31 1 JIEGOU HUAXUE Vol. 31, No.

1
2012. 1 Chinese J. Struct. Chem. 85~92

Structure and Property Characterization

of Oyster Shell Cementing Material

ZHONG Bin-Yang ZHOU Qiang

CHAN Chang-Feng YU Yan
(College of Material Science & Engineering, Fuzhou
University, Fuzhou, Fujian 350108, China)

ABSTRACT Oyster shell powder was used as the admixture of ordinary portland cement. The
effects of different addition amounts and grinding ways on the strength and stability of cement
mortar were discussed and proper addition amount of oyster shell powder was determined. The
structure and property changes of cementing samples with different oyster shell powder contents
were tested by XRD and SEM means. The results revealed that compressive and rupture strengths of
the sample with 10% oyster shell powder was close to those of the original one without addition.
Stability experiment showed that the sample prepared by pat method had smooth surface without
crack and significant expansion or shrinkage after pre-curing and boiling, which indicated that
cementing material dosed with oyster shell powder had fine stability. XRD and SEM observation
showed that oyster shell independently exists in the cementing material.
Keywords: oyster shell powder, cement sand strength, stability

1 INTRODUCTION Eun-Ik Yang etc. (South Korea) have conducted

researches on the feasibility of substituting natural
Oyster shell has special physical conformation sand with oyster shell[8-9], and the experimental
consisting of cuticle, prismatic layer and nacreous results showed that the compressive strength of
layer, with its main part to be the prismatic layer cement did not reduce significantly when the subs-
comprised of foliated structure. It contains a great titution rate of sand increased from 0% to 20%, and
number of micropores sized in 210 m with high this provided a fine concept for the digestive trea-
strength, fine wear resistance, light mass, small tment of oyster shell. In China, with the continuous
density, low coefficient of heat conductivity, wea- prosperity of construction industry, the cement de-
thering resistance and fine stability, so it has great mands are continuously increased and the price rises
and potential applications in such fields as environ- greatly, so the cost is greatly increased. In this study,
[1-5]
mental protection, pharmacy, catalysis and so on . oyster shell powder was utilized to substitute the
The oyster shell mainly contains calcium carbonate cement clinker; the effects of different oyster shell
that accounts for about 95%, and it can be utilized addition amounts on the cement stability and cemen-
[6-7]
for producing medium and high quality cement . ting sand strength were discussed. In addition, the

Received 1 June 2011; accepted 20 August

Supported by the National Natural Science Foundation of China (No. 51102047), Fujian Provincial of Science
and Technology (2011Y0037) Research Foundation for the Returned Overseas Chinese Scholars,
State Education Ministry SRF for ROCS, SEM
Corresponding author. Yu Yan, female, PHD, associate professor. E-mail: [email protected]
Zhong Bin-Yang, male, born in 1987, graduate student
86 ZHONG B. Y. et al.: Structure and Property Characterization of Oyster Shell Cementing Material No. 1

effects of different grinding ways of oyster shell on Waste oyster shell was collected, cleaned and
the cementing mortar was also studied, which can dried. After coarse crushing, the oyster shell was
provide basic data and technical support for elemi- placed into a ball mill (model: QQM light type,
nating oyster shell pollution in maximum degree and produced by Xianyang Jinhong Machinery Plant) for
extending its applications in building-material pro- dry and wet method ball grinding through adding
duction. water, respectively for 24 h. Oyster shell powder
after wet grinding would be dried at 105 for 24 h
2 EXPERIMENTAL METHOD and passed the 100-sieve screen (165 m), and the
AND PROCESS dry powder was obtained for further use (for its
composition, refer to Table 1).
2. 1 Pre-treatment of oyster shell

Table 1. Chemical Compositions of Principal Raw Materials

Composition SiO2 Al2O3 Fe2O3 CaO MgO K2O Na2O TiO2 I.L. Gross quantity
Oyster shell 1.25 0.64 0.11 54.31 0.01 0.01 0.93 0.11 42.96 100.12
L.I. specifies lost on ignition

2. 2 Experiment for cementing then placed into the curing box. After formwork
the sand strength removal, these samples were placed into the
Ordinary Portland cement produced by Taiwan standard curing room to cure up to different time (3,
Cement (Fujian) Plant was utilized. According to the 7 and 28 days). Rupture strength (measured with
formula given in Table 2, the oyster shell powders electronic rupture instrument, peak load: 500 kg;
obtained with dry and wet ball grinding and other accuracy: 1%, model: KZY-500-2) and compressive
raw materials were accurate. After that, these strength (measured with digital-display building
materials were placed into a cementing mortar material compression testing machine; model: JYS-
agitator (model: JJ-5, produced by Wuxi Xiding 2000A; class of testing machine: class 1; YES305-
Construction Engineering Instrument Plant) for 5000 digital display controller) of the test pieces
agitation. With vibration and compaction, the test added with these two types of oyster shell were
pieces sized in 4cm 4cm 16cm were formed and obtained, respectively.

