Accepted Manuscript

Interfacial transition zone of cement composites with steel furnace slag aggregates

Alexander S. Brand, Jeffery R. Roesler

PII: S0958-9465(16)30745-4
DOI: 10.1016/j.cemconcomp.2017.11.012
Reference: CECO 2942

To appear in: Cement and Concrete Composites

Received Date: 17 November 2016

Revised Date: 25 August 2017
Accepted Date: 9 November 2017

Please cite this article as: A.S. Brand, J.R. Roesler, Interfacial transition zone of cement composites
with steel furnace slag aggregates, Cement and Concrete Composites (2017), doi: 10.1016/
j.cemconcomp.2017.11.012.

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 ACCEPTED MANUSCRIPT

1 Interfacial Transition Zone of Cement Composites with Steel Furnace

2 Slag Aggregates
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4 Alexander S. Brand*1 and Jeffery R. Roesler
5 Department of Civil and Environmental Engineering, University of Illinois at Urbana-

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6 Champaign, 205 N. Mathews Ave., Urbana, Illinois, USA, 61801
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8 Abstract

9 As previous studies of mortar and concrete with steel furnace slag (SFS) aggregates have shown

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10 increases or decreases in the bulk mechanical properties, this study investigated the

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11 microstructural cause of these opposing trends through characterization of the interfacial
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12 transition zone (ITZ) with quantitative image analysis of backscatter electron micrographs. Three

13 SFS types – basic oxygen furnace (BOF), electric arc furnace (EAF), EAF/ladle metallurgy
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14 furnace (EAF/LMF) – were examined as aggregates in a portland cement mortar. The ITZ size

15 for all SFS mortar mixtures was similar, with the ITZ of BOF and EAF/LMF being slightly more
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16 porous than mortar mixtures with EAF or dolomite. Microstructural examinations of the SFS
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17 particle revealed that BOF and EAF/LMF aggregates have different outer and interior

18 compositions, with the outer composition consisting of a porous layer, which likely contributes
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19 to the reduced strength relative to EAF. The imaging results demonstrated that the type of SFS
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20 and its spatial composition greatly influences the bulk properties of mortar and concrete, mainly
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21 as a function of porosity content in the ITZ and the outer layer and interior porosity of the SFS

22 aggregate.

*
Corresponding author; abrand2@illinois.edu
1
Present address: Materials and Structural Systems Division, National Institute of Standards and Technology, 100
Bureau Drive, Gaithersburg, MD, USA, 20899

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23 Keywords: interfacial transition zone (ITZ), microstructure, scanning electron microscopy

24 (SEM), steel furnace slag (SFS), basic oxygen furnace (BOF) slag, electric arc furnace (EAF)

25 slag, ladle metallurgy furnace (LMF) slag

26

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27 1. Introduction

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28 A by-product slag is generated during steel production, which can be broadly termed steel

29 furnace slag (SFS), with modern steel productions typically utilizing basic oxygen furnace

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30 (BOF) or electric arc furnace (EAF) processes [1]. SFS consists of various silicate and oxide

31 phases, principally dicalcium silicate (2CaO–SiO2), dicalcium ferrite, (2CaO–Fe2O3), and

32
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wüstite (FeO) [2]. In addition, free calcium oxide (CaO) and free magnesium oxide (MgO) are
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33 often present, which expand by 92% and 120%, respectively, when reacted with water [3]. The

34 free CaO content, which can be around 1-10% for BOF slag and 0-4% for EAF slag [4], and its
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35 potentially expansive nature are the main reasons why SFS aggregates are not often considered
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36 for use as an aggregate in bound (i.e., concrete) applications, but the hard and durable
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37 characteristics of SFS allow it to be used in other applications such as asphalt pavements,

38 railroad ballast, and fill material [5].

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39 When utilized as an aggregate in concrete, SFS has indicated potential enhanced

40 performance relative to virgin aggregate concrete. However, there is disagreement in the

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41 literature as to whether SFS aggregates will increase, decrease, or have little effect on concrete
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42 mechanical and durability properties, as can be seen in Table 1. The observed discrepancy is

43 likely a function of the SFS source type, as the mineralogy and properties of the SFS are

44 dependent on the production process. One study [6] examined two different SFS aggregates, one

45 BOF slag and one EAF slag, and found that the EAF slag increased and the BOF slag decreased

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46 the compressive strength while both slag aggregates decreased the split tensile strength,

47 increased the fracture properties, and increased the drying shrinkage relative to concrete with

48 dolomite aggregates.

49

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50 Table 1. Effects of SFS Aggregates on Concrete Properties*
No. of Studies Proportion (%) of Studies that Showed Effect
Concrete Property

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Surveyed Increase Decrease Similar or No Effect
Compressive Strength 39 72 13 15
Split Tensile Strength 21 71 14 14
Flexural Strength 19 68 26 5

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Modulus of Elasticity 16 81 6 13
Dynamic Modulus 2 100 0 0
Drying Shrinkage 5 20 60 20
Water Absorption 7 29 57 14

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Abrasion Resistance 4 100 0 0
*After a literature review in Ref. [7]
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52 The objective of this study is to examine the microstructure of three different SFS
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53 aggregates and their effects on the interfacial transition zone (ITZ) in a cement mortar in order to

54 evaluate any explanations for these mechanical property discrepancies in the literature. A few
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55 studies have examined the ITZ of cementitious composites with SFS aggregates through
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56 indentation testing, but all of these studies have shown that SFS aggregates will increase

57 concrete strength and improve the ITZ properties [8–12]. In another study that found higher
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58 strengths with EAF aggregates, qualitative image analysis showed that the ITZ with limestone

59 aggregates is more porous than the ITZ with EAF slag aggregates [13]. Therefore, as the
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60 previous ITZ studies have all been in instances when the strength was shown to increase with the
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61 use of SFS aggregates, it is uncertain if the ITZ characteristics are different from natural

62 aggregates in the instances were strength is decreased by the use of SFS aggregates.

63 The variability in the effect of the SFS aggregates on concrete properties may be the

64 result of the properties of the SFS particle. In particular, it has been found that the exterior of the

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65 SFS aggregate may be of different composition than the interior [14]. For example, the exterior

66 of a weathered BOF slag can contain calcite, calcium silicate hydrate, and calcium

67 carboaluminate hydrate phases, which has been argued to be the source of concrete strength

68 reduction as the result of a poorer paste-aggregate bond [15]. However, it has also been argued

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69 that an increase in concrete strength with SFS aggregates is because of the rough surface texture

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70 of the particles as well as a chemical reaction occurring between the slag and the cement [8–10].

