Effects of Calcination on the Crystallography and Nonbiogenic Aragonite Formation of Ark Clam Shell under Ambient Condition

1Department of Physics, Faculty of Science, Universiti Putra Malaysia (UPM), 43400 Serdang, Selangor, Malaysia 2School of Chemistry, The University of Sydney, F11, Eastern Avenue, Sydney, NSW 2006, Australia 3Materials Synthesis and Characterization Laboratory, Institute of Advanced Technology, Universiti Putra Malaysia (UPM), 43400 Serdang, Selangor, Malaysia 4Department of Chemistry, Faculty of Science, Universiti Putra Malaysia (UPM), 43400 Serdang, Selangor, Malaysia

In nature, aragonite formed by geogenic process under high pressure at low temperature or biogenic process [11].Besides, CaCO 3 also exists naturally in three pseudopolymorphs of hydrated CaCO 3 .They are amorphous CaCO 3 ⋅xH 2 O ( ≈ 1), P-hexagonal CaCO 3 ⋅H 2 O (monohydrocalcite), and C-monoclinic CaCO 3 ⋅6H 2 O (ikaite) crystals [12][13][14][15].The species of ark clam is being chosen for our research because it solely consists of biogenic calcite and is the most consumed seafood bivalve in Malaysia and most countries.It is categorized under the kingdom of Animalia, phylum of Mollusca, class of Bivalvia, subclass of 2 Advances in Materials Science and Engineering Pteriomorphia, order of Arcoida, family of Arcidae, genus of Anadara, and species of granosa [16].The shells of ark clam (ACS) contribute large amount of solid waste.ACS is primarily composed of CaCO 3 which is mostly in the form of calcite.When sufficient heat is applied to calcite, it will decompose to form calcium oxide (CaO) and release carbon dioxide (CO 2 ) gas.
In this study, we reported crystallographic evolution and unusual nonbiogenic aragonite formation of disposed ACS powder after calcination at 400-1400 ∘ C for 3 hours followed by slow cooling rate (−10 ∘ C min −1 ) under moist atmospheric air and pressure in Malaysia which has not been reported by other researchers.Disposed ACS was used as a source of high crystallinity biogenic calcite.Utilization of ACS and other seafood shells can reduce lands for mining limestone and reduce solid waste associated with seafood industries.Partial pressures of carbon dioxide in atmospheric air affect the recarbonation of decarbonized ACS, whereas partial pressure of water vapour in atmospheric air affects hydroadsorption of hygroscopic CaO during cooling process.The ambient condition also caused recarbonation of pyrogenic fcc CaO to form atmospheric aragonite and atmospheric calcite by CO 2chemoadsorption.The formation of aragonite from CaO under ambient condition is unusual because it is thermodynamically less stable compared to calcite.It was first discovered by Loy (2012) and further discussed in this paper.PXRD and FTIR analyses were carried out to describe the decomposition of calcite, formation of aragonite, and hydroadsorption of CaO in terms of crystallography and chemical bonds change of ACS [17].

Materials and Methods
The raw material of this study was fresh disposed ACS by seafood industries in West Peninsular Malaysia.The ACS originates from Straits of Malacca.ACS was immersed into bleaching detergent (0.5-2% of sodium hypochlorite, NaClO) for 30 minutes and then rinsed with water.NaClO was practically used by other researchers before to remove organic compounds on calcium-based materials such as aragonite, hydroxyapatite, and bone [18][19][20].Clean ACS was ground into powder (≤63 m) and tested by PXRD under wide range of angles (10-130 ∘ ) to identify the purity of crystals.
Clean ACS was also heated at 400 ∘ C for 3 hours to be brittle, easy to grind, and free of organic compounds.The ACS was ground into powder (≤63 m) for in situ PXRD analysis under ambient condition.In situ PXRD analysis was performed by PANalytical X'Pert Pro PW3050/60 diffractometer with CuK  radiation and stage furnace to characterize ACS powder while being heated at 600-1000 ∘ C under ambient condition.The decomposition temperature and phase transformation of calcite under ambient condition were determined.
