Waste Management 23 (2003) 825834 www.elsevier.

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Chemicalmechanical characteristics of crushed oyster-shell

Gil-Lim Yoon*, Byung-Tak Kim, Baeck-Oon Kim, Sang-Hun Han
Coastal & Harbor Engineering Research Division, Korea Ocean Research & Development Institute, 1270 Sadong, Ansan City, 425-744, South Korea Accepted 16 October 2002

Abstract Enormous amount of oyster-shell waste has been illegally disposed at oyster farm sites along the southern coast of Korea. To seek for a possibility to recycle the waste as construction materials, chemical and mechanical characteristics of crushed oyster-shell were investigated. Chemical and microstructure analyses showed that oyster-shells are predominantly composed of calcium carbonate with rare impurities. Compressive strength tests for soil mortar specimens with varying blending ratio of cement, water, sand, and oyster-shell were compared with normal cement mortar. There was no signicant reduction in the compressive strength up to 40% of dosages of oyster-shell instead of sand. The experimental results demonstrate that oyster-shells can be resources of pure calcareous materials and eective in replacement of sand, indicating promising reusable construction materials. # 2002 Elsevier Ltd. All rights reserved.

1. Introduction Mariculture centered on the blue belt zone along the southern coast of Korea appears to be a high-prot nearshore shery. Especially, the oyster as a dominant product of shellsh farms are remarkable in the economic point of view. However, such industry has a potential of serious problem about disposal of oystershell waste although it is considered to be greatly advantageous to the development of technology and economics. For example, the oyster-shell waste, illegally dumped into public waters and reclaimed lands, over the Dundok/Hachung Dongbu area of Keoje County causes a typical pollution of southern coast. The dumping site, if the waste has been left untreated for long time, can be a source of nasty smell as a consequence of the decay of esh remnant attached to oyster or the microbial decomposition of salts into gases such as NH3, H2S and Amine. To solve this problem, the Korean Government has recently led the investment of public nance in the establishment of a fertilizer plant in order to increase the oyster-shell recycling. However, the eciency of waste disposal compared to a large expenditure on the plant construction comes into question so
* Corresponding author. Tel.: +82-31-400-6348; fax: +82-31-4085823. E-mail address: glyoon@kordi.re.kr (G.-L. Yoon). 0956-053X/02/$ - see front matter # 2002 Elsevier Ltd. All rights reserved. PII: S0956-053X(02)00159-9

that it is an urgent need to seek for another method eliminating massive oyster-shell waste (Yoon et al., 2001; Yoon and Kim, 2001). Since the early 1980s, Japanese researchers have investigated for the use of oyster-shell waste as construction materials. Major researches involve studies on physical properties of the oyster-shell occurring on the Isamaki port as construction materials, the corrected CBR value of surface materials (lling materials and reclaimed materials), and oyster-shell processing methods including non-crushed oyster-shell, crushed oystershell, and mixture of crushed oyster-shell with other grains. In order to investigate the processing methods of crushed oyster-shell with other materials, there were experiments for non-crushed oyster-shell, crushed oyster-shell with a couple of size, and crushed oystershell blended with varying ratio of sand in the years of 1991 and 1992 (Hashidate, 1993a). In Hashidate (1993b) and Miyaji and Okamura (2000), the construction material mixed with crushed oyster-shell and sand was used for sand compaction piles to improve soft soils underneath the breakwater of port in Japan. Recently, the construction material mixed with dredged clays and crushed oyster-shell was investigated for permeability and compaction properties by means of physical tests and numerical methods (Lee et al., 1998). A serious daily problem in the Korean construction industry has been issued from the shortage of construction

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Table 1 State of annual oyster-shell yielding and recycling (Kyungsang Province) Year 1991 1992 1993 Area (ha) 5224 Weight of yield (t) 247,744 241,912 327,528 Weight of recycle (t) 76,573 74,823 100,508 Weight of dispose (t) 171,171 167,088 227,020

materials. Considering the scale of construction industry in the near future, it is essential to guarantee secure supply of high-quality sand resources. Therefore, as one of alternative plans appropriate for our needs, it is necessary to launch a research on the substitution of construction materials with oyster-shells designated to industrial waste. The objective of this paper is to demonstrate that oyster-shells can be reused as construction materials, based on their chemical and mechanical properties. Analyses for chemical composition, surface texture, and microstructure of oyster-shells are made to investigate whether materials like oyster-shells are adequate for calcareous raw materials. As for mechanical properties, uniformly crushed oyster-shells are blended with cement and sand to make soil mortar specimens. Compressive strength characteristics of the soil mortar specimens are examined in terms of varying blending ratio of sand and oyster-shell dosage to suggest a critical dosage of oystershell where the compressive strength of mortar mixture soil is comparable to that of normal cement mortar.

