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Construction and Building

Construction and Building Materials 23 (2009) 5461

MATERIALS
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A chemical analysis method for determining blast-furnace slag content in hardened concrete
Kritsada Sisomphon *
Department of Civil Engineering, National University of Singapore, Block E1A, #07-03, 1 Engineering Drive 2, Singapore 117576, Singapore Received 3 April 2007; received in revised form 8 February 2008; accepted 8 February 2008 Available online 17 March 2008

Abstract This research presents the results of the study on the estimation of blast-furnace slag content in hardened concrete by chemical analysis method. To determine slag content in the mixture, there are two steps of investigation. The fraction of sand content in the mortar extracted from concrete has to be determined, and then the chemical composition of cement paste phase can be calculated. Thereafter, slag content in the mixture can be estimated by the relationship of chemical composition among in cement paste, Portland cement and slag. Articially made mortars and concrete mixes with slag content of 30%, 50% and 70% by mass exposed to dierent curing durations were investigated. The results suggest that the techniques have potential for estimation of blast-furnace slag content in already hardened concrete with acceptable accuracy. 2008 Elsevier Ltd. All rights reserved.
Keywords: Chemical analysis; Ground granulated blast-furnace slag; XRD; XRF

1. Introduction Granulated blast-furnace slag has been widely used in cement manufacturing and concrete mixtures. From both environmental and economical points of view, slag is a very attractive mineral admixture to use in concrete, especially as low heat concrete for massive structures or as high performance concrete. However, it may result in decrement of compressive strength at early ages and delay of setting time depending on percentage and quality of the slag used in the mixture. Moreover, if the batching of the slag relative to cement is not accurate, long-term behaviors of concrete may be aected as well especially durability problems. In situations where there are disputes among project owner, concrete supplier and contractor, determining the quantity of cement and slag used in already hardened concrete is essential.
* Present address: Faculty of Civil Engineering and Geosciences, Delft University of Technology, Stevinweg 1, 2628 CN Delft, The Netherlands. Tel.: +31 0 15 27 8 1325; fax: +31 0 15 27 8 8162. E-mail addresses: k.sisomphon@tudelft.nl, sisomphon@hotmail.com

Analytical methods were proposed by various researchers for determining mix proportion of hardened concrete. In work of Hooton and Rogers [1], the X-ray diraction technique of ignited mixture to determine the slag content in hardened concrete was studied. The method involves ignition of the mortar fraction of concrete at 950 1050 C to devitrify unreacted slag. Thereafter, the resulting crystalline melilite component is compared to that in an ignited sample of blast-furnace slag from the same source. This method is applicable to slag with very ne particle size distribution. More importantly, this technique can be applied only to slag which converts mainly to melilite after the high temperature devitrication, and the calibration curve for each particular slag is essentially required. Hooton and Rogers [1] also proposed a method to determine slag content by optical microscopy on thin sections made from the hardened concrete. This method involves the preparation of thin sections of the concrete and determination of the content of residue slag particles by point counting. Basically, the technique can approximate slag content on the scale: none, a little (<25%), a moderate amount (2560%) and a lot (>60%). If the more detailed

0950-0618/$ - see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.conbuildmat.2008.02.003

