Pergamon

Ccmcnt ancl Concrclc Rcscarch 30 (2000) 1209- 12 14

CEMENTAND CONCRETE RESEARCH

Effect of insoluble residue on properties of Portland cement

Abstract
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. .: . Insoluble residgo is ,$ npn -cementing materidkhich is present id Portland ckment. This residli8 haterial especially its compressive strength. To control the non -cementing material in Portland cement, ASTM standard allows the insoluble residue to be not higher than 0.75%. This limitation is much lower than the allowance provided by the British standard which is 1.5%. To verify the effect of insoluble residue on the properties of Portland cement, artificial insoluble residue was prepared and replaced in Portland cement type I. Finely crushed sand was extracted to represent artificial insoluble residue. Setting times and compressive strengths of cement mortar mixed with insoluble residue were investigated. The Portland cement was replaced by insoluble residue which varied in amounts of 0%, 0.5%, 1.0%, 1.5%, 2.0%, 3.0%, 5.0% and 7.0% by weight. The results showed that the addition of the insoluble residue from 0.0% to 7.0% by weight in Portland cement did not affect the normal consistency or setting times of cement. However, the compressive strength of cement mortar was affected during the early age, but the figure reduced as the cement mortar was older. With 7.28% of insoluble residue in the mortar at 1 day, the compressive strength was reduced by 11.5%, but after 60 days, the strength of the same mortar was only reduced by 5.5% as compared to the control mortar. It was also found that the compressive strength of Portland cement mortar with insoluble residue provided by ASTM standard or British standard was still higher than the compressive strength of Portland cement mortar type I allowed by the standards. The limit of insoluble residue given by ASTM standard as 0.75 is rather low and can possibly be increased to 1.5% according to British standard, or even slightly higher, without significantly reducing the compressive strength of cement. 0 2000 Elsevier Science Ltd. All rights resewed.
Keywords Insoluble reqidue; Portland cement; Mortar; Compressive strength

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1. Introduction
Insoluble residue is a measure o f adulteration of cement, largely coming from impurities in gypsum and can b e found by treating the cement with hydrochloric acid and sodium hydroxide [I]. A S T M C 150 [2] limits the insoluble residue in Portland cement type I not higher than 0.75%. B S 12: 1996 [3] sets the limit for insoluble residue at 1.5% for cement not containing a minor additional constituent, and releases the limit to 5.0% for cement including a minor additional constituent, such as granulated blast furnace slag, natural pozzolana, fly ash o r filler [3]. It is found that in modem cement, there is a higher content o f C3S and a greater fineness than that o f 4 0 years ago. As a consequence, cement mortar has, nowadays, a 2 8 days compressive strength perhaps 25 M P a higher than

in 1925 [I]. It seems that a higher insoluble residue in Portland cement can b e increased to a higher value without any negative effect o n its strength. This premise was confirmed by Poupongphan [4]. They found that with 0.5% o f finely crushed brick as an insoluble residue in Portland cement type I, the compressive strength of cement mortar was reduced by 1.6%, and by increasing the
Table 1 Chemical composition of Portland cement type I and finely crushed sand before and after dissolving in acid and basic solution Finely crushed sand before dissolving (%) 88.94 5.09 1.74 2.79 2.79 0.14 92.8 1 Finely crushed sand after dissolving (%) 91.27 5.07 0.4 1 0.09 2.83 0.15 100.0 Portland cement type I (%) 20.2 5.42 2.92 63.82 0.9

Oxide (%) Si02 A1203 Fe203 CaO K20 Ti02 Insoluble residue (%)

Corresponding author. Tel.: +66-2-470-9133; fax: +66-2-427-

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9063. E-mail address: ichakkul@cc.kmutt.ac.th (C. Jaturapitakkul).

0008-8846/00/$ - see front matter O 2000 Elsevier Science Ltd. All rights reset-ved. PII: SOOO8-8846(00)003 1 5 - X

Fig. 1. The XRD of finely crushed sand after dissolving in acid and basic solution.

insoluble residue up to 1.5%, this mixture resulted in a lowering of the cement mortar strength of less than 4% compared to the control cement mortar strength at 28 days. Normal consistency and setting times are not changed by the addition of insoluble residue in cement. However, this premise still needs more data for support and confirmation that slightly increased rates of insoluble residue are not a major factor affecting its strength.

was also investigated. The results will provide cement researchers an understanding of what happens to the Portland cement given the amount of insoluble residue provided by the cement standards.