71 Furthermore, aggregate particle shape, gradation, phase composition, porosity, and surface

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72 texture are also known factors that can affect concrete strength [16,17], and these factors will

73 vary depending on the SFS type and source. Pang et al. [18] confirmed this by demonstrating

74
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that carbonated SFS has a different porosity (i.e., fewer larger pores and more smaller pores) and
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75 mineralogy (i.e., more calcium carbonate) relative to an unmodified SFS, and these changes were

76 shown to potentially affect improve the bulk concrete strength.

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77
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78 2. Experimental Design
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79 In this study, three different SFS sources – which were characterized previously for

80 chemical, physical, and mechanical properties [6] – were evaluated primarily for microstructural
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81 ITZ properties as well as bulk strength and stiffness. Several pertinent properties of the three SFS

82 sources are summarized in Table 2. When 100% of the coarse aggregate in a concrete mixture
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83 was replaced by the same SFS1 (BOF) or SFS2 (EAF), the split tensile strength was reduced, the
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84 free drying shrinkage was increased, and the freeze/thaw durability was similar to concrete with

85 dolomite aggregates [6].

86 To evaluate the mechanical properties, coarse mortars were created that consisted of 40%

87 aggregate and 60% cement paste by volume. A high paste content was used to allow enough

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88 space between aggregates to provide clear, distinct ITZs to be imaged by backscatter electron

89 microscopy. The cement paste was Type I portland cement with a water-to-cement ratio of 0.42.

90 The aggregates all had the same gradation of particles passing the 3/8-inch (9.5 mm) sieve and

91 retained on the #4 (4.75 mm) sieve; this was performed to avoid particle size effects on the ITZ

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92 (e.g., see Ref. [19]). All aggregates were washed to remove any dust or fines and then were dried

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93 at 50% relative humidity and 23°C. As the aggregates had similar absorption contents (BOF

94 2.3%, EAF 1.8%, EAF/LMF 1.7%, and dolomite 1.8% [6]), it is expected that there is minimal

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95 effect of aggregate water absorption on the ITZ. Cylindrical specimens were cast that measured 2

96 inches (50 mm) in diameter by 4 inches (100 mm) in height and were tested at ages of 1, 7, and

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28 days for compressive strength [20], split tensile strength [21], and dynamic modulus [22]. At
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98 each age, three replicates were tested for each strength test and six replicates were tested for the

99 dynamic modulus test. The specimens were cast, covered and cured for 24 hours at ambient
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100 laboratory conditions, and then stored in lime saturated water at 23°C until testing.
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101
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102 Table 2. Characteristics and Properties of the SFS Sources (from Brand and Roesler [6])
SFS1 SFS2 SFS3
Source Type BOF EAF EAF/LMF*
Free CaO Content 3.4% 0.1% 0.4%
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Free MgO Content 2.2% 0.2% 0.3%

CaCO3 Content 3.0% 2.6% 0.9%
Autoclave
8.8% 0.1% 0.8%
Expansion†
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3.9% Al2O3, 18.8% CaO, 7.1% Al2O3, 27.1%

2.3% Al2O3, 11.0% CaO, 0.1%
0.4% Cr, 23.9% Fe, 8.5% CaO, 0.4% Cr, 25.7%
Elemental Cr, 26.2% Fe, 12.7% MgO,
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MgO, 3.5% Mn, 0.2% P, Fe, 9.5% MgO, 1.9%

Composition‡ 1.8% Mn, 0.3% P, 0.1% S,
0.1% S, 9.6% SiO2, 0.5% Mn, 0.2% P, 0.2% S,
9.3% SiO2, 0.3% TiO2
TiO2 1.0% SiO2, 0.4% TiO2
Larnite, tricalcium silicate,
Primary Larnite, wüstite, magnetite, Larnite, wüstite,
calcium oxide, calcite, wüstite,
Mineralogy** bredigite, mayenite mayenite
magnesioferrite, srebrodolskite
*LMF, or ladle metallurgy furnace, slag is a modified EAF process
†
Autoclave expansion was measured on a compacted sample exposed to steam at 300 psi (2.1 MPa) and 420°F (216°C) for
three hours
‡
By inductively coupled plasma optical emission spectroscopy
**By powder X-ray diffraction
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104 After 1, 7, and 28 days of curing, samples from the mortar specimens were taken for ITZ

105 analysis. Thin sections (<1 mm thick) were cut and vacuum dried for 24 hours prior to epoxy

106 impregnation. Once the epoxy was set, the samples were polished down to 0.25 µm using

107 successively finer grits of silicon carbide paper and diamond paste. Additional preparation

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108 details can be found elsewhere [23,24].

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109 At least 50 images at 500x magnification were taken per age using a JEOL JSM-6060LV

110 scanning electron microscope in compositional backscatter electron (BSE) mode at a 12 keV

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111 accelerating voltage. Each image was 8-bit greyscale consisting of 960 by 1280 pixels with each

112 pixel measuring approximately 0.2 by 0.2 µm. From greyscale thresholding and image

113
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processing, it is possible to obtain details about the distribution of detectable porosity, calcium
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114 hydroxide (CH), and unhydrated (UH) cement in the ITZ as a function of distance from the

115 aggregate interface [25–28]. This study followed the method developed by Brand [23,24], which
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116 built upon ITZ analysis concepts developed by Wong and Buenfeld [29,30] and CH morphology
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117 concepts discussed by Diamond [31] and Gallucci and Scrivener [32].
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118 The cumulative greyscale histogram was used to threshold the detectable porosity based

119 on the pore overflow method by Wong and Buenfeld [29]. The CH and UH were thresholded
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120 from the peak positions in the greyscale histogram (e.g., see Figure 1 in Ref. [23]). Using the

121 Euclidean distance mapping approach [30], a percentage of a given thresholded phase could be
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122 determined as a function of distance from the aggregate interface, accounting for the two-
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123 dimensional tortuosity of the interface (e.g., see Figure 3 in Ref. [23]). By collating the data from

124 a significant number of images, an estimate of the mean ITZ composition can be generated from

125 this method.

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126 Since it is possible that the CH morphology may influence the strength of concrete [33],

127 it is worth examining the CH morphological properties in the ITZ for comparison between the

128 different aggregates. As CH appears as an elongated particle in the ITZ, the equivalent circular

129 diameter of the CH particles is computed for comparative purposes [31]. The equivalent circular

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130 diameter (deq) is determined by 4 / , where s is the pixel size (0.2 µm) and A is the number

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131 of pixels that constitutes a given particle.

