Use of Marble Waste to Obtain Biphasic Bioceramics Based on Calcium and Magnesium Phosphates

Abstract

The ornamental stone industry generates a huge amount of marble waste around the world, which requires sustainable disposal. This investigation aimed to synthesize a new biphasic calcium phosphate-magnesium phosphate bioceramic using marble waste as an alternative carbonate precursor. The phosphate bioceramic was synthesized using a wet chemical precipitation method in different Ca/P ratios. After the synthesis step, the resulting powders were characterized in terms of X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TG), Fourier transform infrared spectroscopy (FTIR) and average crystallite size. For the conditions studied, the results showed that the use of marble waste allowed the obtaining of binary mixtures of the type ß-calcium pyrophosphate (ß-Ca₂P₂O₇)/magnesian whitlockite ((CaMg)₃(PO₄)₂). The new biphasic phosphate powders presented average crystallite size in the range of 42.56 nm to 57.55 nm. Thus, marble waste can be recycled to obtain biphasic phosphate bioceramic for medical applications with relevant repercussions on the circular economy.

Keywords:
Calcium-magnesium phosphate; biphasic bioceramic; marble waste; valorization

1. Introduction

Currently, phosphate-based bioceramics play an important role in medical and dental applications in the field of bone tissue engineering due to their bioactivity and biocompatibility properties, including (Ca-P) calcium phosphate and (Mg-P) magnesium phosphate bioceramics. The phosphate-based bioceramics are used in bone tissue engineering applications, typically in the form of powders, coatings, scaffolds and pastes. The Ca-P and Mg-P bioceramics that are receiving increasing attention in recent years as bone replacement or bone graft materials are β-CPP (β-calcium pyrophosphate), α-TCP (α-tricalcium phosphate), β-TCP (β-tricalcium phosphate), Hap (hydroxyapatite), MgNH₄PO₄.6H₂O (struvite) and Mg-WH (magnesium whitlockite)¹-¹⁰.

Despite being considered good biomaterials, Ca-P and Mg-P bioceramics, when used in isolation, still present some limitations that prevent their wider use for medical and dental applications¹¹-¹². One way to overcome these limitations for bone tissue regeneration applications has been the development of biphasic phosphate materials with improved functionality and properties¹³. More specifically, biphasic phosphate bioceramics correspond the blends of distinct Ca-P or combinations between Ca-P and Mg-P in different proportions.

Various types of biphasic phosphate bioceramics have been reported in the literature¹³-¹⁹, including Hap/β-TCP, Hap/α-TCP, α-TCP/β-TCP, β-CPP/β-TCP and Hap/β-MgTCP.

Brazil occupies a prominent position in the world scenario for the production of natural ornamental stones. According to ABIROCHAS²⁰, Brazilian production of natural stones in 2020 reached approximately 9 million tonnes. Of this amount, approximately 2.3 million tonnes corresponds to the production of carbonate rocks known commercially as marble and travertine. It is estimated that up to 40% of marble extracted from natural rock deposits is discarded as solid waste. In this context, some key issues associated with the disposal of marble waste deserve to be highlighted: i) when disposed of inappropriately, it causes a major impact on the environment and public health²¹,²²; ii) increasingly restrictive Brazilian legislation on solid waste requires ornamental stone companies to dispose of marble waste in a sustainable manner; and iii) disposing of marble waste in landfills is very expensive.

Marble waste is essentially composed of carbonates in form of calcite (CaCO₃) and dolomite (CaMg(CO₃)₂)²³,²⁴. Chemically, it is composed mainly of CaO and MgO, with a predominance of CaO. Given its mineralogical and chemical compositions, marble waste can be potentially attractive for recycling as a source of sustainable raw material, available in large amounts to replace the traditional carbonate raw material in the ceramic industry. In particular, the use of marble waste in the development of new ceramic products opens up perspectives for its valorization with relevant repercussions on the circular economy. In this context, several studies have been concerned with using marble waste as a low cost renewable material raw to produce ceramic materials, including fired clay bricks²⁵-²⁷, wall tiles²⁸,²⁹, mortars³⁰, concrete³¹ and cements²⁴,³². Considering its composition, marble waste can also be potentially attractive as a precursor source of carbonate in the synthesis of bioceramics based on calcium and magnesium phosphates. Despite this, few studies have reported the use of marble waste in the synthesis of calcium phosphate bioceramics. Miculescu et al.³³ synthesized a biphasic calcium phosphate bioceramic of the Hap/β-TCP type via an indirect chemical precipitation method using marble waste as a precursor of calcium carbonate (CaCO₃). Mocanu et al.³⁴ used a dolomitic marble waste to synthesize biphasic calcium phosphate bioceramics of the Hap/brushite or brushite/monetite types through an adapted indirect chemical precipitation method. Algamala et al.³⁵ produced Hap nanoparticles from marble wastes and evaluated their capacity as antimicrobial and antifungal agents. However, till date, the use of marble waste to synthesize a biphasic bioceramic combining calcium phosphate and magnesium phosphate of the ß-CPP/magnesium whitlockite type for bone tissue engineering applications has not yet been reported.