3. Experimental program
In this experiment, river sand was used as an insoluble residue. The artificial insoluble residue was prepared as follows. First, the river sand was crushed by using a ball mill and then sieved through a no. 200 sieve. Second, the fine powder was mixed with water and dissolved in hydrochloric acid followed, after filtration, by further digestion in sodium hydroxide. An ammonium nitrate solution was then used in the final washing. To prevent finely ground insoluble residue from passing through the filter paper, medium-textured paper was used as a filter. The procedure to obtain the artificial insoluble residue material followed ASTM C 114 [5] except that the

2. Objective
The objective of ;is study is to investigate the effect of insoluble residue on the properties of Portland cement. Finely crushed sand was used as the insoluble residue. The particle size distributions of the finely crushed sand and the Portland cement were tested and compared. Normal consistency and setting times of the Portland cement mixed with insoluble residue were evaluated and compared to the cement paste. The compressive strength of cement mortar, with and without the insoluble residue,
Table 2 Added and tested results of the insoluble residue in cement Total insoluble Sample number A00 B05 C10 Dl5 E20 F30 G50 H70 Added insoluble material (%) 0.0 0.5 1. O 1.5 2.0 3.0 5.0 7.0 material in cement(%) Calculation Test 0.28 0.78 1.28 1.78 2.28 3.28 5.28 7.28 0.28 0.54 1.04 1.50 2.14 3.04 4.96 6.86 Difference (%) 0.0 0.24 0.24 0.28 0.14 0.24 0.32 0.42

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Table 3 Results of normal consistency and setting times of cement pastes mixed with insoluble residue Sample number Insoluble residue Normal consistency
(%)

Setting times (min) Initial Final

(%I

-+-

Portland Cement Type I

10

100

1000

Particle Size Distribution (micron)

Fig. 2. Particle size distribution of cement and insoluble residue.

concentrations of the acid and the basic solutions were two times higher than the concentration given by the standard. This guaranteed that the obtained material was not dissolved in acid or basic solution. Chemical compositions between insoluble residue of the finely crushed sand and Portland cement were then compared. Portland cement type I was replaced with the insoluble residue by 0%, 0.5%, 1.0%, 1.5%, 2.0%, 3.0%, 5.0%, and 7.0% by weigh: of cement, plus the existing insoluble residue in cement. The mixed cement specimens were tested to confirm their amount of insoluble residue using the ASTM C 778 [6] standard. Nonnal consistency and setting times of the mixed cement were tested in accordance to ASTM C 187 [7] and ASTM C 191 181, respectively. The mixed ceinent was also used to prepare mortar in according to ASTM C 109 191. After 24 h, the molds were removed and all the 5-cm cube specimens were cured in saturated lime water. The compressive strengths of mixed cement mortar were tested at the age

of 1, 3, 7, 14, 28, and 60 days. At each date of testing, the data are the average of seven specimens.

4. Results and discussion

4.1. Chemical composition of insoluble residue X-ray fluorescence spectrometry was used to test the chemical composition of Portland cement type I and finely crushed sand, before and after dissolving in hydrochloric acid and sodium hydroxide. The results are shown in Table 1. Portland cement and finely crushed sand, after dissolving in the acid and basic solution, consist of the insoluble residue 0.28% and loo%, respectively. The major oxide of the residue material is silicon dioxide which is 91.27% of the total weight, while calcium oxide is the major oxide of Portland cement. It is noted that the oxides of the finely crushed sand before and after dissolving in hydrochlohc

Fig. 3. Scanning electron microscopy of cement.