Fig. 1. XRD pattern of oyster-shell.

required to quantify the salinity content of oyster-shell, which is the basis of limiting the amount of oyster-shell in the mixture. The salinity content in oyster-shells turns out to be approximately 0.35%, derived from the proportion of the whole weight of oyster-shell to the total amount of chloride ions (Cl) pertaining to the relevant provision (Yoon, 2000). Converting this to the regulation value of the chloride ions, 0.3 kgf/m3, the amount of oyster-shell per 1 m3 should not be greater than 85.7 kgf. Therefore, assuming that granular materials in the concrete are 700800 kgf/m3, oyster-shells should not be greater than 10% in the granular materials to prevent the salt damage. It is likely that the granular materials can be substituted with the oyster-shell up to 20% with the consent of buyers.

2. A state of yield and salinity content of oyster-shell More than 90% of oyster yields are produced from oyster farms concentrated on the areas of Tong-young, Keoje and Kosung, where the annual byproducts of oyster-shell reached up to 28 million tons according to the data reported by Tong-young oyster-shery cooperative association in 1997. Table 1 presents a state of annual oyster-shell yield and recycling in the South Kyung-sang Province. In 1993, the amount of oystershell waste was 327,528 t, more than 70% of which was disposed except that only 30% was reused. From this viewpoint, we require urgently to develop a method for oyster-shell recycling. In case that oyster-shell are used as construction materials, especially as a mixture for concrete, it is
Table 2 Chemical composition of oyster-shell CaCO3 (%) 95.994 SiO2 (%) 0.696 MgO (%) 0.649 Al2O3 (%) 0.419 SrO (%) 0.33 P2O5 (%) 0.204 Na2O (%) 0.984 SO3 (%) 0.724 Total (%) 100.0

3. Investigation of the characteristics of crushed oyster-shell Chemical analysis, X-ray diraction analysis (XRD), measurement of specic surface by BET, and microstructure analysis by electron microscope (SEM) were carried out to investigate the properties of oyster-shell as raw materials. Table 2 shows chemical composition of oyster-shell. It is noted that oyster-shell is entirely composed of CaCO3 (approximately 96%) and other minerals of trivial amount. Various oyster-shells due to sources and individual characteristics are almost similar in the chemical composition. The mineral phase of calcium carbonate turns out to be calcite (Fig. 1).

G.-L. Yoon et al. / Waste Management 23 (2003) 825834 Table 3 Physical properties of oyster-shell Mean particle size (mm) 1.65 Bulk density (g/cm3) 1.152 Apparent density (g/cm3) 2.56 Porosity (%) 54.99 BET Surface area (m2/g) 1.75

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In contrast to the chemical composition, physical properties such as texture, porosity, specic surface, and apparent density are dierent even in an oyster-shell. To reduce the variability, oyster-shells are crushed into small pieces from which an averaged value of each physical property is obtained. Table 3 shows the physical properties of oyster-shell powders with a mean diameter of 1.65 mm.

Microstructure of oyster-shell can be divided into two parts, sheet phase layer and porous bulky layer. Sheet phase layer is oriented to the growth direction of oyster shell and porous bulky layer is between sheet phase layers. Although two layers have the similar chemical composition (CaCO3), the microstructure of two layers is dierent as shown in Fig. 2. The sheet layers shown in Fig. 2(a) are oriented to each sheet direction and the sheets of bulky layers shown in Fig. 2(b) wrap the 515 mm pores with non-orientation. Except these two layers, there are two small parts, the growth stem and the parasite. The growth stem is the starting point of oystershells growth and the parasite lives on the outside of oyster-shell. The main compositions of two parts are calcite made of CaCO3. Therefore, it can be concluded that the oyster shell are composed of CaCO3.

