

Recently, the durability of concrete in marine environment hasbeen concerned in concrete industries. The capacities of con-crete to resist seawater attack are not completely identical asthe ones in chloride ion environment. In seawater, there are 35,000 ppm of dissolved salts containing about 78 % sodiumchloride salt, 15 % chloride ion, and sulfate magnesium salt(Hossain 2005b). Based on ACI Committee Guide 301 (2010)and the research results reported by Baghabra et al. (1995), theeffect of sulfate ions on the durability of concrete in marineenvironment is similar to the one caused by sulfate ions only,but the effect has been changed when chloride ions presentedin concrete. The corrosive actions of seawater have beenexpressed as the reactions of MgSO4, MgCl2, and CaCl2 withCaOH2, as follows:

MgSO4 þ CaOH2→CaSO4 þMgOH2 ð1Þ

Fig. 17 Chloride concentration profile of VACs (28 days) (Hossain andLachemi 2004a)


3CaSO4 þ C3Aþ 3H2O ¼ C3A � 3CaSO4 � 3H2O Ettringiteð Þ ð2Þ

MgCl2 þ CaOH2→CaCl2 þMgOH2 ð3Þ

CaCl2 þ C3Aþ 10H2O→C3A � CaCl2 � 10H2O Friedel’s saltð Þ ð4Þ

In the above reactions, there are three important findingswith regard to the durability of concrete in seawater environ-ment, including the following:

1. Expansion caused by Ettringite increase deteriorationcaused by sulfate attack.

2. C3A in solution/concrete is favorable to the solidificationof chloride ion in concrete.

3. The formation of Friedel’s salt leads to a reduction ofconcrete strength.

Therefore, the porosity of concrete, C3A content in bindermaterials (depends on cement type), and concrete itselfstrength are three significant factors affecting the deteriorationof concrete subjected to seawater attacks.

Hossain (2005b) found that the resistance of concreteagainst seawater using 10–20 % VA is caused by the facts thatVA improves the porosity of concrete and produces moresolids by the pozzolanic reaction of VA with Ca(OH)2. Theuse of type I cement with high C3A content is more beneficialin marine environments than using type II/V PCs. For thesereasons, Hossain (2005b) recommended to use the concretesusing type I cement blended with 10–20 % VA can be used inmarine structures.

Dry shrinkage/crack

The dry shrinkage (DS) of concrete is generally affectedby the total aggregate-to-binder (TA/B) ratio, W/B ratio,hydration degree, curing temperature, and relative humid-ity. For example, it usually increases with the decrease ofW/B or curing time and decreases with the increase ofTA/B for normal concrete (Hossain and Lachemi 2009).

Regarding the concretes using VA/VP, the addition of VA/VP can make concrete to have a high DS that up to 600microstrain (Hossain 2004a; Hossain and Lachemi 2006b,2007a, 2009; Chen and Wang 2009; Kaku et al. 1987).When VA replaced more than 20 % of PC, the DS levelsof concrete increased obviously.

According to the descriptions of Gopalan and Haque(1987), the shrinkage level of lightweight concrete is greaterthan the one of normal concrete (NC) by 50%.When LWSCCmixtures use a high VPA-to-binder ratio, the concrete canexhibit a high drying shrinkage (Hossain and Lachemi2007a). Besides, the development of DS with age is negativein LWSCC system. However, this high danger caused by dry-ing shrinkage in LWCmixes at early stages can be adjusted bycuring/internal curing using the water obtained from light-weight aggregates (Hossain 2014). In VP-LWSCC mixes, onthe other hand, for more water can be provided by VPP, gen-erally, lower drying shrinkage was presented comparing withthe ones using VA (Hossain 2014).

Freezing–thawing resistance

Freezing–thawing resistance is one of important durabilityproperties to concrete structures in cold region, whichaffects significantly the entrainment of air in concrete.Chen and Wang (2009) reported that the residual com-pressive strength rate of concrete using VA at 28 dayscan exceed 60 % of the one of control specimen whensubjected to five freezing–thawing cycles, while the rateof the concrete subjected to ten freezing–thawing cycles at180 days is higher than 75 %. Their corresponding massloss ratios reached 2.1 and 2.3 %, respectively. Based onthis research, VA can be applied to improve the ability ofconcrete to resist freezing–thawing in order to satisfytechnical requirements, as shown by Hossain (2014).Further, due to the improvement of VA/VP to the micro-structure of concrete and the effect of a balanced air voidsystem, VA/VP-LWSCCs usually can obtain satisfactoryfreeze–thaw resistant properties, especially for VA-LWSCCs (Hossain 2014).