In order to study the effect of atmospheric air in Malaysia on ACS after calcination, ACS powder was calcined at various temperatures (400-1400 ∘ C) for 3 hours in an electric furnace under ambient condition.Each calcined ACS powder was heated with a rate of +10 ∘ C min −1 , remained at calcination temperature for 3 hours, and then cooled with a rate of −10 ∘ C min −1 to room temperature.The products of calcination were reground into powder (≤63 m) and kept for three and nine months for further analyses.Ex situ PXRD test was also carried out by PANalytical X'Pert Pro PW3050/60 diffractometer with CuK  radiation at room temperature to characterize calcined ACS powder.The scanning angles (2) of ex situ PXRD were 10-70 ∘ .The decomposition temperature and phase transformation of calcite under ambient condition were determined.The result was compared to the in situ PXRD patterns of ACS after calcination under ambient condition.
Chen and Xiang (2009) studied the three polymorphs of synthetic Ca(CO) 3 through displacement reaction of salt solutions (CaCl 2 and NH 4 HCO 3 ) at 30-80 ∘ C [1].They provided PXRD pattern and FTIR spectra to show crystals transformation of vaterite and calcite to aragonite.They stated that V 2 and V 4 vibrations of CO 3 2− bonds in vaterite are 877 and 744 cm −1 , respectively, whereas the vibrations of calcite bonds are 848 and 714 cm −1 , respectively.The IR absorption at V 2 = 854, V 4 = 712, and V 4 = 700 cm −1 corresponds to the vibrations of CO  hydrated CaO has a weaker band at 3643 cm −1 compared to Ca(OH) 2 .

Result and Discussion
PXRD test on ACS before calcination revealed that ACS consists of high crystallinity of R-trigonal CaCO 3 (biogenic calcite).No impure crystal was traced in the PXRD result in 10 ∘ < 2 < 130 ∘ .Figure 1 shows the PXRD result in diffraction angle range of 10-90 ∘ which consists of most informative peaks which corresponded to calcite.These peaks are located at 2 (Miller indices) = 23.12∘ (0 1 2), 29.46 ∘ (1 0 4), 31.84 ∘ (0 0 6), 36.33In situ PXRD scanning was also carried out on ACS heated from room temperature to 1000 ∘ C in a PXRD instrument installed with a stage furnace accessory.Crystallographic evolution of ACS at instantaneous temperature under atmospheric air and pressure was investigated.The in situ PXRD result of ACS at 600-1000 ∘ C is shown in Figure 2. It revealed that biogenic calcite in ACS powder slightly grows at 600-650 ∘ C. CaCO 3 began to decompose to fcc CaO at 650 ∘ C. Three major peaks of fcc CaO were found in the PXRD pattern at 31.79 ∘ , 36.93 ∘ , and 53.28 ∘ .Calcite in ACS does not transform into other polymorphs of CaCO 3 before decomposition.Calcite fully decomposed to form fcc CaO at 800 ∘ C. The fcc CaO only slightly grows towards 1000 ∘ C.
Figure 3 shows the ex situ PXRD patterns of ACS powder after calcination at 600-1000 ∘ C for 3 hours and cooling down to room temperature with a rate of −10 ∘ C min −1 under ambient condition.The PXRD pattern of ACS after calcination at 600 ∘ C showed a set of peaks attributed to calcite.Few major peaks of fcc CaO observed in the PXRD pattern of 700 ∘ C revealed that the biogenic calcite began to be decarbonized to form pyrogenic fcc CaO nucleate [5,26,27].Calcite peaks intensity was diminished in the PXRD patterns   Figure 4 shows the ex situ PXRD patterns of ACS powder after calcination at 400-1400 ∘ C which were kept at room temperature under ambient condition for three months.The main objective of this analysis is to observe time-dependent crystallography evolution of ACS due to recarbonation and hydroadsorption of pyrogenic fcc CaO.The identities of    [28].
The recarbonation process of fcc CaO to CaCO 3 in air may involve two steps of phase transformation (fcc CaO to aragonite and aragonite to calcite).According to Ostwald's Step Rule, nonordered CaCO 3 particles could transform into unstable transient state such as vaterite and aragonite before transforming to the most thermodynamically stable state of calcite [3,34,35].The atmospheric aragonite may be nucleated due to slow cooling process of ACS from calcitearagonite transition temperature to room temperature and then further growing under ambient condition.The calcite peaks in PXRD patterns of 700-800 ∘ C (Figure 4) may be attributed to the diffraction of both biogenic and atmospheric calcite.The formation of atmospheric calcite was significantly traced in PXRD pattern of 900 ∘ C (Figure 4), where few major peaks of calcite appearing at 29.44 ∘ , 36.16 ∘ , 39.50 ∘ , 42.16 ∘ , and 48.42 ∘ are not found in the PXRD pattern in Figure 3.
