Sonochemistry synthesis of zinc silicate ceramic nanoparticles and their characterization

doi:10.21203/rs.3.rs-3235393/v1

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Sonochemistry synthesis of zinc silicate ceramic nanoparticles and their characterization

https://doi.org/10.21203/rs.3.rs-3235393/v1

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published 29 Nov, 2023

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This research aims to present a sonochemical synthesis method for high-purity willemite nanopowders. Initially, zinc silicate hydrate nanoparticles were created using a modified sonochemistry method in which zinc salts and waterglass were used as starting materials to obtain zinc silicate precipitate under pH-controlled conditions (11-12) and Argon gas flux. Following that, the precipitate was heat treated at various temperatures. TGA/DSC, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), dispersive X-ray spectrometry (EDX), and N2 gas adsorption characterizations were also used to assess phase changes, morphological properties, microstructures, and chemical composition.

The formation temperature of a well-crystalline willemite monophase was determined to be 890°C, and this was supported by XRD analysis. The synthetized material had high homogeneity and excellent purity, according to EDX elemental mapping. Its nanometric nature was further confirmed by microscopic observations (SEM, TEM). Notably, compared to previously reported methods, the aforementioned technique uses a moderate synthesizing temperature, making it economical for mass production and potentially useful in a variety of industrial fields, including ceramics, paints, plastics, biomaterials, and composites, among others.

EDX elemental mapping demonstrated high homogeneity and excellent purity of the material. Microscopic observations (SEM, TEM) further confirmed its nanometric character. Notably, the aforementioned method employs a moderate synthesising temperature compared to previously reported methods, making it cost-effective for mass production with potential applications in various industrial fields, such as ceramics, paints, plastics, biomaterials, and composites, among others.

Willemite

Zinc silicate

Ceramic

Sonochemistry

Wet chemical synthesis

Nanopowders

From construction to electronics, their transformative properties contribute significantly, and their presence in steel metallurgy, electrochemistry, radiochemistry, construction, electronic, glass manufacturing, ceramics, pottery, cosmetics, personal care …etc.[1–6], enhances functionality and appeal. They are unsung heroes, leaving an indelible mark on human progress. Once upon a time, in the enchanting world of minerals, a rare and captivating zinc silicate mineral known as “willemite” (Zn₂SiO₄) took center stage[1, 2]. This remarkable gem could be found in the depths of the earth, gracefully forming as a natural wonder, or be carefully synthetized by human. What made willemite truly special was its abundant concentration of zinc, making it a coveted source for the production of valuable zinc metal. But its allure didn't end there, it possessed a magical luminescence that emitted a captivating glow, enchanting all who gazed upon it. [1, 3]. Its luminescence efficiency was unmatched, adding an ethereal charm to its already vibrant and captivating colors. Beyond its visual splendor, Willemite's physico-chemical properties were equally exceptional, showcasing excellent stability and endurance, making it a reliable gem for various industrial applications [1, 2]. Moreover, its thermal stability ensured that it could withstand the test of high temperatures without losing any of its enchanting attributes.

As the tale of willemite unfolded, it became a prized gem in the realm of minerals, weaving a story of beauty, value, and fascination. In the enchanting realm of mineralogy, willemite took on three distinct polymorphs, named α-Zn₂SiO₄, β-Zn₂SiO₄, and γ-Zn₂SiO₄ respectively, each possessing a unique crystalline structure and a mesmerizing array of physical properties [1, 4–6].The first one (α-Zn₂SiO₄) is the most common stable polymorph, which crystallizes in the trigonal system [1]. It is one of the few silicate minerals that have a trigonal–rhombohedral symmetry [7, 8] with phenakite structure, that consists of complex tetrahedral framework [1, 9] Where, each oxygen ion coordinated to one silicon (Si) and two zinc(Zn) atoms [10], and all atoms are generally in the overall position [9]. With this kind of structure this polymorph provides excellent and special optical properties [7, 11]. On the other hand, the two additional polymorphs are considered metastable phases, able to transforming into the stable α-phase at elevated temperatures [6]. Among these, the beta-phase (β-Zn₂SiO₄) is less prevalent and crystallizes in the tetragonal system, exhibiting a crystal structure with square symmetry. Typically, opaque and adorned with brown or yellow-brown coloration, β-Zn₂SiO₄ is deemed metastable and is known to form under specific conditions, such as high temperatures or pressures [1]. In contrast, the γ polymorph is the rarest among the three, featuring a cubic crystal structure that is predominantly stabilized under extremely high temperatures or under specific synthesis conditions [1]. This particular polymorph has received less extensive research attention compared to its α-Zn₂SiO₄ and β-Zn₂SiO₄ counterparts [1].