Table 2. Experimental Ratio

Addition amount Oyster shell Cement Water Standard sand
Sample No.
(wt%) powder (g) (g) (ml) (g)
No.1 0 0 450 225 1350
No.2 5 22.5 427.5 225 1350
No.3 10 45 405 225 1350
No.4 15 67.5 382.5 225 1350
No.5 20 90 360 225 1350

2. 3 Experiment for stability lometer) was used to analyze the particle size
Experiment was conducted with pat method. For distribution of oyster shell powder obtained with dry
formula, refer to Table 3. and wet method techniques; Philips Xpert-MPD
2. 4 Microstructure characterization powder diffractometer (CuK target, current: 40 mA;
of the samples voltage: 40 kV; scanning speed: 4 /min) was used to
Granulometer (model: Winner 2000Z laser granu- test the crystalline phases of pure oyster shell and
2012 Vol. 31 JIEGOU HUAXUEChinese J. Struct. Chem. 87

the cement mortar samples added with oyster shell morphology of cement mortar test pieces after being
powder in proportion (after being cured for 28 d); cured for 28 d before and after adding the oyster
Philips XL30ESEM environment scanning electron shell powder.
microscope was used to observe the micro

Table 3. Formula of Each Sample

Addition amount Oyster shell powder (g) Cement Water
Sample No.
(wt%) (g) (ml)
No.1 0 0 500 142.5
No.2 5 25 475 142.5
No.3 10 50 450 142.5
No.4 15 75 425 142.5
No.5 20 100 400 142.5

3 RESULTS AND DISCUSSION reached the peak at 3, 7 and 28 d, and the value at 28
d was 49.2 MPa, which was 2.3 MPa higher than
3. 1 Experimental result for mortar that of the sample without oyster shell powder
strength and analysis addition with the increase degree of about 5%. After
Fig. 1(a) and (b) shows the cementing com- that, with continuous increase of the addition
pressive strength change after adding oyster shell amount of oyster shell powder, compressive strength
powder that was obtained with wet and dry method of the test pieces in different curing ages reduced
ball grinding, respectively. According to Fig. 1(a), gradually. When the addition amount of oyster shell
the compressive strength of the contrast test piece powder was 10wt%, the strength at 28 d of the test
without oyster shell powder was 46.9 MPa. With piece was 45.3 MPa, which reduced slightly than the
increasing the addition amount of oyster shell pow- strength of the contrast test piece with the reduction
der, the compressive strength of test pieces in degree to be 3.4%; when the addition amount was
different curing ages firstly increased and then 20wt%, the strength was 37.1 MPa, and the
reduced. The compressive strength of the sample reduction degree was 21% compared with that of the
with 5 wt% addition amount of oyster shell powder contrast test piece.

45
(b) Dry grinding
50
(a) Wet grinding 3d
3d 7d
7d 40
45 28d
28d
Comprehensive strength(Mpa)
Comprehensive strength(MPa)

35
40

35 30

30 25

25
20

20
15

15 0 5 10 15 20
0 5 10 15 20
Oyster shell powder(%)
Oyster shell powder(%)

Fig. 1. (a) and (b) Effect of oyster shell powder on the ccompressive strength of cement
88 ZHONG B. Y. et al.: Structure and Property Characterization of Oyster Shell Cementing Material No. 1