Figure 5 showed FTIR spectra of ACS after calcination at 400-1400 ∘ C which were kept at room temperature under ambient condition for three months.ACS which has been calcined at 400 ∘ C has three strong IR absorption bands at 1399, 870, and 711 cm −1 .These bands indicated the presence of CO 3 2 attached to calcium ion (Ca 2+ ) in calcite structure [2,5,22,25].These bands also correspond to the modes of asymmetric stretch (V 4 ), out-plane bend (V 2 ), and in-plane bend (V 3 ) vibrations of C-O bonds in calcite [21,23,24,36].A weak IR absorption band at 1793 cm −1 corresponded to C=O bond in calcite [25].Besides, three weak IR absorption bands were found in the spectrum at 3743 and 2512 cm −1 .They were attributed to bond vibration of H-OH of water and Ca-OH 2 of calcite.We deduced that H 2 O from atmospheric air was adsorbed by CaCO 3 via chemisorption and physisorption.Chemisorption of H 2 O may form tiny hydrated CaCO 3 crystal which is below the detectable range of PXRD.Monohydrocalcite crystal is more likely to be presented in ACS compared to amorphous CaCO 3 and ikaite because monohydrocalcite is more kinetically stable at room temperature and pressure [13,37,38].The chemical equation which represents the hydroadsorption of calcite was shown in (1).The FTIR spectra of ACS after calcination from 400 to 600 ∘ C do not show any significant changes in chemical bonds: FTIR spectrum changed as ACS was being calcined at 700 ∘ C. Two new IR absorption bands appeared at 3640 and 502 cm −1 in the FTIR spectrum of 700 ∘ C.They were contributed by vibration of Ca-OH bond in Ca(OH) 2 and Ca-O bond in CaO [36].The strong and sharp band at 1408 cm −1 was resultant IR absorptions by asymmetric C-O bond vibration in calcite/aragonite and Ca-O bond vibration in CaO [25].The spectrum revealed that biogenic CaCO 3 was partially decomposed to form pyrogenic CaO during calcination (see (2)) and then hydrated to form atmospheric Ca(OH) 2 under ambient condition (see ( 3)) [25,39].The result was consistent with the PXRD result of 700 ∘ C in Figure 4.The IR absorption bands of CaCO 3 in the spectrum may have resulted by the overlapping of IR absorption of biogenic calcite as well as recarbonized atmospheric calcite and aragonite (see ( 4)): CaO (s, pyrogenic fcc) CaO (s, pyrogenic fcc) Ca 2+ has high magnitude of charge and small ionic radius.Therefore, it has high charge density and polarization strength.CO 3 2− in calcite has larger ionic size compared to O 2− in CaO.The large electron cloud of CO 3 2− can be polarized by Ca 2+ and ascended higher covalent character of CaO-CO 2 bond in calcite.At high temperature, Ca 2+ pulls electron pair of Ca-OCO 2 closer towards itself and strengthens the bond.Large ionic size of CO 3 2− caused the CaO-CO 2 bond to experience larger magnitude of bond strain of vibration.It weakens the CaO-CO 2 bond strength at high temperature.With calcination ≥700 ∘ C, calcite gained enough energy to break the CaO-CO 2 bond and form CaO and CO 2 gas as shown in (2).Ca-O bond in CaO has higher ionic character and higher bond strength than Ca-OCO 2 in Advances in Materials Science and Engineering 3600 3200 2800 2400 2000 1600 1200 800 400 0 4000 Wave number (cm −1 ) calcite.Therefore, CaO has higher thermodynamic stability than calcite at high temperature.
CaO has higher hydroadsorption strength than calcite because it is more polar than calcite.Both Ca 2+ and O 2− sites in CaO can undergo physisorption with H 2 O to form Ca-OH 2 bond.Besides, large ionic size of CO 3 2− in CaCO 3 reduced free site of Ca to adsorb H 2 O. CaO also has high chemisorption strength with H 2 O to form Ca(OH) 2 with Ca-OH bonds.Ca(OH) 2 is more kinetically stable than CaO because CaO has low activation energy to react with H 2 O exothermically to form Ca(OH) 2 (see (3)).As a result, Ca(OH) 2 was traced in the FTIR spectrum of 700 ∘ C as CaO formed by decomposition of CaCO 3 .