Fig. 2. SEM micrographs of surfaces and fractured surfaces of the dierent areas of an oyster shell.

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Table 4 Engineering properties of each crushed oyster-shell Types Gs Water D30 D60 No. 200 passing gd(max) (t/m3) content (mm) (mm) percentage (%) (%) 3.7 2.8 0.95 0.12 6.1 4.1 1.4 0.44 3.19 5.08 15.36 25.88 0.95 0.96 0.96 1.08 gd(min) (t/m3) 0.71 0.71 0.71 0.81

1 2 3 4

2.35 6.5 2.37 7.6 2.45 7.7 2.47 11.1

To investigate engineering characteristics of oystershell, a total of four samples, crushed in four dierent types, are used to measure properties such as specic gravity, grain size distribution, water content and maximum/minimum dry weight per unit volume. Summary of experimental results shows in Table 4 and

photographs 1(a)(d) shows four types of crushed oyster-shell with dierent maximum size. The grain size distribution curves for four types of crushed oyster-shell is shown in Fig. 3. Specic gravity measurement for each crushed oystershell followed the provision of ASTM regulations. However, a 500 ml mass ask was used for the sample No. 1 and No. 2 whose maximum grain size is very large, whereas a 100 ml pycnometer was used for the sample No. 3 and No. 4. The result shows that the specic gravity of oyster-shell depends upon the degree of crush. As the size gets smaller, that is, the degree of crush increases, the value of specic gravity approaches to that of calcium carbonate, 2.71, comprising the major component of oyster-shell. However, it can be generalized that naturally crushed oyster-shell is lighter materials than sand because their specic gravity is no more than the range of 2.352.47.

Photo 1. Crushed oyster-shells with each maximum grain size.

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Fig. 3. Grain size distribution curves for four dierent types of crushed oyster-shell.

4. Experimental works The important element of strength reduction occurring by the interaction of cement and oyster-shell is oyster-shell dosage ratio of mixed soil. To consider that, the oyster-shell dosage ratio take dierent with ve types ranging from 0 to 80% and also the ratio of cement/mixed soil take dierent with two types of 1:5 and 1:10. The soil mortar is mixed by the weight ratio and the crushed oyster-shell used to the sample No. 3. Table 5 shows the basic mixture proportions of used soil mortars. The uniaxial compressive strength to investigate the compressive strength of soil mortar was performed with

Table 5 Mixing ratio of soil mortar including the crushed oyster-shell

Mixing Cement/ Oyster-shell Water Cement Crushed Sand type mixed dosage (kgf/m3) (kgf/m3) oyster-shell (kgf/m3) soil ratio ratio (%) (kgf/m3)

the strain rate of 1 mm/min in laboratory according to ASTM C 39 (1999). In experiments, three specimens of each test are used to prevent the laboratory test errors of observed data due to no uniformity of mixed soil mortar. Soil mortars have the water/cement ratio of 1.0, which is larger than the normal values of 0.60.8. This is due to the larger capacity of water absorption of oystershell. And the cement/soil ratios of mixture type A and B are 0.2 and 0.1, respectively. The sand, which is natural water content of 9.3%, has specic gravity of 2.64. After mixing with sand, crushed oyster-shell, cement, and water, the soil mortar was inserted into the mold of f50100 mm. The soil mortar specimens were cured at air dry condition during 1 day and cured under water to the test ages of 6, 13, 20, and 27 days. The curing temperature was controlled in laboratory and the measured temperature was between 18 and 19  C at day and night. Then, the total curing day of the soil mortar is 7, 14, 21, and 28 days.