132 An additional investigation was performed to investigate the SFS interior and exterior

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133 composition. As the SFS interior and exterior (edge) compositions may be different [14],

134 particularly with regard to the formation of calcium carbonate or hydrated phases on the SFS

135
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particle exterior [15], thin sections (<1 mm thick) of aggregate were cut, dried, cast in epoxy,
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136 polished down to 0.25 µm, and examined with BSE microscopy and energy dispersive X-ray
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137 spectroscopy (EDXS).

138
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139 3. Results and Discussion

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140 3.1 Mechanical Properties

141 The mortar split tensile and compressive strengths and dynamic moduli are shown in
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142 Table 3 and Table 4, respectively, for ages of 1, 7, and 28 days. The strength, in general, for the

143 SFS aggregate mixtures was not higher than the control mixture except for a few ages and SFS
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144 types. The split tensile strength was statistically higher than the control at 7 days for mixes with
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145 SFS2 and SFS3 while the compressive strength was only statistically higher than the control at

146 28 days for the mix with SFS2. It should be noted, however, that these mortars had a high paste

147 content, so the effects of the aggregates may not be as drastic as may be seen in concrete.

148 Therefore, for comparison, the concrete strength results for concrete with SFS [6] are also shown

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149 in Table 3, which demonstrated that concrete with SFS1 (BOF) had lower strengths than the

150 control; concrete with SFS2 (EAF) produced a statistically higher compressive strength than the

151 control at 94% confidence.

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153 Table 3. Strengths for Mortar Mixtures with Dolomite and SFS Aggregates
Split Tensile Strength (MPa) Compressive Strength (MPa)

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Age Mix
Average Standard Deviation Average Standard Deviation
Control 2.7 0.1 22.8 1.7
1 Day SFS1 (BOF) 3.0 0.3 22.2 0.8

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Mortar SFS2 (EAF) 3.1 0.4 24.0 0.7
SFS3 (EAF/LMF) 2.6 0.3 20.6 0.7
Control 3.0 0.9 34.8 3.8

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7 Days SFS1 (BOF) 3.0 0.3 34.8 1.3
Mortar SFS2 (EAF) 4.9 * 0.3 31.7 7.3
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SFS3 (EAF/LMF) 4.6* 0.5 36.1 3.1
Control 4.5 0.4 41.1 2.2
28 Days SFS1 (BOF) 4.3 0.7 38.5 1.1
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Mortar SFS2 (EAF) 5.1 0.6 49.8* 2.2

SFS3 (EAF/LMF) 5.1 0.3 43.0 4.3
Control 6.4 0.9 46.1 1.4
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28 Days
SFS1 (BOF) 3.7* 0.2 40.1* 2.0
Concrete**
SFS2 (EAF) 4.4* 0.5 48.3 0.5
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*Means are statistically different from the control with 95% confidence
**Concrete results from Brand and Roesler [6]
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155 At all ages, the dynamic modulus was statistically higher for all SFS aggregate mixtures

156 relative to the control. This increase in dynamic modulus can be attributed, in part, to the
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157 increase in SFS density, as the computed dynamic modulus is directly proportional to the
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158 specimen mass [22]. The apparent specific gravity for these aggregates are 3.5 (BOF), 3.9

159 (EAF), 3.7 (EAF/LMF), and 2.8 (dolomite) [6]. In addition, SFS aggregates have a high stiffness

160 [34,35], largely as a result of the high iron content [36], which may also contribute the greater

161 dynamic modulus values seen for SFS mortars. The BOF and EAF slag aggregates in this study

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162 were also shown to produce a statistically greater concrete stiffness relative to dolomite concrete

163 [7], which further supports that the SFS aggregate have a higher modulus than dolomite.

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165 Table 4. Dynamic Moduli for Mortar Mixtures with Dolomite and SFS Aggregates

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Longitudinal Dynamic Transverse Dynamic
Modulus (GPa) Modulus (GPa)
Age Mix
Standard Standard
Average Average
Deviation Deviation

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Control 21.9 1.0 21.3 1.0
1 SFS1 (BOF) 27.6* 1.1 27.7* 1.3
Day SFS2 (EAF) 1.3 1.2

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30.4* 30.5*
SFS3 (EAF/LMF) 27.7* 1.6 26.8* 2.3
Control 29.6 0.5 29.2 1.2
7 SFS1 (BOF) 36.8* 1.9 37.1* 1.8

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Days SFS2 (EAF) 39.1* 1.2 38.1* 1.5
SFS3 (EAF/LMF) 38.1* 1.4 36.9* 1.4
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Control 32.9 1.0 33.0 1.5
28 SFS1 (BOF) 40.4* 1.8 40.9* 2.2
Days SFS2 (EAF) 43.6* 0.5 43.9* 1.7
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SFS3 (EAF/LMF) 41.3* 1.1 41.0* 1.7

*Means are statistically different from the control (95% confidence)
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167 3.2 ITZ Composition (Porosity, UH, and CH)

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168 Examples of the BSE images of the SFS ITZ are shown in the Appendix. From image

169 processing, the detectable porosity, UH, and CH are reported in Figure 1, Figure 2, and Figure 3
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170 for mortars at 1, 7, and 28 days, respectively. In addition, the total C-S-H content can be
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171 estimated by subtracting the detectable porosity, UH, and CH from 100% [37], but this estimated
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172 content includes what can otherwise be termed “other hydration products,” since it will also

173 include phases such as ettringite or monosulfoaluminate.

174 At 1 day, the ITZ characteristics are practically the same for all mortars (Figure 1). This

175 is in agreement with Table 3 that showed that the 1-day strengths were not drastically different

176 between mixtures with and without SFS. Therefore, the statistical difference in modulus values

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177 at 1 day (Table 4) are a result of the stiffness and density of the SFS and not because of the ITZ

178 properties.

179 At 7 days, the ITZ characteristics begin to deviate slightly relative to the dolomite (Figure

180 2). Near the interface, within approximately 20 µm, the porosity is greater for the BOF and

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181 EAF/LMF slags relative to the dolomite while the EAF slag porosity is similar to dolomite.

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182 While the UH and C-S-H contents and distributions are similar for all mixtures, the CH content

183 appears to be slightly greater for dolomite near the interface (within approximately 10 µm)

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184 relative to the SFS mortars.