Synthetic willemite has rapidly gained significance and widespread adoption as a phosphorescent agent in optoelectronic and lighting devices [1, 12, 13]. Its historical importance is evident as it served as the foundation for the first-generation fluorescent tubes [5, 14, 15]. Particularly, when manganese-doped willemite (Zn₂SiO₄:Mn²⁺) is exposed to specific wavelengths of light, a fascinating phosphorescence effect emerges. The emitted light's specific wavelength and intensity are contingent upon the energy levels and electronic transitions within the dopant ions and the crystal structure of willemite [16].

In the enchanting world of luminescence, there exists a captivating behavior that has made it a beloved choice as a luminescent agent in various realms. This magical property opens doors to a myriad of possibilities, offering its luminescent glow as a guiding light in numerous areas such as:

Optoelectronics, LED, lighting devices [13, 16–18] plasma displays, field emission displays (FEDs ) [19, 20], electronics devices, insulators [21] paints, art, glow-in-the-dark products [22–24], invisible security markings [25, 26], radiation detection and dosimetry [13, 16], scintillation detectors for medical imaging[27, 28],biomaterials [29–35], sensor technology ( temperature, pressure, gas, humidity…) [36, 37] Numerous authors have been conducted various approaches for synthesizing Zn₂SiO₄, such as the sol-gel method [38, 39], solid-state route[40, 41], polymer precursor method[42], spray pyrolysis method[43, 44], and hydrothermal method [45, 46], solvothermal method [47]. However, these conventional methods often entail high-pressure conditions or heat treatment at temperatures exceeding 180°C for extended periods. In contrast, expensive and toxic raw materials and complicated processing technologies, are not appropriate for commercial purposes [48, 49]. Nowadays, researchers are trying to find alternative processes with less expensive, non-toxic, and abundantly available raw materials. To overcome these challenges, the sonochemical method emerges as a promising alternative. This technique has gained prominence in recent years as a valuable tool in the synthesis of novel nano-sized materials under ambient conditions [50–52]. On the other hand, it seen as a very simple, cost effective, eco-friendly and efficient way, for obtaining high purity zinc silicate nanopowders.

In the present work, we report a new way to synthesize a pure zinc silicate nanopowders, through a modified sonochemistry route, using inexpensive and nontoxic raw materials as well as a simplified processing methodology. This nanopowder was synthesized at moderate temperature compared to what is reported by several authors [4, 53–55]. It can be dedicated to numerous applications, particularly, if subjected to subsequent manganese (Mn) doping. The applied procedure is an attractive technique, due to its advantages such as low-processing cost, energy efficiency and high production rate and in particular the ability of this method to carry out doping during synthesis (Mn, Eu, Ce…etc.). After all, this study introduces a novel method for low-temperature synthesis of willemite nanostructures utilizing ultrasonic waves. The process involves ultrasonic treatment at temperatures below 60°C for less than 60 minutes. A similar sonochemical approach was previously employed for wollastonite nanoparticle synthesis [56].

2.1. Chemicals

All the chemical reagents used in this work such as zinc chloride (≥ 99.9%), sodium hydroxide (≥ 97.0%) and absolute ethanol (≥ 99.5%), sodium disilicate (Na₂O.2SiO₂); were commercially obtained from Sigma-Aldrich and PQ corporation respectively. Whereas argon gas (≥ 99.99%), were received from and ALPHAGAZ™. We have also, used deionized and decarbonated water along this work.