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K. Kioffikotilol et ol. / Cerizetrt and

Fig. 4. Scanning electron nnicroscopy of insoluble residue.

acid and sodium hydroxide are almost the same except that the CaO and Fe203 contents were reduced from 2.79% and 1.74%, respectively, to 0.09% and 0.41%, while Si02 is increased from 88.94% to 91.27%. Finely crushed sand, before and after dissolving, has little difference in chemical composition. Fig. 1 showed the result of chemical composition analyzed by X-ray diffraction (XRD). The graph shows the crystalline phase and the amorphous phase of insoluble residue. The quartz content in the sand is very high and similar to the analysis result by X-ray fluorescence spectrometry. XRD analysis reveals that quartz is in the form of the brystalline phase. This means that the finely crushed sand after dissolving in acid and basic solution can be used as an insoluble material which does not react with cement. 4.2. Insoluble residue in Portland cement and in the replaced cement After the insoluble material was replaced in cement at the proposed percentage, the cement and insoluble residues were mixed together to make the sample uniform. Then, the percentage of insoluble residue in the mix was checked. The proposed and the tested results of the
Table 4 Compressive strength of cement mortar containing insoluble residue
Insoluble

insoluble residue material in the mix are shown in Table 2. It is seen that the insoluble residue of cement (sample AOO) is very low; it is 0.28% which is lower than the limit given by the ASTM (0.75%) and BS (1.5%) standards. All of the test results show the lower percentage of insoluble residue compared to the calculated insoluble residue. The difference of insoluble residue ranges from 0.24% in sample B05 (0.5%) to 0.42% in sample H70 (7.0%). However, these figures are still very close to the proposed values.

4.3. Effect of insoluble residue on normal consistency and setting time of Portland cement
The effect of insoluble residue for each percentage as a cement replacement on normal consistency and setting times were presented in Table 3. The replacement of insoluble residue up to 7.0% did not change the normal consistency of cement. The required water for normal consistency was still the same and remains at 26.8%. This is due to the same particle size distribution of the insoluble residue and the cement. Fig. 2 shows the particle size distribution of two materials determined by Particle Analyzer Microtrac 11. Since both materials had almost the same particle size
Table 5 Percentage of compressive strength of cement mortar containing insoluble residue comparing to the control mortar

Compressive strength (MPa)

Sample number MA00 MB05 MClO MD15 ME20 MF30 MG50 MH70

residue
(%)

3 days

7 days

14 days

28 days

60 days

Sample number MA00 MB05 MClO MD15 ME20 MF30 MG50 MH70

Insoluble Percentage of compressive strength (%) 7 1 14 28 residue 3 days days days (%) day days

60 days

k: h'itrllilior~rol cjt ol. / G.rrrcrr/ orrd Corr~rcr~, Revccrr.ch 30 (2000) 1209-1214

10

Insoluble Residue (%)

distribution, they needed the same amount of water to maintain the same normal consistency. Figs. 3 and 4 show pictures of cement and insoluble residue taken by scanning electron microscopy. Both cement and insoluble residues have an irregular, angular and crushed shaped with no spheres. These pictures confirm that the insoluble residue has little effect of normal consistency since cement and insoluble residue had the same shaped particles. Initial and final setting times of sample A00 (only cement paste) were 108 and 195 min, respectively. With the

replacement of cement by insoluble residue up to 7.0%, the setting times were changed little; they varied from 102 to 111 min for the initial setting time and from 195 to 210 min for the final setting time. This means that there is no effect of insoluble residue on setting time of cement paste by replacing insoluble residue up to 7.0%.
4.4. Eflect on compressive strength

The compressive strengths of cement mortar containing insoluble residue up to 7.28% at various ages are shown

65

Insoluble Residue (%)

10

Fig. 6. Relationship between percentage compressive strength of cement mortar and replacement of insoluble residue in the mix.