185 At 28 days, the ITZ characteristics are more noticeably different (Figure 3), particularly

186
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the BOF and EAF/LMF slags relative to the dolomite, as there is greater porosity and less C-S-H
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187 within the ITZ (within about 40 µm). The UH contents and distributions are similar for all

188 mortars, which suggests that the absorption capacity of the aggregate did not influence hydration.
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189 As at 7 days, the CH is greater for dolomite near the interface (within 10 µm) relative to the SFS
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190 mortars.
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191 A number of studies have shown evidence of CH growing on or at virgin aggregate

192 interfaces [25,31,38,39]. Monteiro and Mehta [40] suggested that, for carbonate mineral
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193 aggregates, CH reacts to form a calcium carbonate hydrate phase, which may increase the bulk

194 mechanical strength. Since the amount of CH at the interface is more prominent for dolomite, it
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195 is possible that CH is more energetically or chemically attracted to dolomite (i.e., for reaction
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196 [40]), which may not be the situation for the SFS.

197 Comparing the 7- and 28-day ITZ trends to the strength findings in Table 3, the bulk

198 mortar strengths are statistically similar for BOF and the control despite that the BOF slag ITZ

199 appears to be more porous than dolomite. The EAF slag mortar ITZ is very similar to dolomite

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200 mortar, but the strengths can be statistically greater for EAF slag at later ages, and thus there

201 must be additional factors other than the ITZ causing the strength increase. Likewise, the

202 EAF/LMF slag ITZ trends were in between the trends for the BOF and EAF slags, but it also did

203 not significantly change the strength properties relative to the dolomite control.

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204

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205
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206 Figure 1. Detectable porosity, UH, and CH and estimated C-S-H at 1 day for mortars with
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207 dolomite and three SFS sources.

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209
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210 Figure 2. Detectable porosity, UH, and CH and estimated C-S-H at 7 days for mortars with
211 dolomite and three SFS sources.
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212
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213
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214 Figure 3. Detectable porosity, UH, and CH and estimated C-S-H at 28 days for mortars with
215 dolomite and three SFS sources.
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216

217 Using a statistical z-test to determine the size of the ITZ [23], i.e., when the ITZ porosity
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218 is no longer statistically different (95% confidence) than the bulk porosity, Table 5 shows that

219 the mean size of the ITZ may be slightly larger for mortars with SFS aggregates. Dolomite
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220 mortar was found to have an ITZ thickness of around 40 µm, while the ITZ thickness for mortar
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221 with SFS aggregates was 41 µm to 46 µm.

222 The standard error, defined as the standard deviation normalized by the square root of the

223 sample size, was found to be ≤1.4% for all phase measurements in the ITZ (Table 5). Scrivener

224 [41] reported that the standard error of such measurements could be on the order 5-10% for data

225 collected from 50-100 images, while Crumbie [38] and Brand and Roesler [23] found standard

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226 error values of ≤2% and ≤1.5%, respectively, for phase content measurements in the ITZ of

227 concrete or mortar samples when averaging data from 50 or more images. Therefore, the

228 variability in the measurements for this study are consistent with past literature.

229

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230 Table 5. Size of the ITZ and Average Standard Error within the ITZ at 28 days
No. of Size of the Average Standard Error (%)
Mix

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Images ITZ* (µm) Porosity CH UH
Dolomite 58 40 0.9 1.0 0.8
SFS1 (BOF) 54 44 1.4 0.9 0.9

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SFS2 (EAF) 53 41 1.3 1.0 0.8
SFS3 (EAF/LMF) 57 46 1.3 0.8 1.0
*Determined based on porosity distribution
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232 3.3 CH Morphology

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233 Image analysis techniques were employed to examine the CH morphology [31,32]. This

234 was conducted to evaluate if the SFS aggregate is affecting CH growth or nucleation, as other
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235 recycled materials have been shown to affect CH growth [23]. The mean equivalent CH particle
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236 size is shown in Table 6, indicating that the mean equivalent circular diameter varies very little
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237 as a function of distance from the interface. Immediately near the interface (within 1 µm), the

238 particles are slightly smaller for SFS compared to dolomite, which agrees with Figure 3 that
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239 there is more CH near the interface for dolomite. The mean CH particle size is roughly

240 equivalent in all mixtures when considering all particles within 5, 40, and 100 µm of the
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241 interface, although the EAF slag mortar may exhibit a slightly smaller mean particle size. Figure
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242 4 indicates that all mortars (with and without SFS) have a similar amount of CH particles

243 throughout the ITZ and bulk matrix, and all mortar samples contained the most CH particles

244 within ~25 µm of the interface. Therefore, the SFS does not appear to significantly affect CH

245 nucleation or growth within the ITZ, although there is some evidence (e.g., CH trends near the

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246 interface in Figure 2 and Figure 3) from the BSE image processing to suggest that CH

247 preferentially grows adjacent to dolomite relative to SFS.

248

249 Table 6. Mean CH Equivalent Circular Particle Diameter (µm) at 28 Days

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Dolomite SFS1 SFS2 SFS3
Mortar (BOF) (EAF) (EAF/LMF)
Within 1 µm of
4.7 4.4 4.2 4.4

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the Interface
Within 5 µm of
4.8 4.9 4.3 4.6
the Interface

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Within 40 µm
4.8 4.9 4.4 4.7
of the Interface
Within 100 µm
4.8 4.9 4.4 4.7

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of the Interface
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2.5%
Percent of Total CH Particles

2.0%

1.5%
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1.0%
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0.5%

0.0%
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0 20 40 60 80 100
Distance from the Aggregate Interface (μm)

Dolomite SFS1 (BOF) SFS2 (EAF) SFS3 (EAF/LMF)

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251
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252 Figure 4. Histograms of CH occurrence as a function of distance from the aggregate interface
253 (within 100 µm of the aggregate interface) for each of the mortars (with and without SFS) at 28
254 days.
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256 3.4 SFS Microstructure

257 Based on the previously-presented experimental findings, it is possible that there is an

258 inherent microstructural characteristic of the SFS particle that is affecting the ITZ properties and

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259 the bulk mortar/concrete mechanical behavior. Therefore, polished sections of plain dolomite

260 and SFS particles were qualitatively examined with BSE microscopy and EDXS.

261 Examination of the EAF (SFS2) slag (Figure 5) indicates a matrix rich in calcium and

262 silicon (likely to be larnite, based on X-ray diffraction data in Table 2) with embedded particles

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263 rich in iron (wüstite and magnetite), which is similar to what was shown by Arribas et al. [11].