2.2. Synthesis

The as-prepared zinc silicate nanopowders were synthetized using a new way which has been reported in our previous paper [56]. The experimental protocol was conducted as indicated in Fig. 1 as following: firstly, three clear and stabilized solutions of zinc chloride (ZnCl₂), sodium hydroxide (NaOH) and sodium disilicate (Na₂O.2SiO2) were preprepared using deionized and decarbonated water. This was done by dissolving zinc chloride and sodium disilicate, separately, in given quantity of water so that the ratio zinc to silicon is equal to tow. The first two solutions (CaCl₂, NaOH) were added dropwise into third one (including sodium disilicate) under continuous stirring, argon gas (Ar) flux and ultrasonic waves generated by a Hielscher’s digital ultrasonic processor (UP400St-400w,24kHz). The pH of the reaction medium was adjusted to 11–12, through the control of the addition (dropwise) of both zinc chloride and 1N sodium hydroxide solutions. Subsequently, after 2 hours of stirring at 40°C, the white precipitates were collected, then vacuum filtered repeatedly, and finally washed (with a mixture of ethanol and distilled water) several times. The resulting precipitates were then washed with pure ethanol and dried at 90°C in a vacuum oven, for 48 hours. The final product was then calcined firstly at 650°C and t 800°C respectively for 2 h, in an electric muffle furnace (in ambient air).

2.3. Characterization techniques

Phase analysis was performed with “Panalytical X'PERT PRO MPD” diffractometer, operating with a Cu_Kα radiation (λ = 1.54056Å). The morphology and microstructures of the powders were studied firstly with a scanning electron microscope (SEM, JEOL-7500F) equipped with an energy dispersive X-ray Spectroscopy (EDS) and secondly with a transmission electron microscope (TEM, Philips Tecnai10). Surface area, pore diameter and pore volume were estimated at 77 K according to the Brunauer-Emmett-Teller (BET) method, with a Micromeritics “ASAP 2420” unit. While, thermal analyses were carried out with a “Mettler Toledo TGA/DSC 3+” device. Particle size distribution (PSD) were estimated by “ImageJ” software exploiting TEM or SEM photographs (by measurement of hundreds of particles size).

3.1. Thermal analysis

Thermal analysis curves for the main dried powder, are shown in Fig. 2. From the TGA curve, a total weight loss ratio of about 13%, is measured in the temperature range of 25-1100°C. The stepped shape of the TG curve is due to the successive removal of various forms of water present in the powder. In fact, this weight loss spans over three distinct stages. The first one: 25–200°C, in which the weight loss is 4.0 wt.%, can be attributed to the dehydration process generated by the removal of adsorbed and free water.

The second stage 200–450°C, in which the weight loss is 4.0 wt.%, suggests a dehydration (removal of molecular and crystallized water). The third stage: 500–850°C, the weight loss is 4 wt.%; it is probably, related to the dehydroxylation of the substance. The process of water removal and dehydroxylation tacks place with the simultaneous formation of the crystalline zinc orthosilicate Zn₂SiO₄. The DSC curve shows two small exothermic peaks in the temperature range 700–900°C.

The first at 760°C may be associated with the crystallization of β-Zn₂SiO₄; and the second at about 890°C, may be linked to the formation of α-Zn₂SiO₄.

3.2. X-Ray diffraction analysis

In order to confirm the purity and crystalline structure of the main products, XRD analyses were carried out. XRD patterns of the main synthesized products and those calcined at different temperatures (650°C,800°C and 900°C) are shown in Fig. 3. We can see that the XRD patterns of the as-synthetized powder, we have initially a broad hump centered around 2θ ~ 28°; it may originate from an amorphous characteristic caused by the long-range disorder, due to a poorly formed crystal phase.