Fig. 2(a) and (b) show the cementing flexural 15 to 20 wt%, the rupture strength reduced to 6.90
strength change curves after adding oyster shell and 6.50 Mpa, respectively, and the reduction degree
power obtained with dry and wet methods ball was 4% and 10% correspondingly.
grinding, respectively. According to Fig. 2(a), the According to Figs. 1 and 2, the effect on the
change rules of the rupture strength of different strength of test piece was not great when the
samples are similar to those in Fig. 1(a). When the addition amount of oyster shell powder reached
addition amount of oyster shell powder was 5wt%, 10wt% from the perspectives of compressive and
the rupture strength reached the peak, increased rupture strengths. The compressive and rupture
from 7.20 MPa without any addition to 7.55 MPa, strengths of the samples added with oyster shell
and the increase degree was about 5%; after that, the powder obtained with wet method ball grinding were
value reduced gradually; when the addition amount better than those with dry method ball grinding.
was 10wt%, the rupture strength, 7.40 MPa, of the Therefore, the wet method ball grinding technique
test piece was close to that of the test piece without was selected to make pre-treatment for the oyster
addition; when the addition amount increased from shell.

8 9
(a) Wet grinding 3d (b) Dry grinding 3d
7d 7d
28d 8 28d
7
Flexural strength(Mpa)

7
Fexuralstrength(Mpa)

5
5

4 4

3
3 0 5 10 15 20
0 5 10 15 20
Oyster shell powder(%)
Oyster shellpowder(%)

Fig. 2. (a) and (b) Effect of oyster shell powder on the flexural strength of cement

Fig. 3(a) and (b) show the particle size distribu- with wet ball grinding were better than those with
tion of oyster shell powder obtained with dry and dry grinding.
wet ball grindings. According to Fig. 3(a), the 3. 2 Experimental result for cement
median particle sizes of oyster shell powder obtained stability and analysis
with wet and dry balling grindings were D50 = 1.61 All pat samples added with oyster shell powder
and D50 = 58.53, with their powder granularity obtained with dry and wet ball grinding were cured
distributed at intervals of 0.608.01 and 11.07 at 20 with humidity greater than 90% for 24 h,
218.77 um, respectively. This indicated that oyster and then heated up to boiling within 305 min and
shell powder obtained with wet ball grinding was kept under constant boiling for 1805 min. The
much finer and more homogeneous, so it was better samples had smooth surface without cracks and
for particle close stacking in cementing mortar test deforms, and the overall volume did not expand or
piece to achieve better filling effect and densifica- shrink significantly, indicating that the cementing
tion of cement hardened mortar structure. Therefore, material added with oyster shell powder had
the rupture and compressive strengths of such qualified stability. The major composition of oyster
samples added with oyster shell powder obtained shell was CaCO3 of mineral crystallization. It was
2012 Vol. 31 JIEGOU HUAXUEChinese J. Struct. Chem. 89
2+
stable and would not produce free Ca , so it would not affect the cement stability.

(a) (b)
Fig. 3. (a) and (b) Particle size distribution of different oyster shell powder
(a)-Oyster shell powder obtained with wet ball grinding
(b) Oyster shell powder obtained with dry ball grinding

3. 3 XRD characterization of the sample columnar cement hydration product distributes ran-
XRD analysis was conducted for sample added domly; the oyster shell distributes in irregular shapes
with oyster shell powder in 10% and pure oyster and is difficult to be identified because the oyster
shell powder. For results, refer to Fig. 3, according shell addition amount was little. In Fig. (c)-(e), there
to which the main crystalline phase of oyster shell is is a great deal of needlelike cement hydration pro-
CaCO3, and the main crystalline phases of cement duct interspersed, which is a typical morphology of
mortar sample added with oyster shell powder in ettringite phase. In addition, oyster shells in different
10% are SiO2, Ca(OH)2 and CaCO3. Ettringite phase shapes (mainly in flat shapes) could be clearly
is not detected because of its lower content. It had identified. Generally, it can be found that oyster shell
serious scattering against X-ray, so the spectrum powder and cementing materials exist independently,
peak is not obvious. Comparing the XRD patterns of and there is not any chemical reaction between them.
two kinds of samples, the CaCO3 phase of oyster Therefore, as one mineral admixture, oyster shell
shell exists stably in the cement mortar samples, powder mainly plays its role through morphologic
which means its addition does not cause the change effect and micro-aggregate filling effect in ce-
of crystalline phase of cement mortar, revealing that menting material. Morphologic effect refers to the
the oyster shell powder has no chemical reaction in effect caused by external morphology, internal struc-
the cement mortar system, just existing indepen- ture, surface property, grain composition and other
dently with only filling effect. physical properties of the particles; micro-aggregate
3. 4 Sample micro-morphology analysis filling effect is that the micro particles of mineral
Fig. 5(a)(e) show the SEM patterns of samples admixture distribute homogenously in the basic
added with oyster shell powder obtained with wet phase of cement mortar with the filling and
ball grinding in 020% after being cured for 28 d, consolidation effect. These two effects supplement
respectively. In Fig. (a), a lot of jelly aggregates in each other and mutually affect and restrict. Oyster
the cement mortar without adding oyster shell shell powder obtained with wet ball grinding is
powder. In Fig. (b), the jelly aggregates and pin- much finer and more homogeneous, and thus its
90 ZHONG B. Y. et al.: Structure and Property Characterization of Oyster Shell Cementing Material No. 1