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264 The iron-rich phase also appears to contain magnesium, which is expected since a

265 magnesiowüstite phase is common in EAF slags rather than pure wüstite [42]. The aluminum-

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266 containing phases (i.e., mayenite) are also evident in the matrix and appear to preferentially

267 occur along the edge of the particle. In Figure 6, the edge of the EAF particle appears to contain

268
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less of the iron-rich phases compared to the interior of the EAF particle; with image processing,
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269 for Figure 6a it is estimated that, within 50 µm of the particle edge, 12% of the area consists of

270 the iron-rich phase compared to 41% of the area in the interior (assumed to be the region greater
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271 than 50 µm from the particle edge) whereas Figure 6b in total consists of approximately 41% of
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272 the iron-rich phase by area.

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273

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(c) Si (d) Fe
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(e) Al (f) Mg
279 Figure 5. Compositional BSE (a) and EDXS maps (b-f) of the edge of an EAF slag particle. The
280 black phase along the right hand side in the BSE micrograph is epoxy. Note: EDXS images have
281 been contrast-enhanced to better indicate the elemental density.
282

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(a) (b)

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283 Figure 6. Compositional BSE micrographs of the edge (a) and interior (b) of an EAF slag
284 particle.
285

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286 In contrast to the EAF slag, the BOF (SFS1) slag exhibits a clear compositional
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287 difference along the edge of the particle relative to the interior, as shown in Figure 7, which is

288 consistent with the BSE micrographs of BOF slag shown by Coomarasamy and Walzak [14].
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289 This outer layer with different composition did not exist in some sections of the particle and

290 ranged up to 1 mm thickness, but more commonly was on the order of a few tens to hundreds of
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291 microns thick. EDXS mapping indicates that this outer layer is rich in calcium and contains less
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292 silicon and iron than the interior. This layer is also more porous; by the porosity thresholding
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293 technique used previously, the BOF interior (Figure 7a) has 0.3% porosity, while the estimated

294 porosities of the edge and interior of the particle in Figure 7b are 24% and 0.1%, respectively,
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295 and the estimated porosities of the edge and interior of the particle in Figure 7c are 10% and
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296 0.1%, respectively. The greater porosity of this outer layer is also the source of the slightly

297 higher water absorption of the BOF slag relative to other SFS and dolomite: 2.3% for BOF

298 compared to 1.7-1.8% for EAF, EAF/LMF, and dolomite [6]. Ultimately, this outer layer is

299 likely to be composed of calcium carbonate and other reaction products (e.g., calcium hydroxide

300 or some form of a calcium silicate hydrate, since both calcium and silicon are present in the outer

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301 layer), as suggested in the literature [14,15,18]. This BOF slag was found to contain about 1.3%

302 calcium hydroxide, 3.0% calcium carbonate, and 3.4% free calcium oxide [6,7]. The interior of

303 the BOF slag appears to be composed of a calcium- and iron-based matrix (possibly

304 srebrodolskite) with areas of calcium silicates (larnite and tricalcium silicate) and iron- and iron-

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305 magnesium-based phases (wüstite and magnesioferrite), which can be deduced from the EDXS

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306 maps in Figure 8.

307

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(a) (b)
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308 Figure 7. Compositional BSE micrographs of the interior (a) and edge (b-d) of a single BOF slag
309 particle.
310

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(c) Si (d) Fe
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311 Figure 8. Compositional BSE (a) and EDXS maps (b-f) of the edge of a BOF slag particle. The
312 black phase along the left hand side in the BSE micrograph is epoxy. Note: EDXS images have
313 been contrast-enhanced to better indicate the elemental density.
314

315

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316 The EAF/LMF slag (SFS3) appears to exhibit different microstructural behavior, as

317 shown in Figure 9. Both the interior and the edge of the particle can consist of a microstructure

318 that is similar to the EAF slag (Figure 9a,d), though not all sections of the edge appeared to

319 exhibit the same microstructure (Figure 9e). However, sections of the interior of the particle also

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320 exhibited large circular pores with some smaller pores (Figure 9b) as well as substantial porosity

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321 (Figure 9c). The large circular pores were also found to exist along the edge of the particle

322 (Figure 9f), while other sections of the particle were found to be significantly porous at the

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323 interior as well as at the edge (Figure 9c,g,h). While not consistent throughout the entire particle,

324 sections of the edges also showed evidence of the outer layer of different composition (Figure

325
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9e-h), similar to what was seen in the BOF slag. The estimated porosities by image analysis are:
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326 0.8% for Figure 9a, 3.8% for Figure 9b, 17% for Figure 9c, 0.1% (interior) and 24% (edge) for

327 Figure 9e, 16% (interior) and 44% (edge) for Figure 9f, and 23% (interior) and 34% (edge) for
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328 Figure 9g. In examining the EDXS elemental maps (Figure 10), the solid composition contains a
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329 calcium silicate (larnite) matrix with an iron-rich phase (wüstite) and a calcium aluminate phase
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330 (mayenite). The outer layer is rich in calcium and aluminum along with some silicon and carbon,

331 suggesting the presence of calcium carbonate, calcium hydroxide, calcium carboaluminate
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332 hydrate, and/or calcium silicate hydrate phases [14,15,18]. This EAF/LMF slag was found to

333 contain about 0.2% calcium hydroxide, 0.9% calcium carbonate, and 0.4% free calcium oxide
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334 [6,7].
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335

336

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(a) (b) (c)

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(d) (e) (f)
Figure 9. Compositional BSE micrographs
of an EAF/LMF slag particle showing the
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solid interior (a), interior with some pores
(b), porous interior (c), edge with
composition similar to the solid interior
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(d), edge of different composition with a

small outer layer (e), edge with large pores
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(f), and porous edge with an outer layer (g,

h).
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(a) BSE (b) Ca

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(c) Si (d) Fe
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337 Figure 10. Compositional BSE (a) and EDXS maps (b-f) of the edge of an EAF/LMF slag
338 particle. The black phase along the left hand side in the BSE micrograph is epoxy. Note: EDXS
339 images have been contrast-enhanced to better indicate the elemental density.
340

341 In comparison, examination of dolomite (Figure 11) reveals a relatively homogenous

342 single-phase microstructure with some porosity. The white interstitial phase seen in the

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343 microstructure was reasoned to be silica, based on evidence from EDXS. In contrast to some of

344 the SFS types, the dolomite does not exhibit a weakened edge, i.e., higher porosity or a different

345 phase along the particle edge.