5. Experimental results and discussions

A 0.2 0 20 40 60 80 0 20 40 60 80 311 308 306 303 300 196 194 191 189 187 311 308 306 303 300 196 194 191 189 187 0 308 611 908 1200 0 387 765 1135 1497 1556 1233 917 606 300 1958 1548 1148 757 374

0.1

Fig. 4 shows relationship between the compressive strength and curing time for crushed oyster-shell dosage in terms of two dierent mixing types. The compression strength in the gure is the averaged value of three tested results under the same test conditions. At the crushed oyster-shell dosage ratio of 0% the compressive strength for the mixing type A and for the mixing type B ranges from 20 to 60 kgf/cm2, from 9 to 14 kgf/cm2,

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Fig. 4. Compressive strengthcuring time relationship for each mixing type and crushed oyster-shell dosage ratios.

respectively. However, at the crushed oyster-shell ratio of 80% the compression strength for mixing types A and B decreases signicantly to the ranges from 5 to 10 kgf/cm2 and from 1 to 2 kgf/cm2, respectively. This indicates that the compressive strength for the mixing type A is much larger than that for the mixing type B regardless of the curing time. The higher values of cement/mixed soil ratio may be responsible for the increase of the compressive strength of soil mortar due to enhanced quantity of cement hydration.

5.1. Eect of cement/mixed soil ratio Fig. 5 shows the change of compressive strength with respective to the two cement/mixed soil ratios for three dierent crushed oyster-shell dosage ratios of 0, 40, and 80%. The gure also presents the standard error mean of three compressive strength test results. As shown in Fig. 5(a), the compressive strength of mixing type A without crushed oyster-shell (=0%) increases with the curing time. Especially, the increase of compressive

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Fig. 5. Eect of cement/mixed soil ratio on the compressive strength for each crushed oyster-shell dosage ratio.

strength between curing time of 7 and 14 days is steeper than that after curing time of 14 days. Also, the compressive strength after the curing time of 21 days is almost constant. However, the compressive strength for mixing type B increases slightly with the curing time. Fig. 5(b) and (c) show that soil mortar including the crushed oyster-shell dosage ratios of 40 and 80% also increase slightly in compression strength with increasing

the curing time. Especially, the compressive strength of mixing type B with the crushed oyster-shell dosage ratio of 40% increases rapidly up to 21 days rather than that of the crushed oyster-shell dosage ratio of 80%. For the soil mortar without the crushed oyster-shell (=0%), at curing time of 28-days, the compressive strength ratio of mixing type A to mixing type B is about 4.5. However, the ratios of soil mortar including

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Fig. 5. (continued).

the crushed oyster-shell dosage ratios of 20, 40, 60, and 80% are 4.1, 1.2, 1.4 and 2.9, respectively. That is to say, the compressive strength ratio decreases with increasing the crushed oyster-shell dosage ratio, but this tendency is reversed beyond the crushed oyster-shell dosage ratio of 40%. 5.2. Eect of oyster-shell dosage ratio Fig. 6a and b show the eect of the crushed oystershell dosage ratio on the compressive strength development at the curing time of 7 and 28 days. The gures also present the standard error mean of compressive strength. It is found that the compressive strength decreases with increasing the crushed oyster-shell dosage ratio and the decreasing rate of mixing type B is smaller than that of mixing type A. As shown in Fig. 6a, at the curing time of 7 days, the compressive strength of mixing type A decreases linearly with increasing the crushed oyster-shell dosage ratio. However, at the curing time of 28 days in Fig. 6b it decreases rapidly until the crushed oyster-shell dosage ratio reaches up to 40% and then becomes almost constant after the ratio of 40%. For the case of mixing type B, Fig. 6a and b show that the compressive strengths decrease relatively rapidly when the crushed oyster-shell dosage ratio is between 40 and 60%. The dierence of compressive strength between mixing type A and B decreases with increasing the crushed oyster-shell dosage ratio and curing time. Therefore, at the curing

time of 28 days in Fig. 6b, the compressive strength of mixing type A with the crushed oyster-shell dosage ratio of up to 30% is 4 times, 3 times and twice as large than that of mixing type B. Based on the experimental results, an empirical model is proposed to relate the compressive strength with the crushed oyster-shell dosage ratio . The compressive strengths of soil mortar including the crushed oystershell are normalized by the compressive strength without the crushed oyster-shell. The measured compressive strength ratio are shown in Fig. 7 from which the regression curves for two dierent mixing types are obtained. The coecient of determination is 0.88 in case of the mixing type B. The gure also presents the standard error mean of compressive strength ratio. The regression curves can be formulated as follows: for mixing type A, qu =qu0 1 1 0:000262:30 1

for mixing type B, qu =qu0 1 1 0:000132:23 2

where  is a crushed oyster-shell dosage ratio (%), qu0 is the compressive strength of soil mortar without crushed oyster-shell, and qu is the compressive