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estimation is required, point counting may be used, but the importance of knowing the particle size distribution of the slag is crucial to obtain an estimation that is accurate within 10%. Grantham [2] examined results of quantitative X-ray uorescence (XRF) analysis of concrete, and applied a mathematical approach to obtain the content of the individual components. The method has been successfully employed by a number of UK laboratories and provides another possible way of resolving the composition of concrete in which it is suspected that mis-batching may have occurred. A previous study [3] presented results for estimating slag content in hardened cement paste using chemical analysis method and w/cm of hardened concrete using petrographic technique. Cement paste mixtures with a controlled w/cm ratio of 0.40 and slag contents of 0%, 30%, 50% and 70% by mass of total cementitious materials were investigated at the age of 28 and 91 days. The results reveal a good estimation of slag contents. If the chemical compositions of raw materials are known, the absolute error of estimation of the slag content is within 5% by mass of cementitious materials. However, the method can be applicable to only cement paste mixtures without presence of sand and gravel. To determine the quality of hardened slag concrete, several parameters have to be investigated, such as water to cementitious ratio (w/cm), slag to total cementitious ratio (r), sand to aggregate ratio (s/a) and total aggregate content. Among these parameters, w/cm and r play an important role on properties of concrete. Petrographic method has been used for many years to determine w/cm of hardened concrete [39]. However, in modern concrete where the mixture has been added more mineral and chemical admixtures, capillary porosity may have a more signicant inuence on concrete durability, and would be a more useful parameter than the original value of w/cm ratio. In case of aggregate content and particle shape, it can be investigated using image analysis mentioned in various studies elsewhere [1012]. This research introduces techniques and results on the determination of slag content in already hardened mixtures by chemical methods. As preliminary investigation, nely ground hardened slag cement pastes were blended with sand powder at various mass ratio to simulate articial mortar mixes. Thereafter, the verication of the techniques was performed on actual hardened concrete with the age up to 91 days. 2. Experimental investigation 2.1. Materials Ordinary Portland cement (ASTM Type I), ground granulated blast-furnace slag, natural quartz sand and granite stone with maximum size of 10-mm were used for all mixtures. For cement paste mixtures, a normal Portland cement, OPC1, was used. However, another batch of Port-

land cement (OPC2) was used for concrete mixtures. Three dierent sources of quartz sand, Sand A, B and C, were used in this study to investigate the inuence of quartz content (SiO2) in sand on the analysis results. Chemical compositions of raw materials are shown in Table 1. 2.2. Mix proportions, curing conditions and sample preparations For cement paste mixes, three cement paste mixtures were prepared with a controlled w/cm ratio of 0.40 and slag contents of 30%, 50% and 70% by mass of total cementitious materials. The pastes were cured in a sealed condition in the rst 24 h followed by curing in a fog room with a relative humidity of 100% and temperature of 30 C until 28 and 91 days. At these ages, the pastes were broken into small pieces, and dried in a vacuum oven at 40 C until constant weight was reached. The samples were then ground into ne powders passing through 75 lm sieve. The powder samples were kept in glass bottles and stored in a desiccator for analyses. The chemical composition of the cement pastes determined by XRF is presented in Table 2. For concrete specimens, three concrete mixtures with a controlled w/cm ratio of 0.45 were prepared. Cubes of 100 mm were cast from each concrete mix. The mix proportion and properties are presented in Table 3. After 24 h curing in steel moulds covered with plastic sheet, the samples were cured in the fog room until 14, 28 and 91 days. At specied ages, the specimens were crushed for compressive strength test, and the result strength was obtained from an average of three cubes. Thereafter, the outer surfaces of the concrete cubes were deposed. To extract mortar, the samples were further crushed to be small pieces, and the coarse particles were removed by using 1.18 mm sieve. The mortar grains were dried at 105 C for 24 h, and nally sieved passing through 150 lm. The extracted mortar powders were kept in glass bottles and stored in a desiccator for chemical analysis purposes. 2.3. Methods of investigation To determine slag content in hardened concrete, there are two steps of investigation. The sand content (z) in the mixture has to be estimated, and then the oxide content
Table 1 Chemical composition of cements, slag and aggregates used Oxide content (% by mass) CaO SiO2 Al2O3 Fe2O3 Na2O K2O MgO SO3 OPC1 65.3 20.8 4.9 3.2 0.17 0.30 3.4 2.0 OPC2 66.0 20.8 4.7 3.5 0.10 0.35 2.6 1.9 Slag 42.4 30.4 16.0 0.42 0.15 0.24 7.9 2.6 Granite 0.11 72.1 17.4 3.4 3.45 3.04 0.13 Sand A 95.1 4.2 0.44 0.31 Sand B 96.2 3.0 0.62 0.12 Sand C 99.8 0.14

: Non-detectable due to zero or small content.