addition made the particle stacking in the cement xCaOSiO2yH2O+(2x)Ca(OH)2 (2)

mortar much closer. There is fairly better interface In addition, Ca(OH)2 separated from cement
binding among particles, so the cementing mortar hydration process in the early stage reacted to the
strength is improved, especially for early strength. little amount of active SiO2 in oyster shell powder
Therefore, when the addition amount of oyster shell and produced calcium silicate hydrate with
powder is increased to 5%, cementing mortar cementing effect, namely the secondary hydration
strength shows an increase trend; however, structural reaction (3). It becomes hard with certain strength.
characteristics of oyster shell are its porosity and SiO2 + xCa(OH)2 + mH2O =
fairly larger specific surface area and water demand xCaOSiO2nH2O (3)
is greater. On one hand, this makes balance reaction In this case, cementing mortar strength would
in cement hydration reactions (1) and (2) shift increase in some degree when the addition amount is
toward left; one the other hand, this causes the 510%. With continuous increase of the addition
water-cement ratio to be smaller. Under the same amount of oyster shell powder, water demand is also
cement grade, cement stone strength would be increased, which would affect the completion of
higher and its binding power with aggregation would cement hydration reaction. Thus, the strength would
[10]
be greater if the water-cement ratio is smaller . reduce when the addition amount reaches 10%.
Thereby, under the same water consumption, with Energy spectroscopy was conducted for micro-
the increase of addition amount of oyster shell, areas in Fig. 5 (c), and the results are shown in Figs.
water-cement ratio would reduce gradually, then the 6 and 7. According to the EDS analysis results, there
mixture became drier and harder, and there would be are mainly two compositions in the micro-areas in
fairly much honeycomb macro-pore hole in the test Fig. 5 (c). The first is cement hydration product
piece. Thus, cementing mortar strength would show shown in Fig. 6 with its major composition to be
a decrease trend after reaching one peak value with Ca(OH)2 and SiO2; and the second is oyster shell
increasing the addition amount of oyster shell powder whose major composition is CaCO3. In
powder. consideration of XRD analysis results, there is not
3CaOSiO2 + nH2O = any obvious chemical reaction between oyster shell
xCaOSiO2yH2O+(3x)Ca(OH)2 (1) powder and the cement.
2CaOSiO2 + nH2O =

Fig. 4. XRD patterns of the samples

2012 Vol. 31 JIEGOU HUAXUEChinese J. Struct. Chem. 91

(a) 0%-oyster shell (b) 5%-oyster shell

(c) 10%-oyster shell (d) 15%-oyster shell

(e) 20%-oyster shell

Fig. 5. (a)-(e) SEM photos of samples of different oyster shell powder

Fig. 6. EDS patterns of fixed zone

92 ZHONG B. Y. et al.: Structure and Property Characterization of Oyster Shell Cementing Material No. 1

Fig. 7. EDS patterns of the fixed zone

4 CONCLUSION amount of oyster shell powder is 5%, compressive

strength (49.2 MPa) and rupture strength (7.55 MPa)
(1) Ball grinding way of oyster shell has signi- of the test piece are higher than those of blank
ficant effect on the cementing mortar strength. Com- samples without addition, and reach the optimum
pared with sample added with oyster shell powder values. Strength of the test pieces added with oyster
obtained with dry ball grinding, oyster shell power shell powder in 10% is similar to that without
obtained with wet ball grinding is much finer and addition. Thus, the proper addition amount of oyster
distributes homogenously. Thus, strength of ce- shell powder is 510%.
menting materials added with oyster shell power (2) Oyster shell powder mainly has the inert
obtained with wet ball grinding is higher than that filling effect in the cement mortar, and would not
afforded with dry ball grinding. When the addition affect the cement stability.

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