The IR absorption bands of calcite/aragonite decreased in the spectrum of 800 ∘ C and disappeared in the spectrum of 900 ∘ C. Four IR absorption bands in the FTIR spectra of 800 ∘ C positioned at 2190, 1415, 875, and 520 cm −1 were attributed to the presence of CaO [25].The IR absorption bands of CaO increased from 700 to 1000 ∘ C. It revealed that the content of CaO increased.Since CaO has a hygroscopic property, the formation of Ca(OH) 2 increased parallel with the increases of CaO particles.It was supported by FTIR spectra which showed that IR absorption bands of Ca(OH) 2 increased from 700 to 1000 ∘ C. The highest hydroadsorption strength of ACS was achieved as it was cooled down from 1000 ∘ C. A new broad band at 3640-2800 cm −1 appeared in the FTIR spectrum of 1000 ∘ C. It represented the presence of Ca-OH 2 and H-OH bonds due to physisorption of water by CaO.
The FTIR spectra of 1200 and 1400 ∘ C showed that the IR absorption bands of CaO decreased.It was due to the fact  that further crystallization of fcc CaO at higher temperature limited the magnitude of Ca−O bond vibrations.However, the intensity of IR band attributed to hydroxide ions (OH − ) at ∼3640 cm −1 does not change significantly.It revealed that the high crystallinity of fcc CaO at high temperature limited the nucleation and growth of Ca(OH) 2 crystal (Figure 3).No IR absorption band attributed to calcite and aragonite was found in the spectra.we deduced that high crystallinity of fcc CaO can slow down rate of CaO.In order to further investigate the time-dependent recarbonation hydration of calcined ACS at 600-1000 C exposed to air, PXRD tests were carried out after nine months of calcination the result was shown in Figure 6.The results revealed that ACS samples underwent decarbonation, and recarbonation.pattern of 600 ∘ C was matched with the diffraction patterns of calcite, aragonite, vaterite, and portlandite.The major phase was calcite.The result showed that the original biogenic calcite was decarbonized and hydrated by atmospheric air to form portlandite.Conversion of stable calcite phase to less stable aragonite and vaterite polymorphs under ambient temperature and pressure is not thermodynamically favourable crystallographic transformation.The crystallization of aragonite and vaterite reflects the fact that the original biogenic calcite in ACS was decarbonized and recarbonized by atmospheric air.The recarbonized CaCO 3 might form the least stable of amorphous CaCO 3 polymorphs first before recrystallization.The amorphous CaCO 3 underwent nucleation of vaterite first followed by transformation towards more stable aragonite and then the most stable calcite [35].The presence of aragonite was observed at 2 = 26.16∘ , 27.10 ∘ , 33.12 ∘ , 35.92 ∘ , 37.85 ∘ , 38.45 ∘ , 45.80 ∘ , 50.04 ∘ , 52.39 ∘ , and 52.95 ∘ , whereas vaterite was observed at 2 = 24.96∘ , 27.10 ∘ , 32.71 ∘ , 43.81 ∘ , 48.58 ∘ , and 50.04 ∘ .Hence, the diffraction of calcite observed in the pattern resulted by both biogenic calcite and atmospheric calcite.The crystallization of portlandite reflects the fact that the original biogenic calcite in ACS was decarbonized to CaO, hydrated to Ca(OH) 2 , and then crystallized to form portlandite by atmospheric air.The presence of portlandite was observed at 2 = 17.93 ∘ , 28.56 ∘ , 34.02 ∘ , 47.06 ∘ , 50.68 ∘ , and 54.25 ∘ .
The PXRD patterns of 700-900 ∘ C in Figure 6 also showed the presence of calcite, aragonite, vaterite, and portlandite.However, the patterns have lower diffraction intensity of calcite compared to the pattern of 600 ∘ C. It reflects the fact that the biogenic calcite in ACS was decarbonized to fcc CaO during calcination but does not fully recover by atmospheric recarbonation.The patterns do not show the presence of fcc CaO.It revealed that fcc CaO that crystallized during calcination is not stable when exposed to atmospheric air.In addition, CaO which decarbonized by atmospheric air does not crystallize to fcc CaO.The high hygroscopic behaviour of CaO made CaO adsorb water rapidly from atmospheric air to form portlandite and made it unable to retain its fcc CaO structure for long period.Besides, the pyrogenic fcc CaO also underwent recarbonation to form calcite, aragonite, and vaterite phases as shown in the patterns of 700-900 ∘ C. The sequence of hydration and recarbonation of CaO by atmospheric H 2 O and CO 2 is expressed as follows: The PXRD pattern of 1000 ∘ C in Figure 6 only consists of diffraction pattern of portlandite and a main calcite peak at 29.32 ∘ .The result revealed that high crystallinity of pyrogenic fcc CaO which was exposed to atmospheric air formed a stable atmospheric portlandite phase.The portlandite phase has a high resistivity to inhibit recarbonation.Hence, small amount of atmospheric calcite was nucleated.No intermediate phase transition of CaCO 3 (aragonite and vaterite) was observed.