346

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347 Figure 11. Compositional BSE micrographs of the interior (a) and edge (b) of a dolomite
348 aggregate.
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349

350 3.5 Microstructure Relative to Bulk Properties

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351 The SEM analysis demonstrated that, depending on the SFS type, the ITZ porosity can be
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352 different from dolomite aggregates. EAF slag aggregates can produce mortar and concrete bulk
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353 strengths that are statistically greater than the control (dolomite), which can be reasoned to be a

354 result of the similar ITZ composition to dolomite (e.g., porosity distribution), the angularity and
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355 rough texture of the EAF particle [43], which provides better mechanical interlock, and the
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356 higher modulus (stiffness) of the aggregate. In general, SFS is denser and stiffer than carbonate

357 aggregates, which, along with the higher density, is the cause for the statistically greater dynamic

358 modulus values, given that the ITZ composition was not necessarily the same for all SFS types.

359 This BOF slag was found to reduce the concrete strength at 28 days relative to dolomite

360 [6], which can be argued to be a result of: 1) the more porous ITZ, allowing for easier crack

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361 initiation and propagation, and 2) the outer layer on the BOF particles, which was also more

362 porous, thus also allowing for easier crack initiation and propagation. Therefore, the BOF slag

363 can be thought of as containing two ITZs, one surrounding the SFS particle that is likely to be

364 composed of reaction products (e.g., calcium carbonate, which was identified by X-ray

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365 diffraction) and the other formed with the cement paste. Either or both of these ITZs can be

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366 sources of the failure of the bulk mortar or concrete, thus yielding the reduction in strength. The

367 EAF/LMF slag exhibited some evidence of a similar porous outer layer, but the layer was not

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368 present everywhere. Rather the EAF/LMF slag microstructure was rather porous in some areas,

369 which is an additional source of weakness, potentially allowing for easier crack propagation

370
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through the particle. Comparatively, EAF slag did not exhibit such an outer layer and was found
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371 to lead to statistically higher strengths relative to dolomite. Since the EAF/LMF slag was not

372 porous throughout the entire particle and the outer layer was not present along all edges, it is
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373 possible that the EAF/LMF slag experiences similar bonding and mechanical interlock to the
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374 EAF slag, thus potentially yielding higher strengths relative to dolomite.
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375 An additional consideration concerns the possibility of chemical reaction of the cement

376 paste with the SFS surface. While SFS mineral composition may have some similarities to
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377 portland cement clinker, the dicalcium silicate (larnite) that is present has been argued to be

378 nonreactive [44]. Studies have demonstrated that EAF slag is relatively inert [45], but BOF slag
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379 may be somewhat (weakly) reactive [46,47], primarily as a result of the higher free CaO content,
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380 although more reactive phases such as tricalcium silicate can be present (Table 2). Other studies

381 have shown that weakly reactive SFS has to be reprocessed in order to enhance its reactivity

382 [48,49]. Regardless, a number of studies have argued that the increase in concrete strength with

383 SFS aggregates is because of such a chemical reaction [8–10], although the reacted outer layer

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384 has also been argued to be the cause of the decrease in concrete strength with SFS aggregates

385 [15]. Therefore, it can be argued that SFS aggregates have the potential to increase mortar or

386 concrete strength because of the rough angularity and high stiffness of the particles in addition to

387 the potential for a chemical reaction. This potential for increase in strength is counteracted by

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388 weaknesses, such as a greater ITZ porosity, a porous outer layer on the SFS aggregate, and/or a

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389 porous interior of the SFS aggregate. These weaknesses counteracted any strength increasing

390 factors such that the BOF slag aggregates produced lower concrete strengths relative to dolomite.

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391 The lack of such weaknesses is why the EAF slag aggregates produced higher concrete strengths

392 relative to dolomite.

393
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Based on the findings presented herein and those presented in the literature, it can be
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394 concluded that a number of factors affect the mechanical behavior of cementitious composites

395 with SFS aggregates. An increase in performance may be attributed to the roughness, angularity,
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396 density, and stiffness of the SFS aggregate as well as potential for chemical reaction. A decrease
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397 in performance may be attributed to a more porous ITZ, a larger ITZ width, the presence of a
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398 porous outer layer on the SFS aggregate, the composition of the outer layer on the SFS

399 aggregate, and a porous interior of the SFS aggregate.

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400

401 4. Conclusions
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402 Steel furnace slag (SFS) aggregates are a waste by-product consisting of dense, stiff
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403 particles with significant variability in chemical composition, morphology, and properties

404 depending on the steel production process. In this study, SFS aggregates from three different

405 processes – basic oxygen furnace (BOF), electric arc furnace (EAF), and EAF/ladle metallurgy

406 furnace (EAF/LMF) slags – were evaluated for their effect on microstructure development in

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407 cementitious composites. Relative to a dolomite aggregate source, all three SFS aggregate types

408 statistically increased the dynamic modulus in a high paste mortar. The EAF slag resulted in

409 statistically greater mortar compressive strengths at 28 days, while concrete with BOF slag

410 yielded statistically lower compressive strengths at 28 days. The reported trends are consistent

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411 with the variability in the literature, where SFS aggregates have been shown to increase,

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412 decrease, or have no effect on concrete properties.

413 Backscatter electron microscopy and quantitative image analysis were employed to

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414 observe changes in the composition of the SFS aggregates and its influence on the interfacial

415 transition zone (ITZ) of SFS mortars. The ITZ was more porous for the BOF and EAF/LMF slag

416
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mortars while the EAF slag mortar had a similar porosity to the dolomite mortar. The unhydrated
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417 cement distributions were similar for all mortars. The dolomite mortar had a greater amount of

418 calcium hydroxide immediately near the aggregate interface, while the SFS mortars had calcium
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419 hydroxide contents that were relatively consistent along the length of the ITZ.
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420 In examining the microstructure of SFS aggregates, BOF slag and some sections of the
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421 EAF/LMF slag were found to contain a more porous outer layer with different composition than

422 the interior of the particle. This outer layer was not seen in the EAF slag. Thus, mortar with SFS
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423 aggregates that have this outer layer can be thought of as consisting of two ITZs, the one

424 surrounding the SFS particle and the other formed with the cement paste, both of which can
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425 allow for easier crack initiation and propagation, and therefore, can result in a reduction in
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426 hardened properties such as strength.

427 From the findings in this study in conjunction with previous studies, the mechanical

428 properties of cementitious composites are affected by the roughness, angularity, density, and

429 stiffness of the SFS aggregates. In addition, the potential for chemical reaction between the SFS

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430 aggregate and the cement paste may increase bonding and improve mechanical performance.

431 However, some SFS aggregates may result in a larger or more porous ITZ and the SFS aggregate

432 may have a porous outer layer or a porous interior, all of which may negatively affect the

433 mechanical behavior.