Indeed, according to the JCPDS references n°: 01-089-4326, n°: 00-029-1393 and n°: 00-024-1467 respectively, this hump originated from the coexistence, of three poorly crystalized phases: Hemimorphite [Zn₄(Si₂O₇)(OH)₂.(H₂O)], Samsonite [Zn₃Si₄O₁₀(OH)₂·4H₂O] and Zinc Silicate respectively. However, as the annealing temperature is raised to 650°C, a sharp peak begins to appear from the background noise approximately at 2θ ~ 36° (Fig. 3) signaling the formation of β-Zn₂SiO₄ according to the JCPDS n°: 00-014-0653. This behavior was reported by Taylor [57], as the result of the formation of zinc silicate metastable phases. Meanwhile, when heating up to 900°C, the last formed phase(β-Zn₂SiO₄), transforms into a new well crystalized phase (α-Zn₂SiO₄), characterized by a rhombohedral structure and a space group of R-3 with the cell constants: a = 13.9381 Å, b = 13.9381 Å, and c = 9.3100 Å according to JCPDS card n^o: 00-037-1485. This last one, is the most common crystalline phase of zinc silicate [1, 58], so called willemite (α-Zn₂SiO₄). Those results are in accordance with Taylor’s and Kang’s observations respectively [57, 59].

It is very instructive to point out that no XRD impurity peaks from other phases, were detected (zinc oxide, silicon oxide…Etc.); which confirms the high purity of the product. This behavior is completely consistent with Mu-Tsun Tsai obfindings [6].

3.3. Electron microscopy (SEM/TEM) analysis

Powders morphology, before and after calcinations, were investigated using SEM &TEM microscopy. As we can see on the SEM image (Fig. 4-a), the sample before calcination presents a loose fluffy cloud-like morphology. The use of microphotography reveals aggregate, characterized by a very rough surface, made of small particles (mainly in the range 50 ~ 100 nm) as can be seen on the corresponding TEM images in Fig. 5-a. These fine grains are elongated as tiny nano-sticks (50 nm length x 100 nm width) as revealed by ImageJ software. These observations are consistent, in terms of the morphology with a previous reports Samigullina [60] and Zhiying Ding [61].

As regards Fig. 4-b, it shows the SEM micrographs for the powders calcined at 650°C. It has a morphological structure similar to that of the as prepared powder.

On the other hand, TEM images (Fig. 5-b) show a mixed morphology; (a combination of the as prepared and that obtained after heating at 650°). However, TEM image (Fig. 5-b), reveals that some fine grains coalesce to give elliptical and larger ones as a result of heating. These particles are in general, not isolated, but clustered. Furthermore, Fig. 4-c presents the SEM micrograph of the powder heat treated at 900°. Inward, we can notice a new morphology (corresponding to the willemite phase). In all cases, SEM and TEM images (Fig. 5-c), reveal clearly, that the powder is less agglomerated, but characterized by a smooth particle surface (when compared to the precedent one). In addition, the particles are separated (distinguishable) and the surface presents fewer pores. In the meanwhile, grain size tends to increase with temperature (500 nm length x 800 nm width). It is worth noting that Quadri’s TEM results are in good agreement with our observations [62].

3.4. Energy-Dispersive X-ray Spectroscopy (EDS) analysis

Figure 6, and Fig. 7 shows both the Energy Dispersive X-Ray Spectroscopy (EDS) qualitative elemental spectrum evolution and quantitative elemental evolution respectively. First of all, EDS qualitative elemental spectrum (Fig. 6) shows evidently, that all samples (whether calcined or not), are basically made of three elements: O, Zn and Si (these are the major constituents of zinc silicate). Regarding gold (Au), its presence can be attributed to the applied metallization layer. It is crucial to underscore that only these elements are present, within the detection limit of the EDS analysis, and no other elements have been detected. This confirmation validates both the high purity and excellent quality of the synthesized material.

According to the data obtained from the EDS quantitative analysis (Fig. 7), the variations in the atomic percentages of Zn, O, and Si with temperature do not exhibit a consistent pattern. However, as illustrated in Fig. 8, a clear correlation is evident between the Zn/O atomic ratio percentage (Zn/O %) and the heat treatment process. It exhibits a direct proportional relationship with the calcination temperature. This behavior can be ascribed to the process of dehydration and/or dihydroxylation occurring within the powder during the calcination process, resulting in the removal of water molecules that contain an excess of oxygen atoms.