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Table 2 Chemical compositions of the hardened cement pastes determined by XRF technique Oxide content (% by mass) 30% Slag (30S-28d) 50% Slag (50S-28d) 49.30 25.50 10.35 6.44 0.04 0.20 2.86 0.78 50% Slag (50S-91d) 52.33 25.21 8.74 2.07 0.07 0.19 4.67 1.62 70% Slag (70S-28d) 43.25 28.00 13.81 8.14 0.04 0.23 2.81 0.56 70% Slag (70S-91d) 48.34 27.65 11.04 1.49 0.09 0.22 5.63 1.88

(a) Cement paste samples cured for 28 days CaO 55.33 23.30 SiO2 7.57 Al2O3 5.09 Fe2O3 0.07 Na2O 0.19 K2O MgO 2.82 0.93 SO3 Oxide content (% by mass) 30% Slag (30S-91d)

the isopropanol had evaporated, powder XRD slides were prepared and analyzed by a Shimadzu XRD-6000 using copper Ka radiation with scanning speed of 2/min. As shown in Fig. 2, the peak at about 28.3 (2h) represents the calcium uoride that acted as an internal standard for quantitative determination. Instead of the highest peak at 26.6 (2h), the peak of quartz at about 20.8 (2h) which has no overlapping of spectrum with any hydrated cement phases was selected to identify the quantity of sand in mixture. The relationship between peak intensity ratios of quartz (20.8) to the internal standard (28.3) obtained from three replicate scans and sand content can be constructed. Thereafter, the relationship has been veried with the analysis results of the actual mortar extracted from concrete mixes. 2.3.1.2. Technique by HCl dissolving. In this method, the mortar powders were dissolved in hydrochloric acid (HCl). The 5 g of the sample was dissolved into 250 ml of 0.5 M HCl in a conical ask. The solution was shaken for 30 min on a rotating table then ltrated through a dense lter paper. The lter paper with the residue was washed with deionized water and isopropanol, and then oven-dried at 105 C for 24 h. Finally, the residual weight after dissolution process can be measured. Fig. 3 shows results of the dissolving test on hardened slag cement paste and various sources of sands separately. It was found that all slag cement paste powders can be almost completely dissolved into the HCl acid, whereas only small fraction of sand will be diluted into the acid solution. Therefore, if the technique is performed on concrete or mortar mixes, the amount of the nal residue would be able to present the aggregate content in mixture. However, it would be remarked that only Sand A was used in all articial mortars and concrete mixes. Sand B and C were dissolved to conrm the stability of quartz sands obtained from various sources in the acid dissolution as obviously seen in the gure. 2.3.2. Determination of slag to total cementitious material ratio In Singapore, quartz sand and granite stone are the aggregates most commonly used in concrete mixes. Generally, quartz sands contain more than about 95% of SiO2, and only minor Al2O3 is another oxide that can be possible detected. For granite, it is basically a composition of quartz and alkali feldspar. Therefore, its major compositions would be SiO2 and Al2O3, with some Fe2O3, Na2O and

(b) Cement paste samples cured for 91 days CaO 55.82 22.93 SiO2 6.58 Al2O3 2.52 Fe2O3 0.06 Na2O 0.18 K2O MgO 3.80 1.38 SO3

is cement paste phase can be calculated. Thereafter, the ratio of slag to total cementitious material content (r) in the mixture can be determined. The ow chart of investigation is as in Fig. 1. In this section, the methods for determining sand content and slag to cementitious ratio in the mixtures will be explained in detail. Two dierent techniques for determining sand content have been proposed, namely XRD analysis and HCl dissolving. Eventually, slag content in the mixtures (r) can be estimated by using mass balance equation of oxide content. 2.3.1. Determination of sand content 2.3.1.1. Technique by using XRD analysis. The assumption of this method is that all coarse aggregate grains have been completely removed from the crushed concrete. Thereafter, quartz content in the specimen representing sand content in mixture can be determined by XRD analysis. In the preliminary experiment, the slag cement paste powders were mixed with sand powder to simulate articial mortar. The sand content has varied between 0.30 and 0.75 as shown in Table 4. After that, the prepared mixtures were blended with 10% reagent grade calcium uoride (CaF2) by mass as internal standard in isopropanol and further uniformly mixed with an agate mortar and pestle. After
Table 3 Mix proportions, slump and compressive strength of concrete Mix Materials (kg/m3) Cement BFS30 BFS50 BFS70 280 200 120 Slag 120 200 280 Water 180 180 180 Sand 712 712 712 Gravel 1068 1068 1068