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434

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435 Acknowledgements

436 The SEM and EDXS analyses were carried out in part at the Frederick Seitz Materials Research

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437 Laboratory Central Research Facilities, University of Illinois. The authors would like to thank

438 the National Slag Association, Tube City IMS, South Shore Slag, and Edw. C. Levy Co. for

439 providing SFS materials.

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440

441 References
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442 [1] C. Shi, Steel slag - its production, processing, characteristics, and cementitious properties,
443 J. Mater. Civ. Eng. 16 (2004) 230–236.
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444 [2] H. Motz, J. Geiseler, Products of steel slags: an opportunity to save natural resources, in:
445 G.R. Woolley, J.J.J.M. Goumans, P.J. Wainwright (Eds.), Waste Materials in
TE

446 Construction, Elsevier Science, Oxford, 2000: pp. 207–220.

447 [3] B. Erlin, D. Jana, Forces of hydration that can cause havoc in concrete, Concr. Int. 25
448 (2003) 51–57.
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449 [4] N. Balcázar, M. Kühn, J.M. Baena, A. Formoso, J. Piret, Summary report on RTD in iron
450 and steel slags: development and perspectives, Proceedings No. EUR 19066 EN,
451 European Commission, Luxembourg, 1999.
452 [5] R.J. Collins, S.K. Ciesielski, Recycling and use of waste materials and by-products in
C

453 highway construction, NCHRP Synthesis 199, Transportation Research Board,

454 Washington DC, 1994.
AC

455 [6] A.S. Brand, J.R. Roesler, Steel furnace slag aggregate expansion and hardened concrete
456 properties, Cem. Concr. Compos. 60 (2015) 1–9. doi:10.1016/j.cemconcomp.2015.04.006.
457 [7] A.S. Brand, J.R. Roesler, Concrete with Steel Furnace Slag and Fractionated Reclaimed
458 Asphalt Pavement, Report No. ICT-14-015, Urbana, 2014.
459 [8] D.G. Montgomery, G. Wang, Instant-chilled steel slag aggregate in concrete - strength
460 related properties, Cem. Concr. Res. Res. 21 (1991) 1083–1091.
461 [9] Y. Wang, The effect of bond characteristics between steel slag fine aggregate and cement
462 paste on mechanical properties of concrete and mortar, Mater. Res. Soc. Symp. Proc. 113
463 (1988) 301–306.

28
 ACCEPTED MANUSCRIPT

464 [10] G. Wang, Properties and utilization of steel slag in engineering applications, PhD
465 Dissertation, University of Wollongong, Wollongong, Australia, 1992.
466 [11] I. Arribas, A. Santamaría, E. Ruiz, V. Ortega-López, J.M. Manso, Electric arc furnace slag
467 and its use in hydraulic concrete, Constr. Build. Mater. 90 (2015) 68–79.
468 doi:10.1016/j.conbuildmat.2015.05.003.
469 [12] B. Pang, Z. Zhou, X. Cheng, P. Du, H. Xu, ITZ properties of concrete with carbonated
470 steel slag aggregate in salty freeze-thaw environment, Constr. Build. Mater. 114 (2016)

PT
471 162–171. doi:10.1016/j.conbuildmat.2016.03.168.
472 [13] J.T. San-José, I. Vegas, I. Arribas, I. Marcos, The performance of steel-making slag
473 concretes in the hardened state, Mater. Des. 60 (2014) 612–619.

RI
474 [14] A. Coomarasamy, T.L. Walzak, Effects of moisture on surface chemistry of steel slags
475 and steel slag-asphalt paving mixes, Transp. Res. Rec. 1492 (1995) 85–95.
476 [15] M. Kawamura, K. Torii, S. Hasaba, N. Nicho, K. Oda, Applicability of basic oxygen

SC
477 furnace slag as a concrete aggregate, in: V.M. Malhotra (Ed.), Fly Ash, Silica Fume, Slag
478 and Other Mineral By-Products in Concrete, ACI Special Publication 79, American
479 Concrete Institute, Detroit, 1983: pp. 1123–1141.
480 [16] S. Mindess, J.F. Young, D. Darwin, Concrete, 2nd ed., Pearson Education, Upper Saddle

U
481 River, 2003.
482 [17] P.K. Mehta, P.J.M. Monteiro, Concrete: microstructure, properties, and materials, 4th ed.,
AN
483 McGraw-Hill, New York, 2014.
484 [18] B. Pang, Z. Zhou, H. Xu, Utilization of carbonated and granulated steel slag aggregate in
485 concrete, Constr. Build. Mater. 84 (2015) 454–467.
486 doi:10.1016/j.conbuildmat.2015.03.008.
M

487 [19] A. Elsharief, M.D. Cohen, J. Olek, Influence of aggregate size, water cement ratio and age
488 on the microstructure of the interfacial transition zone, Cem. Concr. Res. 33 (2003) 1837–
489 1849. doi:10.1016/S0008-8846(03)00205-9.
D

490 [20] ASTM C39, Standard test method for compressive strength of cylindrical concrete
491 specimens, ASTM International, West Conshohocken, 2015.
TE

492 [21] ASTM C496, Standard test method for splitting tensile strength of cylindrical concrete
493 specimens, ASTM International, West Conshohocken, 2011.
494 [22] ASTM C215, Standard test method for fundamental transverse, longitudinal, and torsional
EP

495 frequencies of concrete specimens, ASTM International, West Conshohocken, 2008.

496 [23] A.S. Brand, J.R. Roesler, Bonding in cementitious materials with asphalt-coated particles:
497 part I – the interfacial transition zone, Constr. Build. Mater. 130 (2017) 171–181.
498 doi:10.1016/j.conbuildmat.2016.10.019.
C

499 [24] A.S. Brand, Interfacial transition zone composition and bonding in cementitious systems
500 with asphalt-coated particles, University of Illinois at Urbana-Champaign, 2015.
AC

501 http://hdl.handle.net/2142/88969.
502 [25] K.L. Scrivener, A.K. Crumbie, P. Laugesen, The interfacial transition zone (ITZ) between
503 cement paste and aggregate in concrete, Interface Sci. 12 (2004) 411–421.
504 doi:10.1023/B:INTS.0000042339.92990.4c.
505 [26] K.L. Scrivener, E.M. Gartner, Microstructural gradients in cement paste around aggregate
506 particles, Mater. Res. Soc. Symp. Proc. 114 (1988) 77–86.
507 [27] K.L. Scrivener, Backscattered electron imaging of cementitious microstructures:
508 understanding and quantification, Cem. Concr. Compos. 26 (2004) 935–945.
509 doi:10.1016/j.cemconcomp.2004.02.029.