A series W/B=0.45 B series W/B=0.35

Fig. 18 Weight loss of concreteversus sulfate immersion period(Hossain and Lachemi 2006a)


Electrical resistivity

Three parameters strongly influence the electrical resistivity ofvolcanic ash itself, i.e., moisture content, soluble slats content,and compaction (Wardman et al. 2012). When they increased,the resistivity of VA decreased. In internal concrete/mortar, theflow of ions passes through pores to form an electrical current.When reinforcements in reinforced concrete structures sub-jected to an aggressive corrosion, the electrical resistivity ofthe concrete also affects the corrosion current and hence therate of corrosion. On the basis of this, some researchers con-sidered that the electrical resistivity of concrete can be oneindirect measurement of porosity and diffusivity of concrete(Ping et al. 1995; Hossain and Lachemi 2004a).

When VAwas added into concrete, as shown in Fig. 19, theelectrical resistivity of VA-PCmortars increased rapidly as theincreasing of curing time and the volume of VA (Hossain andLachemi 2004a). It can be clearly explained by the reactivityof VRMs at letter stages, which was verified by the results ofno-VA mortars. From this view, the improvement of electricalresistivity using VA can enhance the capacity of VAC to resistenvironment impacts.

Carbonation

The carbonation resistance of concrete mainly involves in thecompactness and the surface characteristics of concrete, etc.The carbonation of concrete will reduce the alkalinity ofconcrete which affects the corrosion of reinforcements inconcrete. Until now, however, the research focusing on thecarbonation of VRMCs is limited, very much. In Japan,Okuda (1987) investigated the carbonation resistance of con-crete using VRMs in a dam structure built 93 years ago andfound that VRMCs can present a very excellent carbonationresistance, just only with a maximum carbonation depth of10 cm from the surface of the concrete.

Abrasion resistance

Abrasion is a gradual process to concrete structures, includingscuffing, scratching, wearing, and rubbing away which can beevaluated via measuring the wear deep in concrete. The mainfactors affecting the abrasion resistance of concrete includeaggregate property, concrete strength, mixture proportion, fi-ber addition, curing condition, and surface situation. Previousstudies indicated that comparing to PC concretes, the con-cretes containing composite portland cement using VA havebetter abrasion resistance (Ramezanianpour et al. 2012),which similar to the concrete using limestone (Tsivilis et al.2002).

Stability properties of pastes/concretes containingVRMs

Strength, stiffness, and stability are three most importantindexes to evaluate and analyze materials. Simply, stabilityis an ability to maintain material itself original formation andstructure under various impacts including environmentalimpacts, loads, etc. In this section, the main stabilityproperties of VRMCs was summarized, including alkaliaggregate reaction, water susceptibility, creep and fatigue,thermal expansion, and strength activity.

Alkali aggregate reaction

The ASTM C618 (2001) suggested the effectiveness of thealkali–silica reactions of test mortar can be evaluated using areduction ratio in expansion, which is the ratio between thelength change of test mix and that of control mix. The codefurther requires this reduction ratio should have a maximumlevel of 100 % at 14th day. According to this, by the experi-mental investigations of some mortars using VP to replace10–40 % of PC, comparing average expansion ratio of thelengths of specimens at 14 days to the ones measured at1 day, Hossain (2004b) reported that the expansion reductionratio and the change of length of VP concretes both increasewhen low VP was increasingly used in mortars, as shown inTable 9. In addition, the author also found that the specimensstill can satisfy the requirement in code ASTM C618 whenused VP was controlled less than 40 % of PC. In case of usingVA, even with a little small, a similar result was presented andthe concretes using 30–40 % VA still can satisfy the require-ments of ASTM C618 (Hossain 2005c).

Water susceptibility, creep, and fatigue resistance of VAasphalt concrete

The improvements of water susceptibility, creep, and fatigueresistance are significant to enhance the stability of asphalt

Curing time (days)

Elec

tric

al re

sistiv

ity (Ω

-cm

)

0 50 100 150 200

0

5

0

10

0

150

200

250

40%VA20%VA0%VA

Fig. 19 Electrical resistivity of VA mortar by curing age (Hossain andLachemi 2004a)


concrete. Water susceptibility is an index related on the resis-tance to the stripping of asphalt concrete. Based on AASHTOT-283 test procedure, by examining the loss of indirect tensilestrength (ITS) of VA asphalt concretes (VAACs), Naji and Asi(2008) indicated that the increase of VA has resulted in a largerstrength ITS loss of concrete, which meaning water damage inthe concrete was increased, as shown in Fig. 20a. The impor-tant one is that the loss of ITS can be controlled under anallowable limit (i.e., 20 %) when just using 10 % VA. WhenVAwas added to replace 30 % of PC in asphalt concrete, thetensile strength decreased to 70 % of the one of control con-crete. That means when more than 10 % VA is used in asphaltconcretes, some antistripping agents should be applied.