The major objective of this investigation is to study the feasibility of using marble waste from the ornamental stone industry in the synthesis of a biphasic bioceramic powder of the calcium phosphate-magnesium phosphate type for potential use in the field of bone tissue regeneration.

2. Experimental Procedure

The marble waste sample was provided by an ornamental stone company, Cachoeiro de Itapemirim-ES, Brazil. The marble waste in the form of fine powder was dried at 110 ºC for 24 h and classified by sieving into the < 75 µm fraction. Table 1 gives the chemical analysis of the marble waste. The chemical reagent HNO₃ (65%) was purchased from VETEC and Na₂HPO₄ (98%) was purchased from Sigma-Aldrich.

Table 1
Chemical analysis of marble waste (mass %).

CaO	MgO	SiO2	K2O	Others	LoI*
52.43	9.62	0.91	0.58	0.46	36.00

• ^*
  LoI – loss on ignition

In this work, biphasic bioceramic powders (calcium phosphate + magnesium phosphate mixture) were synthesized from marble waste through a wet precipitation process¹⁹,³⁶ using a molar ratio Ca:P (1:1). The synthesis process of biphasic phosphate bioceramics is briefly described. First, the marble waste powder was added to a HNO₃ solution (1 M) under stirring for 2 h until it is fully dissolved and resulted in the formation of a Ca(NO₃)₂ solution. Second, Na₂HPO₄ (disodium phosphate) dissolved in distilled water was slowly added by titration to the Ca(NO3)2 solution and stirred by 1h at 50 ºC. This process resulted in the formation of a white precipitate. Third, the solution with the white precipitate was vacuum filtered, the retained white powder was washed with deionized water, dried at 110 °C for 24 h, and calcined in a muffle furnace at 900 °C for 2 h, resulting in the biphasic calcium phosphate/magnesium phosphate powder. This synthesis process was repeated for the other studied molar ratios (Ca/P: 0.5:1, 1.5:1, 2:1, 2.5:1 and 3:1).

The marble waste and as-synthesized powders were structurally characterized by X-ray diffraction using a Shimadzu XRD-7000 powder diffractometer (Cu-Kα radiation, λ = 0.15418 nm, 0.05°/s step and 2θ = 10º - 90º). In this work the average crystallite size (D) of the powders was obtained from the Scherer’s equation (D = 0.9λ / βcosθ; λ = 0.15418 nm, β is the full-width at half maximum of the phosphate lines, and θ is the diffraction angle). The morphology of the synthesized powders was studied by scanning electron microscopy (model VEGA 3, TESCAN SEM). Thermal analyses (TG-DTA) were performed using a Netzsch Instrument Jupiter STA 449C simultaneous thermal analyzer at a heating rate of 10 ºC/min under air atmosphere. Fourier Transform Infrared (FTIR) Spectroscopy analysis of the synthesized powders was done in the range of 400 cm^-1 to 4000 cm^-1 with a Perkim-Elmer Spectrum 400 FTIR spectrophotometer.

3. Results and Discussion

3.1. Characteristics of the marble waste

The XRD pattern of the marble waste is shown in Figure 1. Structural analysis indicated that all the diffraction peaks of the marble waste powder were indexed to calcite (CaCO₃) and dolomite (CaMg(CO₃)₂). This result is in agreement with chemical analysis of the marble waste (Table 1). Therefore, marble waste can be considered as a relevant source of cheap alternative carbonate to replace traditional carbonate material.

Figure 1
X-ray diffraction pattern of marble waste.

Figure 2 displays the TG-DTA curves of the marble waste. It was found that the thermal behavior of marble waste is characterized by the occurrence of three thermic events at different temperatures in DTA curve, which can be described as: i) endothermic event at approximately 150 ºC, which indicates release of water absorbed on the particle surface; ii) small endothermic event at 771.6 °C that is related to dolomite decomposition; and iii) intense endothermic event at 864.9 °C that is related to the calcite decomposition. The TG curve showed that the decomposition of carbonates (dolomite and calcite) was accompanied by a high mass loss (42.26%) due to the release of CO₂. The total mass loss obtained corroborates the high value of the loss on ignition (Table 1).