Slump (mm) Deracem 100 2.50 1.77 1.61 105 65 75

Compressive strength (MPa) 14 days 41.7 45.0 40.1 28 days 62.0 60.0 47.9 91 days 65.3 64.8 57.1

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Concrete
Crushing & Sieving

Extracted mortar

XRD

Determined CaO content (CaOm)

Determined sand content (z)

HCl dissolving

Estimated CaO in paste (CaOp )

Estimated slag content (r)

Fig. 1. Flow chart of determination.

Table 4 Estimation of aggregate content by XRD technique

1.00 0.90

98.6%

98.6%

98.5%

Residual weight

Age

Mixture

Actual aggregate content 0.40 0.55 0.75 0.65 0.50 0.30

Mean intensity ratio 0.4486 0.7973 1.2089 0.9694 0.5937 0.3127

Estimated aggregate content 0.393 0.561 0.760 0.645 0.463 0.327

Error (%) 0.7 1.1 1.0 0.5 3.7 2.7

0.80 0.70 0.60 0.50 0.40 0.30 0.20 0.10 0.00

70 S28 d 50 S28 d 91 d 70 S91 d 28 d 30 S91 d A Sa nd B 30 S50 SSa nd Sa nd C
1.1% 1.4% 0.8% 0.5% 0.0% 1.0%

28 days 91 days

30S 50S 70S 30S 50S 70S

Fig. 3. Residue weight of the powder after dissolving in 0.5 M HCl.

Quartz

Intensity

Feldspar

Quartz

CaF 2

which are cement paste phase (p) and aggregate phase (a). By using mass balance equation, the relationship among the oxide content in hardened concrete or mortar, in cement paste and in aggregate can be written as follows. xm 1 z xp z xa 1

Kaolinite

20

21

22

23

24

25

26

27

28

29

30

2
Fig. 2. XRD analysis result of articial mortar with 10% CaF2.

K2O as minor components. The benet of these aggregates on the chemical analyzing technique is that they contain negligible amounts of CaO. Hence, if any CaO content can be detected from the hardened mortar or concrete mixes, it would be able to assume that all content arises from cement paste phase. To estimate the slag ratio in mixture, the oxide content of cement paste phase in the mixture has to be investigated. Basically, the mixtures (m) consisted of two components

where xm, xp and xa are the oxide content (% by mass) in the mixture, cement paste phase and aggregate phase, respectively, and z is an aggregate ratio in the mixture. Since CaO content in the aggregate is very minor and negligible (CaOa % 0), Eq. (1) can be rearranged, and the CaO content in the cement paste can be calculated by using the following equation. CaOp CaOm z1 2

where CaOm and CaOp are CaO content in the mixture and cement paste phase, respectively. z is the aggregate ratio in the mixture which can be estimated by using the method described in Section 2.3.1.1 or 2.3.1.2. In case of hardened concrete analysis, CaOm is the CaO content in the mortar extracted from the concrete.

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Eventually, the slag ratio (r) can be calculated as an equation shown below r CaOp CaOOPC CaOslag CaOOPC 3