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Fig. 6. Eect of crushed oyster-shell dosage ratio on the compressive strength for each curing time.

strength of soil mortar including the crushed oystershell of %. As shown in Fig. 7, the regression curve estimates the compressive strength ratio in a little error range. Fig. 7 also shows that the normalized compressive strength of soil mortar with the crushed oyster-shell dosage ratio of 20% is about 0.80 times comparing with the compressive strength of soil mortar without

the crushed oyster-shell (=0%). Therefore, with the proper crushed oyster-shell dosage ratio not larger than 20%, the oyster-shell can be a good alternative material for existing sands of insucient. Also, it may conclude in Fig. 7 that the normalized compressive strength of soil mortar with the crushed oyster-shell of 40% for the mixing type B is about 0.7 times the case of =0%.

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Fig. 7. Normalized compressive strengthcrushed oyster-shell dosage ratio for each mixing type.

6. Conclusions The mineral CaCO3 of calcite structure is a dominant component of oyster-shells. Also the chemical composition on the whole oyster-shells is so similar that oystershells themselves can be pure resources for calcareous materials. In order to investigate the applicability of oyster-shell as the alternative materials of sand, a series of the compressive strength tests of soil mortar blended with crushed oyster-shell were performed. Based on this study, following conclusions are drawn as. 1. Regression models for normalizing the compressive strength of soil mortar are proposed in terms of two types of cement/soil ratio (0.1 and 0.2), curing times (728 days), crushed oystershell dosage (080%), which may be used to determine mix design in making oyster-shell mixed soil mortar for viable applications such as backll materials in breakwater and seawall structure construction. 2. The compressive strengths of soil mortar with the cement/soil ratio of 0.2 decreases rapidly when the crushed oyster-shell dosage ratio is about between 20 and 40%. However, the compressive strength of soil mortar with the cement/soil ratio of 0.1 decreases rapidly when the crushed oystershell dosage ratio reaches between 40 and 60%. 3. Based on the compressive strength test of soil cement mortar, the critical ratio of the crushed

oyster-shell dosage is 20% for the mixing type A and 40% for the mixing type B, respectively. It can be recognized that the crushed oyster-shell is a good alternative material of insucient sand.

References
ASTM C 39-96, 1999. Standard Method for Compressive Strength of Cylindrical Concrete Specimens. Annual Book of ASTM Standards, ASTM 4.02, pp. 1822. Hashidate, Y.T., 1993a. Engineering characteristics of sand mixed with crushed oyster-shell. In: 29th Proceeding of Japan Geotechnical Society, pp. 869872. Hashidate, Y.T., 1993b. Application to sand compaction pile and characteristics of sand mixed with crushed oyster-shell. In: 29th Proceeding of Japan Geotechnical Society, pp. 717720. Miyaji, Y., Okamura, T., 2000. Geo-material properties of wasted oyster-shellsand mixture and its application as material for sand compaction pile. In: Proc. of Coastal Geotechnical Engineering in Practice. Balkema, Rotterdam, pp. 675680. Lee, G.H., Fumon, K.K., Daikon, D.M.M., 1998. Consolidation characteristics of saturated soil mixed with crushed oyster-shell and clay. In: 33rd Proceeding of Japan Geotechnical Society, pp. 423424. Yoon, G.L., 2000. Development of special concrete blended with crushed oyster-shell. Report of the Ministry of Marine Aairs and Fisheries (in Korean). Yoon, G.L., Kim, B.T., Kim, J.H., Chae, Y.S., Seo, S.N., Shim, J.S., 2001. Strength characteristics of mortar soil with oyster-shell. J. of Korea Geotechnical Society 17 (5), 5160 (in Korean). Yoon, G.L., Kim, B.T., 2001. Strength characteristics of mixture soils with oyster-shell for recycling. In: Proc. of the KGES 2001 National Conference, Korea Geo-Environmental Society, pp. 71 76 (in Korean).