Furthermore, the observed Zn/Si ratio in the as-synthesized powder (Fig. 7) does not exhibit a scientifically meaningful correlation. Where, the lack of the significant correlation in the Zn/Si can be attributed to the precision of the EDS analysis (semi-quantitative technique). As a result, the measured Zn/Si ratio may have some level of uncertainty, making it difficult to establish a precise correlation with other factors or properties.

Figure 9 presents the elemental mapping and chemical composition analysis of the final synthesized willemite powder. The results demonstrate a uniform distribution of colors corresponding to each element (Zn, Si and O), indicating a homogeneous dispersion of Zn, Si, and O throughout the sample. It is necessary to note that, no im-purities are detected, which confirms both the purity and the quality of the samples. However, it's important to consider that the uniformity of the EDX mapping can also be influenced by other factors, such as the detection limits of the instrument, the resolution of the mapping technique. Furthermore, it should be noted that this uniformity may also be influenced by factors such as sample preparation techniques and the surface characteristics of the powder.

Anyway, EDS analysis unequivocally confirms the absence of impurities, such us chloride, carbonates, or nitrides anions, within the limits of the optimal EDS acquisition conditions. This finding provides compelling evidence for the high purity of the final product "willemite" (Fig. 8). Although EDS may lack precision compared to quantitative analytical methods, it is still valuable and informative in providing qualitative and approximate quantitative information.

3.5. BET surface area and pore properties analysis

Figure 10 shows nitrogen adsorption–desorption isotherms of the as-synthetized and calcined powders (starting powder, powder annealed at 650°C and powder annealed at 900°C).

As expected, through these results, it appears that there is a complete agreement with the previously mentioned structural and morphological behaviors. First of all, the as-synthetized powder’s physisorption isotherm, belongs to the IV^th type (associated with capillary condensation in mesopore structures) [63]; it is also characterized by an H₃ hysteresis loop (IUPAC classification) [64–67].

The latter indicates the presence of excessive and slit shaped pores; this results from the coexistence of loosely coherent particles (as presented by TEM & SEM images previously).

Figure 11, shows the evolution of the Barret-Joyner-Halenda (BJH) pore size distribution (PSD) as a function of temperatures, obtained by BET nitrogen adsorption and desorption measurements.

As it can be seen, pore size distribution (PSD) curves do not follow a coherent and ordinary behavior. The curve corresponding to the as-synthesized powder, is characterized by a broad peak centered around 56nm (mesopores region) and a very small one at 3nm (micropores region). This is a family of slit-like pores or empty spaces created during the synthesis of the nanopowders. After the first heat treatment (650°C), PSD maximum peak, moves towards smaller pore sizes values; getting a value of 17 nm. We have the same behavior with the peak intensity, the number of pores decreases after firing at 650°C. However, the sharp peak belonging to the micropore zone (3nm), remains unchanged. This could be due to the presence of tiny spaces between the sheets because of the release of water during the dehydration process or free water by evaporation.

Moreover, when the temperature reaches 900°C, the PSD peak; shifts again to higher values (22 nm). while, the intensity of the peak increases, indicating an increase in the amount of mesopores. This can be explained by the stacking/fusing of previous nano-sheets in addition to a phase transformation (β-willemite to α willemite).

As shown in Fig. 12, the specific surface area (SSA) decreases as the temperature is raised. This is because of the increase in particle size leading to agglomeration, as a result of the heating effect at high temperatures (650–900°C) [68]. In fact, we are in the presence of a process consisting in dehydration and dehydroxylation, accompanied by pore clogging, coalescence or open porosity decline, taking place when the annealing temperature is increased [69]. As examples, we have the following SAA measurements: 75.6 m² g^− 1, 6,1 m²g^− 1 and 1.69 m²g^− 1 corresponding to the as synthetized, heat treated at 650°C and heat treated at 900°C, respectively. The same behavior is also observed (Fig. 12) concerning the total pore volume (TPV); the maximum value (TPV ≈ 0,41 cm³.g^− 1) was recorded for the as-synthetized powder, while a smaller one (≈ 4.10^− 5 cm³.g^− 1) was obtained for the powder calcined at high temperature(T = 900°C).