where CaOOPC and CaOslag are CaO content in Portland cement and slag, respectively, and CaOp is the CaO content in paste which can be determined and calculated by Eq. (2). 3. Results and discussion 3.1. Determination of sand contents in articial mortars As mentioned early, three sources of sand were involved in this study. However, only Sand A was used in concrete mixes. Therefore, by using Sand A, the relationship between the mean intensity ratio and sand content in articial mortars were constructed as shown in Fig. 4. The results show a good relationship between them. The empirical equation is nally obtained, and the sand content in mixtures can be estimated by relationship shown following:   Iq 0:1763 4 z 0:4831 I ref where z is the sand content in mixture (mass/mass); Iq is the peak intensity of quartz (counts); Iref is the peak intensity of CaF2 (counts). The amounts of sand content in articial mortar are estimated by using Eq. (4) as the results shown in Table 4. The estimation results show the accuracy of 4% sand content by mass. The XRD analysis results on pure slag paste show that there is no signicant peak can be detected at both angles, 20.8 and 28.3 (2h). Hence, the ratio between these two peaks would permit to estimate sand content eectively without any interference of other cement phases presence. With up to 91 days age results, the degree of cement and slag hydration does not show any eect on the values of peaks intensity. However, it would be kept in mind that this method is applicable only if the source of sand used in the concrete is known. Normally, quartz content in sand can be variable depending on origin and composition of the
0.80 0.70
y = 0.4831x + 0.1763 R2= 0.9819

sand. As seen in Fig. 4, Sand B and C mixtures show higher intensity ratio values which may be due to their higher SiO2 content as presented in Table 1. Moreover, the crystallinity of SiO2 in each source of sand may dierent, which would also aect the intensity of quartz peak detected by XRD. Therefore, calibration curve for each particular source of sand is essentially required for an accurate estimation. Another technique for determining sand and aggregate content in mixture is the method dissolving the sample powder in 0.5 M HCl. The method shows a better eectiveness of analysis than the XRD method as results shown in Table 5. The technique can be applied to any quartz sand and granite stone whereas assuming that the aggregates are stable under dissolving in the acid. The results on articial mortar testing indicated that the technique can estimate sand content with high accuracy of 1% by mass. 3.2. Determination of slag contents in articial mortars The determined results of slag content in articial mortars are as shown in Table 6. There are two techniques to investigate sand content, and therefore two sets of estimation results can be obtained and compared as shown follows. As obviously seen in Table 6, the investigation of sand content in articial mortar mixes using HCl dissolving technique yields more accurate estimation than those from XRD method. The error of estimation by HCl dissolving method is on average less than 1.0% as shown in Table 5. From reason mentioned above, the investigation results indicated that the HCl dissolving method shows a more accurate estimation on slag content. The maximum error of estimation is about 6.0%, whereas the highest error of 24.6% was obtained from the XRD method. Moreover, in practice, the HCl dissolving method would be more convenient, and can be applied regardless the fact that the properties of original aggregates are unknown. For XRD method, if the source of sand used in mixture has been changed, the present chart for predicting sand content may be not applicable. As seen in Fig. 4, the articial mortars made from Sand B and C show overestimation which may due to higher quartz contents (SiO2) in those sands. The crystallinity of SiO2 also plays an important role on XRD detection. It seems that there are some diculties

Sand Content

0.60 0.50 0.40 0.30 0.20 0.10

Pure paste

Table 5 Estimation of aggregate content by 0.5 M HCl dissolving

Sand A Sand B Sand C

Age

Mixture

Actual aggregate content 0.40 0.55 0.75 0.65 0.50 0.30

Estimated aggregate content 0.397 0.541 0.738 0.645 0.503 0.301

Error (%)

28 days

0.00 0.00

30S 50S 70S 30S 50S 70S

0.3 0.9 1.2 0.5 0.3 0.1

0.20

0.40

0.60

0.80

1.00

1.20

1.40

Iq / Iref
Fig. 4. Relationship between peak intensity ratio and sand content.

91 days

K. Sisomphon / Construction and Building Materials 23 (2009) 5461 Table 6 Estimation of slag content in articial mortars Sample Actual z CaOm 0.3647 0.2517 0.1325 0.2101 0.2781 0.3428 Actual r XRD method Estimated z 30S-28d 50S-28d 70S-28d 30S-91d 50S-91d 70S-91d 0.40 0.55 0.75 0.65 0.50 0.30 0.30 0.50 0.70 0.30 0.50 0.70 0.393 0.561 0.760 0.645 0.463 0.327 Estimated r 0.251 0.365 0.454 0.292 0.602 0.637 Error r (%) 4.9 13.5 24.6 0.8 10.2 6.3 HCl dissolving method Estimated z 0.397 0.541 0.738 0.645 0.503 0.301 Estimated r 0.251 0.484 0.662 0.309 0.440 0.722