in Table 4. Table 5 shows thc percentage of co~nprcssivc strength of cement mortar mixcd with insoluble residue compared to the control (sample MAOO) mortar strength. Fig. 5 shows the relationship between the compressive strength of cement mortar and pcrcentage of insoluble residue in the mix. Fig. 6 shows the relationship between the percentage of compressive strength of cement mortar and percentage of insoluble residue. It is seen that the higher the percentage is of insoluble residue in cement mortar, the lower the compressive strength becomes. The compressive strengths of control samples vary from 18.2 MPa at 1 day to 49.2 MPa at 60 days. The sample with 0.5% replacement of insoluble residue has the compressive strengths of 17.8 MPa at 1 day and increases to 48.6 MPa at 60 days. These strengths are lower than the control stren* 552% at 1 day and 1.2% at 60 days, respectively. The co*f$ssrive s w a g t h i of cum@pt mortar with 1.5% of insoluble tesidos, sample @ ~ 1 $ ,418 ,ypgctiiely, ,g\2di MPa at 1 day and 47.9 MPa at 60 days.'~hey are lower than the control strength - about 5.5% at 1 day and 2.6% at 60 days. It is noted that the reduction of strength due to insolvble residue is rather high at the early ages and tends to reduce when the age of cement mortar increases. @ the highest amount of insoluble residue in the mix; 7.28%, in sample MH70, it is found that the comfjressive strength is still higher than the limit given by ASTM C 150 [2]. For ASTM C 150 [2], the cement mortar strength with 0.75% of insoluble residue has to be not lower than ,12.4 MPa at 3 days and 19.3 MPa at 7 days for Portland cement type I. Sample MH70 gives compressive strength of mortar at 3, 7 and 28 days equal to 26.8, 34.0 and 42.3 MPa, respectively. This means that the frikatdBle miflue''up to 7.28% in :t?mntbr is aot4 seriously harmful to its strength. It reduce; the strength of cement mortar, but it is not the main factor affecting the strength of cement mortar. The value of the insoluble residue limited by ASTM C 150 [2], 0.75%, seems to be rather low and can be slightly increased without lowering the standard of cement. P ,
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(2) The normal consistency and setting times of cement were not significantly affected by finely divided sand at cement insoluble residue material levels up to and including 7.28%. This may be because the particle size distril.;ution and the shape of the insoluble residue were similar to that of the Portland cement. . (3) The compressive strength of ASTM C 109 mortar cubes reduced progressively as the insoluble residue was increased. The strength reduction was greater at 1 and 3 days than at test ages from 7 to 60 days. (4) The limit of insoluble residue given by ASTM C 150 at 0.75% may be rather low and could possibly be increased to 1.5% (as in BS 12: 1996), or even slightly higher without significantly reducing the compressive strength of cement mortar.

The authors would like to thank the research team comprised of Mr. Mitree Sakulkitimasak and Mr. Chansak Leesomprasong. This project was supported by the Department of Civil Engineering, King Mongkut's University of Technology Thonburi for which we are also most grateful.

References
[I] A.M. Neville, Properties of Concrete, 3rd edn., Pitman Book, London, 1982, p. 10. [2] ASTM C 150, Standard specification for Portland cement, ASTM C 150-95, in: Annual Book of ASTM, Vol. 04.01, 1995. !$3]~3s$ k%fkh& '*fapeaifi$#l@q. fqk+&ttland~.~i#ent, 1.jQ edn., .British standards Institution, Ldndon, 1996. [4] P. Poupongphan, S. Boonsiri, V. Karunyavanich, Effect of insoluble material on properties of hydraulic cement, Bachelor Degree Project, Department of Civil Engineering, King Mongkut's Institute of Technology Thonburi, 1992. [5] ASTM C 114, Standard test method for chemical analysis of hydraulic cement, ASTM C 114-94, in: Annual Book of ASTM, Vol. 04.01, 1995. [6] ASTM C 778, Standard specification for standard sand, ASTM C 778 92, in: Annual Book of ASTM, Vol. 04.0 1, 1995. [7] ASTM C 187, Standard test method for normal consistency of hydraulic cement, ASTM C 187-86, in: Annual Book of ASTM, Vol. 04.01, 1995. [R] ASTM C 191, Standard test method for time of setting of hydraulic cement by vicat needle, ASTM C 1'9 1-92, in: Annual Book of ASTM, Vol. 04.01, 1995. [91 ASTM c 109, Standard test method for compressive strength of hydraulic cement mortars (using 2-in. or 50-mm cube specimen), ASTM C 109-95, in: Annual Book of ASTM, Vol. 04.01, 1995.

5. Conclusions
From the results of these experiments, the following conclusions can be drawn. (1) The major constituent of the insoluble residue used in this research was silicon dioxide (quartz) derived from acidtreated river sand. Quartz is normally recognised to be a non -cementing material.