Figure 2
TG-DTA curves of the marble waste.

Morphological aspects of the marble waste powder particles can be observed in the SEM image in Figure 3a. It is noted that the marble waste particles have an irregular morphology and a smooth surface. The marble waste powder has a wide particle size distribution, but the most of the particles are concentrated in the size range < 10 µm. The EDS spectrum in Figure 3b shows characteristic peaks of calcium (Ca), magnesium (Mg), carbon (C) and oxygen (O), reinforcing the results of chemical analysis (Table 1) and XRD analysis (Figure 1). The detected platinum peaks are associated with the sample metallization process.

Figure 3
a) SEM image of the marble waste particles and b) EDS spectrum.

3.2. Structural characterization of the synthesized powders

The structural characterization via X-ray diffraction of the synthesized powders are presented in Figure 4. XRD results revealed that all the synthesized powders were composed of β-calcium pyrophosphate (β-CPP, β-Ca₂P₂O₇) and magnesium whitlockite (Mg-WH, (CaMg)₃(PO₄)₂). These obtained phosphate phases are in accordance with the literature³⁷-³⁹. In fact, the marble waste used in this work contains 52.43 wt.% CaO and 9.62 wt.% MgO (Table 1), resulting in a Mg/Ca ratio of 0.18. On the other hand, it is known that an Mg/Ca ratio > 0.05 favors the replacement of calcium by magnesium in the crystalline lattice of calcium phosphates, leading to the formation of magnesium whitlockite⁴⁰,⁴¹. It is also worth mentioning that the diffractograms in Figure 1 did not show any diffraction peaks of calcite and dolomite from the marble waste. This result suggests that the digestion process of carbonates (calcite and dolomite) present in the marble waste was fully efficient¹⁷,³⁶,³⁹.

Figure 4
XRD patterns of the synthesized powders: a) Ca/P (0.5:1); b) Ca/P (1:1); c) Ca/P (1.5:1); d) Ca/P (2:1); e) Ca/P (2.5:1) and f) Ca/P (3:1).

As found in Figure 4, all the synthesized powders corresponded to a biphasic phosphate bioceramic of the β-CPP/Mg-WH type, regardless of the Ca/P ratio. However, small but important differences can be observed in the new synthesized biphasic phosphate bioceramics. For the biphasic bioceramics obtained with Ca:P (1:1) and Ca:P (2:1) molar ratios, it was observed that the main peak at ~ 29.4º corresponded to the calcium β-CPP phase. In this case, the formation of β-CPP was facilitated by the molar concentration used in these samples associated with calcination at 900 ºC⁴². It is also noted that these biphasic bioceramics presented low intensity magnesium whitlockite diffraction peaks. For the other molar ratios (Ca:P), it was observed that the main peak at ~ 31.1° corresponds to the magnesium whitlockite phase. In addition, the diffraction peaks related to the β-CPP phase had their intensities decreased. This fact may be related to the increase in magnesium concentration in these samples, since by varying the proportion of calcium, a greater quantity of marble waste was supplied to the digestion solution. In fact, as shown in Table 1, marble waste is rich in calcium and magnesium.

The synthesized biphasic phosphate bioceramic powders of the β-CPP/Mg-WH type presented the following average crystallite size values determined by the Scherrer equation: i) Ca:P (0.5:1) = 55.94 nm; ii) Ca:P (1:1) = 42.56 nm; iii) Ca:P (1.5:1) = 43.16 nm; iv) Ca:P (2:1) = 57.55 nm; v) Ca:P (2.5:1) = 45.56 nm; and vi) Ca:P (3:1) = 47.84 nm. Therefore, all β-CPP/Mg-WH biphasic bioceramics present mean crystallite sizes within the nano-sized range. This result is very relevant, since calcium phosphate-based bioceramic nanoparticles have unique properties and functions that are highly attractive for medical applications²,¹¹.