59

Error r (%) 4.9 1.6 3.8 0.9 6.0 2.2

in XRD method. However, if the technique is extended to investigate other mixture that hardly dissolved in acid solution, such as y ash concrete, the XRD method may have an advantage particularly for inspection of suspected misbatching concrete mix in laboratory where properties of all original materials are known. To improve accuracy of analysis, further modications of XRD setting and sample pre-treatment are essentially required to ensure the precision of the analysis in future study. 3.3. Determination of slag contents in hardened concrete Hardened mortars in concrete mixes with slag content of 30%, 50% and 70% cured in fog room for 14, 28 and 91 days were extracted in accordance with the method explained in Section 2.2. The aggregate contents were ana-

lyzed by two dierent methods: XRD technique and HCl dissolving. The CaO contents in extracted mortars (CaOm) were measured by XRF, and the CaO contents in paste (CaOp) can be calculated by using Eq. (2). Eventually, slag contents in the mixtures were determined by Eq. (3). The estimation results of CaOp and slag content (r) are demonstrated and compared to the actual values as shown in Tables 7 and 8, respectively. As obviously seen in Table 7, two analyzing methods show marginally dierent results of sand content (z) investigation. The XRD method yields much higher contents than results obtained from HCl dissolving technique in most samples. In view of estimated CaOp, the results from XRD method shows unrealistic overestimated contents compared to the calculated CaOp in most cases. It would be explained that the quartz content in ne sand powders

Table 7 Estimation of CaO content in cement paste phase Sample CaOm 0.3834 0.3376 0.3238 0.3674 0.3759 0.3466 0.3785 0.3080 0.3161 Calculated CaOp XRD method Estimated z BFS30-14d BFS50-14d BFS70-14d BFS30-28d BFS50-28d BFS70-28d BFS30-91d BFS50-91d BFS70-91d 0.5859 0.5415 0.4914 0.5859 0.5415 0.4914 0.5859 0.5415 0.4914 0.465 0.457 0.441 0.478 0.403 0.407 0.429 0.575 0.499 Estimated CaOp 0.716 0.622 0.579 0.703 0.629 0.584 0.665 0.725 0.63 Modied XRD Estimated z 0.358 0.354 0.343 0.367 0.318 0.321 0.336 0.430 0.380 Estimated CaOp 0.579 0.523 0.493 0.580 0.551 0.510 0.572 0.540 0.510 HCl method Estimated z 0.352 0.360 0.356 0.378 0.311 0.298 0.360 0.429 0.363 Estimated CaOp 0.592 0.528 0.503 0.590 0.546 0.493 0.593 0.539 0.496

Table 8 Estimation of slag content in concrete mixes Sample Actual r Modied XRD method Estimated CaOp BFS30-14d BFS50-14d BFS70-14d BFS30-28d BFS50-28d BFS70-28d BFS30-91d BFS50-91d BFS70-91d 0.30 0.50 0.70 0.30 0.50 0.70 0.30 0.50 0.70 0.579 0.523 0.493 0.580 0.551 0.510 0.572 0.540 0.510 Estimated r 0.266 0.582 0.708 0.338 0.461 0.634 0.375 0.507 0.636 Error r (%) 3.40 8.20 0.80 3.80 3.90 6.60 7.50 0.70 6.40 HCl dissolving method Estimated CaOp 0.592 0.528 0.503 0.590 0.546 0.493 0.593 0.539 0.496 Estimated r 0.290 0.561 0.666 0.295 0.485 0.706 0.284 0.513 0.696 Error r (%) 1.0 6.1 3.4 0.5 1.5 0.6 1.6 1.3 0.4