29
 ACCEPTED MANUSCRIPT

510 [28] S. Diamond, Considerations in image analysis as applied to investigations of the ITZ in
511 concrete, Cem. Concr. Compos. 23 (2001) 171–178. doi:10.1016/S0958-9465(00)00085-
512 8.
513 [29] H.S. Wong, M.K. Head, N.R. Buenfeld, Pore segmentation of cement-based materials
514 from backscattered electron images, Cem. Concr. Res. 36 (2006) 1083–1090.
515 doi:10.1016/j.cemconres.2005.10.006.
516 [30] H.S. Wong, N.R. Buenfeld, Euclidean distance mapping for computing microstructural

PT
517 gradients at interfaces in composite materials, Cem. Concr. Res. 36 (2006) 1091–1097.
518 doi:10.1016/j.cemconres.2005.10.003.
519 [31] S. Diamond, Calcium hydroxide in cement paste and concrete – a microstructural apraisal,

RI
520 in: J. Skalny, J. Gebauer, I. Odler (Eds.), Material Science of Concrete, Special Volume:
521 Calcium Hydroxide in Concrete, American Ceramic Society, Westerville, 2001: pp. 37–
522 58.

SC
523 [32] E. Gallucci, K. Scrivener, Crystallisation of calcium hydroxide in early age model and
524 ordinary cementitious systems, Cem. Concr. Res. 34 (2007) 492–501.
525 [33] S. Mindess, The strength and fracture of concrete: The role of calcium hydroxide, in: J.
526 Skalny, J. Gebauer, I. Odler (Eds.), Material Science of Concrete, Special Volume:

U
527 Calcium Hydroxide in Concrete, American Ceramic Society, Westerville, 2001: pp. 143–
528 154.
AN
529 [34] Federal Highway Administration, User Guidelines for Waste and Byproduct Materials in
530 Pavement Construction, Report No. FHWA-RD-97-148, Washington DC, 1997.
531 [35] G.C. Wang, The Utilization of Slag in Civil Infrastructure Construction, Elsevier,
532 Amsterdam, 2016.
M

533 [36] R.S. Kalyoncu, Slag—Iron and Steel, in: Miner. Yearb., United States Geological Survey,
534 Reston, 2001.
535 [37] S. Diamond, J. Huang, The ITZ in concrete - a different view based on image analysis and
D

536 SEM observations, Cem. Concr. Compos. 23 (2001) 179–188. doi:10.1016/S0958-

537 9465(00)00065-2.
TE

538 [38] A.K. Crumbie, Characerisation of the microstructure of concrete, PhD Dissertation,
539 University of London, 1994.
540 [39] D. Bonen, Calcium hydroxide deposition in the near interfacial zone in plain concrete, J.
EP

541 Am. Ceram. Soc. 77 (1994) 193–196.

542 [40] P.J.M. Monteiro, P.K. Mehta, Interaction between carbonate rock and cement paste, Cem.
543 Concr. Res. 16 (1986) 127–134. doi:10.1016/0008-8846(86)90128-6.
544 [41] K.L. Scrivener, Characterisation of the ITZ and its quantification by test methods, in:
C

545 M.G. Alexander, G. Arlinguie, G. Ballivy, A. Bentur, J. Marchand (Eds.), Engineering

546 and Transport Properties of the Interfacial Transition Zone in Cementitious Composites,
AC

547 RILEM Publications, Cachan Cedex, 1999: pp. 3–15.

548 [42] J. Geiseler, Composition and structure of slags, in: Verein Deutscher Eisenhüttenleute
549 (Ed.), Slag Atlas, 2nd ed., Verlag Stahleisen, Düsseldorf, 1995: pp. 215–224.
550 [43] I.Z. Yildirim, M. Prezzi, Chemical, mineralogical, and morphological properties of steel
551 slag, Adv. Civ. Eng. 2011 (2011) 463638.
552 [44] J.J. Emery, Slag Utilization in Pavement Construction, in: Extending Aggreg. Resour.
553 ASTM Spec. Tech. Publ. 774, American Society for Testing and Materials, Philadelphia,
554 1982: pp. 95–118.
555 [45] M.F. Rojas, M.I. Sánchez de Rojas, Chemical assessment of the electric arc furnace slag

30
 ACCEPTED MANUSCRIPT

556 as construction material: Expansive compounds, Cem. Concr. Res. 34 (2004) 1881–1888.
557 doi:10.1016/j.cemconres.2004.01.029.
558 [46] P.Y. Mahieux, J.E. Aubert, G. Escadeillas, M. Measson, Quantification of Hydraulic
559 Phase Contained in a Basic Oxygen Furnace Slag, J. Mater. Civ. Eng. 26 (2014) 593–598.
560 doi:10.1061/(ASCE)MT.1943-5533.0000867.
561 [47] E. Belhadj, C. Diliberto, A. Lecomte, Properties of hydraulic paste of basic oxygen
562 furnace slag, Cem. Concr. Compos. 45 (2014) 15–21.

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563 doi:10.1016/j.cemconcomp.2013.09.016.
564 [48] J.N. Murphy, T.R. Meadowcroft, P.V. Barr, Enhancement of the cementitious properties
565 of steelmaking slag, Can. Metall. Q. 36 (1997) 315–331. doi:10.1179/cmq.1997.36.5.315.

RI
566 [49] L. Muhmood, S. Vitta, D. Venkateswaran, Cementitious and pozzolanic behavior of
567 electric arc furnace steel slags, Cem. Concr. Res. 39 (2009) 102–109.
568 doi:10.1016/j.cemconres.2008.11.002.

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569

570 Appendix

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571 Examples of BSE images of the ITZ are shown in Figure A.1, detailing the relevant
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572 features. The SFS particle is highly visible as a large white feature because of the high iron

573 content. The UH cement particle are also visible as white features. CH is light grey and porosity
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574 is black. Any intermediate greyscale between porosity and CH is considered C-S-H and other

575 hydration products. The outer layer, as discussed in Section 3.4 for the BOF and EAF/LMF
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576 slags, is also visible and labeled in Figure A.1. This outer layer, while of similar greyscale
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577 characteristics to sections of the ITZ, could be segmented from the rest of the ITZ because it was
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578 continuous.

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(a)

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(b)
580 Figure A.1. Example BSE images of the ITZ for (a) BOF slag at 1 day and (b) EAF/LMF slag at
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581 7 days. The interior (I) and outer layer (OL) of the SFS are detailed as well as the approximate
582 ITZ width. Examples of porosity, UH, and CH are also highlighted.
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583

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