*Dhruvi Dave, 1Mansi Jani
*Associate Professor, 1Assistant Professor
*SAL College of Pharmacy, 1Anand Pharmacy College
Article Details
Title: Navigating Arc Discharge and Beyond: Emerging Strategies and Applications in Silver Nanoparticle Synthesis
Authors: Dhruvi Dave, Mansi Jani
Published in: PEXACY International Journal of Pharmaceutical Science
Volume/Issue: 3(12)
Pages: 75–93
Publication Date: 29/12/2024
ISSN: 2584-024X
Language: English
Publisher: PEXACY International Journal of Pharmaceutical Science
PDF Download: Access Full Paper
Abstract
Silver nanoparticles (AgNPs) have solidified their position as essential nanomaterials in a wide range of industries, including electronics, healthcare, environmental remediation, and catalysis. This review provides a comprehensive overview of the diverse methods used to synthesize AgNPs, with particular emphasis on arc discharge and hybrid approaches that have recently emerged to address scalability and customization challenges. We begin by exploring traditional physical and chemical techniques—such as electrochemical reduction, chemical reduction, and photochemical methods—underscoring their advantages and limitations. We then delve into the growing interest in biological and green synthesis methods, particularly those involving algae, fungi, and bacteria, which offer safer and more sustainable pathways for AgNP fabrication. Moreover, this review explains how hybrid processes, combining arc discharge with chemical or biological methods, can further tailor AgNP properties. The mechanisms of nanoparticle formation, alongside the roles of surfactants and capping agents, are also discussed. Key applications are surveyed, including their growing use in electronics, photocatalysis, biomedicine, and food packaging. Finally, critical safety and regulatory considerations are presented, highlighting the importance of rigorous toxicity assessments to ensure environmental and public health. Collectively, this survey underscores how arc discharge and other emerging synthesis routes are shaping the next generation of AgNPs, moving toward a paradigm of safe, robust, and application-oriented nanomaterials.
Keywords: Arc discharge, Green synthesis, Silver nanoparticles, Hybrid methods, Surfactant-free fabrication, Microbial synthesis, Nanocatalysis, Biomedical applications, Scale-up production, Nanotoxicity.
Article can be accessed online on: PEXACY International Journal of Pharmaceutical Science
DOI: 10.5281/zenodo.14568527
Corresponding Author-*Dhruvi Dave
Email- dhruvimehta09@gmail.com
Update: Received on 03/12/2024; Accepted; 10/12/2024, Published on; 29/12/2024
1. INTRODUCTION
Silver nanoparticles (AgNPs) have been of sustained research interest for decades due to their versatile properties and broad utility in sectors such as electronics, medicine, environmental remediation, textiles, and catalysis (Wang et al., 2019). Compared to their bulk silver counterparts, AgNPs exhibit unique physiochemical characteristics—particularly a large surface-to-volume ratio and size- or shape-dependent electronic and optical features—that make them attractive for a host of applications. For example, they are widely applied as antimicrobial agents in healthcare and consumer products, offering potent biocidal effects against bacteria, fungi, and viruses (Iravani, Korbekandi, Mirmohammadi, & Zolfaghari, 2014).
Although numerous chemical and physical methods have traditionally been employed for nanoparticle synthesis (Gudikandula & Charya Maringanti, 2016), arc discharge has gained attention as a promising route for producing high-quality metallic nanoparticles (Zhang et al., 2017; Ashkarran, 2010). This method produces nanoparticles via plasma-induced vaporization of a silver source, yielding highly pure products. Moreover, arc discharge can be efficiently combined with other synthesis routes—particularly chemical or biological processes—to create “hybrid” techniques that leverage complementary benefits from each approach.
This review offers a detailed exploration of the latest trends in silver nanoparticle synthesis, emphasizing arc discharge and the hybrid methods that build upon it. By blending physical, chemical, and biological principles, researchers can now achieve unprecedented control over nanoparticle characteristics such as size, shape, composition, and surface chemistry (Tseng et al., 2018). We also provide a broad perspective on how these advancements are influencing the next generation of AgNP applications, whether in advanced electronic circuits or eco-friendly antimicrobial formulations for food packaging. Furthermore, we address regulatory and safety concerns, underscoring the importance of designing and implementing sustainable nanomaterial production processes (Wang et al., 2019).