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K. Sisomphon / Construction and Building Materials 23 (2009) 5461

presence in the extracted mortar can not well represent the properties of the original sand used in mixture. Due to unrealistic high contents, it would not be able to calculate the slag content from these estimated CaOp values. For the HCl method, the technique dissolves only cement paste phase, and leaves all aggregate as residue. Hence, HCl dissolving technique would give reliable results of the aggregate content in the extracted mortar. As the rst milestone of verication, the CaOp calculated from the HCl dissolving method shows very precise estimation compared to the actual value calculated from raw materials. Because of good estimation of CaOp, the analysis results show that the HCl dissolving method gives accurate estimation on slag content as shown in Table 8. There is no obvious eect of curing age on the determination results. It seems that the method is acceptable in most situations with good accuracy. According to the experimental results in this study, the absolute error of the estimation is averagely less than 5%. However, in case of XRD method, it seems that the calibration line is needed to have modication. The estimated sand content obtained from HCl dissolving was plotted against peak intensity ratio as the results shown in Fig. 5. Thereafter, a new relationship between the sand content and the intensity ratio of mortar extracted from the concrete can be constructed. A new equation gives better estimation of sand contents, and therefore also more precise slag contents in mixture compared to the original results were obtained as shown in Table 7 and 8. However, the accuracy of estimation is still not as good as obtained from HCl technique. The maximum absolute error of estimation is about 8%. Based on the experiment performed in this study, the chemical analysis method with using the HCl dissolving technique to investigate the aggregate content would be a proper method which has a potential for estimation slag content in already hardened concrete.

4. Conclusion In situations where there are disputes among project owner, concrete supplier and contractor, determining blast-furnace slag content in already hardened concrete is essential. The fraction of sand content in the extracted mortar has to be determined, and thereafter slag content can be calculated by the relationship of chemical composition. There are two sets of specimens, articially made mortars and the mortars extracted from concrete, were used in the investigation. For articial mortar mixes, the investigation method using HCl dissolving technique yield a more accurate result in estimation of sand content and therefore more accurate slag content estimation was obtained. Slag content estimated by this method shows reasonable accuracy of 6%. The determined results of articial mortars by XRD method provide estimation with lower accuracy. In case of concrete mixes, mortars extracted from hardened concrete mixes were analyzed. The analysis results reveal that the technique using HCl dissolving method can estimate slag content with acceptable accuracy. The contents estimated by this method yield precise accuracy of 6%. The XRD technique shown the overestimated results in sand content, and therefore underestimation of slag content was obtained. Based on the experimental results, the chemical analysis method incorporating HCl dissolving technique would be an eective method for investigation of slag content in already hardened concrete. In future study, further modications of XRD setting and sample pretreatment are essentially required to ensure the precision of the analysis. More importantly, the techniques proposed in this study would not be able to analyze the mixtures with calcareous aggregates. To extend the limitation of investigation, the application of the methods on the concrete with presence of aggregate apart from granite stone and quartz sand would also be studied. Acknowledgements

0.60 0.55 Equation 4: y = 0.4831x + 0.1763

Sand Content

0.50 0.45 0.40 0.35 0.30 0.25 0.20 0.40 Modified relationship: y = 0.3125x + 0.1719

The author would like to express sincerely thanks to Associate Professor Minhong Zhang (Department of Civil Engineering, National University of Singapore) for her invaluable comments and discussion. References
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0.50

0.60

0.70

0.80

0.90

Iq/ Iref
Fig. 5. Modied relationship between peak intensity ratio and sand content.

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[9] Jakobsen UH, Laugesen P, Thaulow N. Determination of water cement ratio in hardened concrete by optical uorescence microscopy, watercement ratio and other durability parameters techniques for determination. ACI international SP-191-3; 2000. [10] Mertens G, Elsen J. Use of computer assisted image analysis for the determination of the grain-size distribution of sands used in mortars. Cement Concrete Res 2006;36(8):14539. [11] Yang R, Buenfeld NR. Binary segmentation of aggregate in SEM image analysis of concrete. Cement Concrete Res 2001;31(3): 43741. [12] Garboczi EJ. Three-dimensional mathematical analysis of particle shape using X-ray tomography and spherical harmonics: application to aggregates used in concrete. Cement Concrete Res 2002;32(10): 162138.