3.3. FTIR analysis

Figure 5 displays typical FTIR spectra of the biphasic calcium-magnesium phosphate bioceramic powders synthesized using marble waste. The FTIR spectrum obtained for the biphasic bioceramic synthesized using a Ca:P (1:1) ratio is shown in Figure 5a. This biphasic phosphate bioceramic (β-CPP/Mg-WH) mainly presented a main phase corresponding to the β-CPP phase (Figure 4b). The identification of the vibrational groups of calcium-magnesium phosphate materials are described as follow¹⁷,²³,⁴³-⁴⁵. Vibrational bands were found at 3438.74 cm^-1 and 1628.58 cm^-1, indicating the presence of water molecules and OH^- groups on the particle surface. The vibrational band at 2356.86 cm^-1 corresponds to the CO₂ group, which is related to the atmosphere of the environment where the equipment is installed. The vibrational bands at 1219.31 cm^-1 and 969.58 cm^-1 demonstrate the presence of the PO₄^3- group. The vibrational band detected at 740.81 cm^-1 represents the bonds corresponding to the Ca²⁺ ion. The vibrational bands detected at 553.70 cm^-1 and 484.26 cm^-1 are associated with the Ca-O and Mg-O groups, respectively. The FTIR spectrum of the biphasic bioceramic synthesized using a Ca:P (2.5:1) ratio was very similar, as shown in Figure 5b. More precisely, only small differences can be observed between the FTIR spectra, which are probably related to the different amounts of the β-CPP and Mg-WH phases present in these biphasic bioceramics.

Figure 5
FTIR spectra of the synthesized powders: a) Ca:P (1:1) and b) Ca:P (2.5:1).

3.4. Morphological analysis

The morphological aspects of the synthesized calcium phosphate-magnesium phosphate powders can be observed in Figure 6. SEM micrographs revealed that the nano-sized biphasic powders are composed of highly agglomerated plates with non-uniform sizes. Such observed agglomerated plates are due to the calcination step at 900 ºC, which caused the initial solid sintering between the synthesized nanoparticles. However, apparently, the morphology of the nanoparticles presents equiaxed shapes. This result is relevant, since nanometric powders tend to favor the wettability and capillarity properties of phosphate-based bioceramics, and, thus, can aid in the repair and reconstruction of damaged bone tissue¹¹,¹³.

Figure 6
SEM images of the synthesized powders: a) Ca/P (0.5:1); b) Ca:P (1:1) c) Ca/P (1.5:1); and d) Ca/P (2.5:1).

3.5. Thermal stability

The thermal behavior described in terms of TG-DTA curves of the biphasic calcium phosphate-magnesium phosphate bioceramics synthesized using marble waste is shown in Figure 7. The results indicated that the synthesized biphasic bioceramics showed high thermal stability when heated to ~1000 ºC, independently of the molar ratio (Ca:P) used. In fact, the biphasic bioceramic obtained with a Ca:P (1:1) molar ratio presented a total mass loss of 0.60% (Figure 7a), while that obtained with Ca:P (2.5:1) molar ratio had a total mass loss was of 0.87% (Figure 7b). In the DTA curves, endothermic events are observed at 192.2 °C (Figure 7a) and 186.3 ºC (Figure 7b) due to the loss of adsorbed water from the biphasic bioceramics (β-CPP/Mg-WH). These results are quite relevant, since bioceramics, when implanted in a biological environment, must present high thermal stability without weight loss, in case of temperature changes.

Figure 7
TG-DTA curves of the synthesized powders: a) Ca:P (1:1) and b) Ca:P (2.5:1).

4. Conclusions

The experimental results indicated that it is feasible to synthesize calcium phsophate-magnesium phosphate bioceramics using marble waste composed essentially of carbonates (calcite and dolomite). The valorization of marble waste to produce bioceramics for medical applications can be an attractive technological alternative for the final disposal of this polluting solid waste. It was found by XRD analysis that all the synthesized powders were composed of a biphasic mixture of β-CPP (β-calcium pyrophosphate) and Mg-WH (magnesium whitlockite). However, the predominance of β-CPP or Mg-WH in biphasic bioceramics is dependent on the molar ratio (Ca:P). The synthesized powders presented an average crystallite size in the 42.56 -57.55 nm range, indicating a nanostructured nature. FTIR results confirmed the presence of vibrational bands related to the β-CPP and Mg-WH phases identified in the biphasic bioceramics. SEM images revealed that the powder particles are highly agglomerates with equiaxed morphology. TG-DTA analyses indicated low mass loss and high thermal stability during heating. Therefore, these findings suggest that the marble waste offers a promising strategy for use as a cheap carbonate source in the manufacture of biphasic calcium phosphate-magnesium phosphate bioceramics.

5. Acknowledgements

The authors acknowledge the Foundation for Research Support of the State of Rio de Janeiro – Brazil (FAPERJ) - Process No. E-26/201.137/2022 and National Council for Scientific and Technological Development – Brazil (CNPq) - Process No. 306147/2023-8.

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Publication Dates

• Publication in this collection
  23 May 2025
• Date of issue
  2025

History

• Received
  10 Jan 2025
• Reviewed
  31 Mar 2025
• Accepted
  21 Apr 2025