Conclusion
A series of calcinations at variation temperature (400-1400 ∘ C) was carried out on disposed ACS which originates from Straits of Malacca.In situ PXRD analysis was conducted on ACS powder at instantaneous temperatures under ambient condition, whereas ex situ PXRD analysis was conducted on ACS powder after calcination and cooling down (−10 ∘ C min −1 ) to room temperature.In general, both in situ and ex situ PXRD analyses showed that the biogenic calcite in ACS is decarbonized to form pyrogenic fcc CaO at 650-800 ∘ C under ambient condition.The crystallinity of pyrogenic fcc CaO increases as calcination temperature increases.In situ PXRD result showed that the biogenic calcite grew at 600-650 ∘ C and is completely decarbonized at 800 ∘ C. The pyrogenic fcc CaO was nucleated at 650 ∘ C and further crystallized at higher temperature.However, ACS after decarbonation at ≥700 ∘ C and cooling down to room temperature under ambient condition induced reestablishment of new dynamic equilibrium via H 2 O and CO 2 adsorption of pyrogenic CaO.Evidence of reestablishment of new dynamic equilibrium was the PXRD analysis of decarbonized ACS after three months of atmospheric air exposure.Hydration of pyrogenic fcc CaO in atmospheric air induced crystallization of atmospheric portlandite in ACS after calcination at 700-1400 ∘ C. Recarbonation of pyrogenic fcc CaO in atmospheric air caused crystallization of atmospheric calcite as well as intermediate phase of aragonite and vaterite in the ACS after calcination at 700-900 ∘ C. The result agrees with Ostwald's Step Rule, where recarbonation of fcc CaO crystallizes the least stable polymorph of CaCO 3 first before transforming to stable calcite.The PXRD result also revealed that high crystallinity of pyrogenic fcc CaO has higher resistivity to recarbonation.fcc CaO is not a stable phase in atmospheric air.FTIR analysis on the ACS after calcination and three months of atmospheric air exposure under ambient condition reflects the hygroscopic effect on both calcite and CaO.Calcite slightly adsorbed H 2 O to form monohydrocalcite in short range order.CaO is very hygroscopic.It adsorbed H 2 O spontaneously to form Ca(OH) 2 .ACS has highest degree of H 2 O adsorption as ACS after decarbonation at 1000 ∘ C. FTIR spectrum also revealed that calcite decomposed at 600-800 ∘ C. CaO and Ca(OH) 2 coexisted in the ACS after cooling down from 700-1400 ∘ C to room temperature.Overall, PXRD analysis is more appropriate to study polymorphic transformation in recarbonation of pyrogenic CaO, whereas FTIR analysis is more appropriate to study hydration of biogenic calcite and pyrogenic CaO.

Figure 4 :
Figure 4: PXRD patterns of ACS after calcination at 400-1400 ∘ C for 3 hours and cooling down with −10 ∘ C min −1 , which were kept under ambient condition for three months (C = calcite; A = aragonite; H = P-trigonal Ca(OH) 2 ; and O = fcc CaO).

Figure 5 :
Figure 5: IR absorption spectra of ACS after calcination at 400-1400 ∘ C for 3 hours and cooling down with −10 ∘ C min −1 , which were kept under ambient condition for three months (C = bonds of calcite; OH = O-H and Ca-OH 2 bonds of water; H = Ca-OH in Ca(OH) 2 ; and O = Ca-O bond in CaO).

Table 1 :
Several crystal structures of calcium compounds present in ACS after calcination and kept under ambient condition for three months.
crystals found in the ex situ PXRD patterns are listed in Table1.Biogenic calcite phase remains in the patterns of 400-800 ∘ C. The calcite peaks in the PXRD pattern of 600 ∘ C were matched with ICSD 073446 of calcite.