The review is structured as follows: we begin by outlining the main synthetic routes—physical, chemical, and biological—and highlight their benefits and downsides. Next, we delve into arc discharge and hybrid methods specifically, illustrating how combining arc discharge with approaches such as biological synthesis can yield uniquely tailored nanoparticles. We then discuss core applications that drive the commercial and scientific interests in AgNPs, and conclude with key challenges, future directions, and an overview of the regulatory environment.
2. Traditional Approaches to Silver Nanoparticle Synthesis
2.1 Physical Methods
Physical methods generally involve top-down processes that convert a bulk silver source into nanoparticles. Examples include arc discharge, laser ablation, inert gas condensation, and high-energy ball milling (Kim, Osone, Kim, Higashi, & Seto, 2017). While these approaches can produce high-purity nanoparticles, they sometimes have scalability issues, require expensive equipment, or offer limited control over product morphology (Wongrat et al., 2019).
2.1.1 High-Energy Ball Milling
High-energy ball milling uses mechanical energy to fragment bulk silver into nanoscale particles. The choice of milling speed, time, and process control agents—such as surfactants or cryogenic coolants—determine the final properties (Kumar, Biswas, & Gupta, 2016). However, contamination from the milling media and broad particle size distributions pose persistent challenges.
2.1.2 Laser Ablation
Laser ablation entails focusing a high-power laser onto a silver target in a liquid or gaseous medium, generating a plasma plume that condenses into nanoparticles (Kim et al., 2017). This method enables contaminant-free production but suffers from relatively low yields and often necessitates specialized laser systems with significant power consumption (Amendola, Polizzi, & Meneghetti, 2007).
2.1.3 Inert Gas Condensation
In inert gas condensation, silver is evaporated in a vacuum chamber filled with an inert gas (Raffi, Rumaiz, Hasan, & Shah, 2007). Cooling causes atomic silver to nucleate into clusters, forming nanoparticles. While this technique yields highly pure materials, controlling particle size distribution remains a challenge.
2.2 Chemical Methods
Chemical methods rely on reducing silver salts in solution to form metallic silver nuclei that grow into nanoparticles (Do Kim, Han, & Kim, 2004). Reaction conditions—such as temperature, pH, and precursor concentration—significantly impact particle size, morphology, and stability (Mallick, Witcomb, & Scurrell, 2004; Ahmad, Ang, Amalina, & Bong, 2018).
2.2.1 Chemical Reduction
Chemical reduction involves mixing a silver salt (e.g., silver nitrate) with a reducing agent like sodium borohydride, hydrazine, or citrate (Abou El-Nour, Eftaiha, Al-Warthan, & Ammar, 2010). Stabilizers, including polyvinylpyrrolidone (PVP) and citrate ions, cap the nanoparticles to prevent agglomeration. This is one of the most widely used approaches due to its simplicity and cost-effectiveness (Li, Dong, Wu, Shen, & Xu, 2020).
2.2.2 Electrochemical Reduction
In electrochemical synthesis, a silver anode is oxidized, releasing Ag^+ ions into solution. Simultaneously, electrons gained at the cathode reduce these ions to metallic silver (Khaydarov et al., 2009). Process variables such as current density and electrolyte composition can be tuned for specific size distributions, and the method can be integrated with polymeric or hydrogel matrices for advanced applications (Jovanović, Stojkovska, Obradović, & Miskovic-Stankovic, 2012).
2.2.3 Photochemical Methods
In photochemical synthesis, light energy drives the reduction of silver ions (Jara et al., 2021). By selecting specific wavelengths or using photosensitizers, researchers can control nucleation and growth phases, achieving narrow size distributions. This approach can be environmentally friendly when combined with mild solvents and nontoxic reducing agents.