These results have shown that the specific surface area and pore volume are affected by the heat treatments of samples.

3.6. Particle size distributions

Figure 13 shows particle size distributions for the nanopowders heat treated at different temperatures. Image J software was utilized to make measurements on several hundreds of particles using TEM images. It is found that the average particle size increases with the annealing temperature, due to the nucleation process. At higher temperatures, the latter becomes slow, thus allowing amorphous zinc silicate hydrated nanoparticles to grow. As it can be seen the particle size of willemite (194.03 nm) is larger than that of amorphous zinc silicate annealed at 650°C(82.3nm), it is also greater than that of the prepared powder (30.5 nm). Another fact, the growth of nanoparticles depends on the surface reaction. All this means that the temperature helps the coalescence process. At elevated temperatures, the coalescence process slows down, facilitating the growth of amorphous zinc silicate hydrated nanoparticles. The particle size of willemite was determined to be approximately 194.03 nm, which is larger than that of the amorphous zinc silicate annealed at 650°C (estimated at 82.3 nm) and significantly greater than the initially prepared powder (estimated at 30.5 nm). This indicates that temperature plays a crucial role in influencing the nanoparticle growth, and the process is governed by surface reactions, leading to the coalescence of nanoparticles.

A simple, cost effective, environment friendly and very efficient method has been used to synthesize high purity willemite (α-Zn₂SiO₄) nanopowders, via a modified wet chemical route. Pure monophasic willemite (α-Zn₂SiO₄) powder was obtained after heat treatment at a 900°C, this temperature remains moderate compared to other techniques. The method is characterized by its ability to inject other reagents, in particular dopants (Mn, Ce, Eu, etc.). Were, dopant salts (e.g., MnCl₂, Ce(NO₃)₃, Eu(NO₃)₃) can be added to the reaction medium along with the precursors. XRD and EDS analysis indicate the high purity and the good homogeneity of the final willemite nanopowder. On the other hand, it is found that heat treatment has an important influence on the morphology of the samples, indeed, as the temperature increases, as-synthetized powders exhibit several micro-structural changes; this is confirmed by SEM and TEM microscopy. Furthermore, BET textural analysis reveals an inverse proportionality between the specific surface area (SAA) and the calcination temperature. We can add that the particle size diameter (PSD) changes with temperature through the coalescence process.

Finally, we conclude that the method in question, can be used to synthesize pure massive zinc silicate materials on a large scale at a lower cost, which opens up an interesting perspective for use in several industrial fields such as ceramics, paints, plastics, biomaterials, composites, and sensors.

Acknowledgements

The authors would like to thank Dr. N. Tumanov (PC² platform), D^r. J-.CO-LOMER & M^r_.C. CHARLIER (Microscopy service). P^r. B-L. Su (C.M. I), P^r. Z. Mekhalif (C.E. S) and P^r. S. Lucas (LARN), from university of Namur-Belgium, for their scientific collaboration.D^r Bouatrous would like to thank P^r. F. DJAZI (L.R.P.C.S.I: University of Skikda - Algeria) for his help during the first this research.

Author contributions

All authors had contributed to the paper’s conception and design. Characterizations and analysis had been had been carried out by Q-BIZOT & M. BOUATROUS. The initial draft of the manuscript was prepared by M-BOUATROUS and subsequently reviewed by F. BOUZERARA. It was also mentioned that the final manuscript had been read and approved by all authors.

Competing interest:

The authors declare that they have no competing interests

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Sonochemistry synthesis of zinc silicate ceramic nanoparticles and their characterization

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Abstract

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1. Introduction

2. Materials and methods

2.1. Chemicals

2.2. Synthesis

2.3. Characterization techniques

3. Results and discussion

3.1. Thermal analysis

3.2. X-Ray diffraction analysis

3.3. Electron microscopy (SEM/TEM) analysis

3.4. Energy-Dispersive X-ray Spectroscopy (EDS) analysis

3.5. BET surface area and pore properties analysis

3.6. Particle size distributions

4. Conclusion

Declarations

References

Additional Declarations

Supplementary Files

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