The dynamic creep of concrete can be evaluated by mea-suring the deformation of concrete under some repeated orpulsed loads. Naji and Asi (2008) indicated that asphalt con-cretes with high volume VA have a low accumulated strain(see Fig. 20b), which implies that the positive effects of VA on

the creep properties of asphalt concretes. Some researchersconsidered that rough VA particles may be helpful to improvethe interlocking properties of aggregates in VAACs (Asi andShalabi 2007). In addition, a creep stiffness analysis (the ratioof deviator stress to axial accumulated strain) in the studyreported by Naji and Asi (2008) proved that the capacity ofVAACs to resist creep increased with VA content.

The fatigue resistance of asphalt concrete depends usuallyon the properties of the bottom of asphalt concrete layer. Byexperiment under controlled-stress repeated indirect tensileloading, the number of loading cycle in concretes was usedto evaluate their fatigue life in the research from Naji and Asi(2008). Figure 20c shows that the fatigue life of VAACs wasimproved by using VA to replace 10 % PC in asphalt con-cretes; however, the negative influence of VA was presentedwhen the replacement of VA was more than 10 %. Naji andAsi (2008) considered the rough surface of VA has resulted inan improvement in fatigue resistance when VA content is low,

Table 9 Effect of VRMs onalkali aggregate reaction (AAR) VP ratio

(%)Length change(mm)

Expansion(%)

VA ratio(%)

Length change(mm)

Expansion(%)

0 0.089 – 0 0.089 –

10 0.115 129 10 0.101 113

20 0.095 105 20 0.088 99

30 0.087 98 30 0.082 92

40 0.081 91 40 0.075 84

Source: Hossain (2004b, 2005c)

Fig. 20 Effect of VA on thestability of asphalt concrete (Najiand Asi 2008)


while the low strength of VA became the most dominant af-fecting factor to the fatigue life of VAACs when more VAswere used.

Heat-insulating property of VRMCs

The low density and good heat insulation properties ofmaterials usually make VRMCs to be highly candidates forthe resistant to heat flow. Based on this, Hossain (2004b)considered that VP can be used in the manufacture of heat-insulating building blocks. On the basic of the investigationsabout the heat conductivity of some concrete disks using VPor VPAs, it was found that the thermal conductivity of VPACsreduces as the increase of applied fine VPAs (Hossain 2004b).In the same research, however, all measured specimens stillcan satisfy the requirement in American Society for Testingand Materials (ASTM) (2009a, b).

Autoclave expansion property

ASTM C151 (2009a, b) described that autoclave expansiontest can be used to evaluate the potential delayed expansionsof concrete materials, which is possibly caused by the furtherhydrations of CaO or MgO or both in PC system at laterstages. Hossain (2004b) reported that the autoclave expansionof the paste mixes using 10–40% finely ground VP decreasedwhen VP content increased. Referring to the requirements inASTM C618 (2001), however, the property of these VRMCsstill can satisfy design of concrete when the replacement of VPis controlled less than 40 %.

Strength activity index

In order to determine whether ash or natural pozzolanic mate-rials in concrete can develop an acceptable strength, a strengthactivity index test usually was suggested, as the one in ASTMC311 (2000). Based on this, Hossain (2004b) investigated thestrength activity of mortars using VP of less than 40 % of PCand indicated that the strength activity index (SAI) values ofthese VRMSs decrease as the increase of VP at 7 and 28 days.

As shown in Table 10, expect for the mixtures using 40 % VPat 28 days, the SAI levels of all specimens are more than 75%,the low limit required by ASTM C618 (2001).

Conclusions and recommendation

The use of VRMs in concrete as part cement/aggregate replace-ment materials will significantly reduce the environmental haz-ards associated with volcano eruptions; produce economicaland low carbon concretes which contributing on the reductionof greenhouse gas emissions and helping to promote the sus-tainability development in construction industries. As indicatedin many studies, the accepted fresh, hardening, strength, dura-bility, and stability properties of VRMs/VRMCs demonstratedthat VRMs can be used to develop the concretes with moderateproperties, with appropriate initial concern and curing carefully.On the other hand, the replacement ratio of VRMs in concretesshould be selected carefully in combination with water/binderratio to achieve desired properties (Osawa 1950).

Based on this review, some recommendations on futureresearch can be provided, in the aspects of material and struc-tural properties of VRMCs. Similar to the research situation ofother SCMs in concretes, the research on the thermodynamicanalysis and modeling of VRMCs will be helpful to under-stand well their pore solution composition and hydrate assem-blage. Meanwhile, in order to clearly understand the internalstructures, durability, and strength development of VRMCs,the experimental study of C–S–H characteristics in VRMCs isvery helpful, especially the effective density/space filling ca-pacity of C–S–H in paste or concrete, in spite of currently thiskind experiment is difficult. On the other hand, as presented inthis review, previous studies mainly focused on the materialproperties of VRMCs, there are not studies provided regardingtheir structural properties of RC members using VRMCs suchas flexural resistance, cyclic shear strength, seismic behavior,etc., which should be concerned in the future to understandand proper the further application of VRMC in RC structuresunder various loadings.

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