2.2.4 Microemulsion Method
Microemulsions serve as nanoreactors where silver salts and reducing agents encounter each other in stabilized droplets (Malik, Wani, & Hashim, 2012). Adjusting surfactant concentration, co-surfactant type, and droplet size confers tight control over nanoparticle dimensions and morphology (Dondi et al., 2012).
2.3 Biological Methods
Biological or “green” methods harness organisms—bacteria, fungi, algae—or plant extracts to reduce Ag^+ to Ag^0 (Klaus, Joerger, Olsson, & Granqvist, 1999; Mustapha et al., 2022). These approaches are often seen as more sustainable and safer, though controlling particle size and monodispersity can be challenging (Castillo-Henríquez et al., 2020).
2.3.1 Plant Extracts
Phytofabrication uses plant extracts rich in phenolics, flavonoids, and other antioxidants as natural reducing agents (Jain & Mehata, 2017). For example, leaves from Plantago major or Brachychiton populneus have been demonstrated to reduce silver ions to metallic nanoparticles (Küünal et al., 2019; Naveed et al., 2022). While eco-friendly, variations in plant phytochemicals can make large-scale reproducibility difficult.
2.3.2 Microbial Synthesis
Fungi, bacteria, and microalgae can produce AgNPs both intracellularly and extracellularly. Species like Fusarium oxysporum and Staphylococcus aureus have been repeatedly employed in such biosynthetic routes (Ahmad et al., 2003; Nanda & Saravanan, 2009). One advantage of microbial synthesis is the potential for “one-pot” processes that do not require additional capping agents, as proteins and polysaccharides naturally stabilize the nanoparticles (Balaji et al., 2009; Li, Xu, Chen, & Chen, 2011).
2.3.3 Algal-Mediated Synthesis
Marine macroalgae, microalgae, and cyanobacteria are emerging as attractive green platforms for AgNP production, given their robust growth conditions and rich bioactive profiles (Aziz et al., 2015; Sathishkumar et al., 2019). Researchers have used species such as Sargassum muticum and Chlamydomonas reinhardtii to yield stable AgNPs with documented antimicrobial efficacy (Azizi, Namvar, Mahdavi, Ahmad, & Mohamad, 2013; Rahman, Kumar, Bafana, Dahoumane, & Jeffryes, 2018).
3. Arc Discharge: Foundations and Parameters
3.1 Principle of Arc Discharge
Arc discharge is a physical top-down method that entails forming a plasma between two conducting electrodes—often silver rods or wires—under a controlled atmosphere (Zhang et al., 2017). The high temperature and energy density vaporize silver, and as the vapor cools, the atoms cluster into nanoparticles. Conditions like arc current, electrode gap, chamber pressure, and ambient gas (e.g., Ar, N_2) determine yield, particle size, and overall purity (Ashkarran, 2010).
3.2 Role of Surrounding Medium
Arc discharge can be performed in various media, including distilled water, organic solvents, or inert gas environments (Tseng et al., 2018). Conducting arc discharge in liquids tends to produce smaller nanoparticles due to rapid quenching, whereas inert gas arcs permit more controlled growth (Zhang et al., 2017). The choice of medium influences particle morphology and the degree of oxidation or contamination.
3.3 Process Variables Influencing Product Characteristics
- Arc Current and Voltage: Higher current densities typically yield smaller and more numerous nanoparticles but can also cause rapid electrode erosion (Ashkarran, 2010).
- Electrode Geometry: The gap between electrodes affects plasma stability and evaporation rates (Tseng et al., 2018).
- Cooling Rate: Rapid cooling in liquids often leads to smaller, more irregular particles. Slower cooling in inert gas can favor more uniform shapes (Zhang et al., 2017).
- Additives: Incorporating surfactants or capping agents in the liquid medium can stabilize nanoparticles during their formation (Munkhbayar, Tanshen, Jeoun, Chung, & Jeong, 2013).
3.4 Advantages and Challenges
Advantages
- Produces high-purity nanoparticles without chemical reducing agents (Zhang et al., 2017).
- Flexible control of particle size and distribution through plasma conditions.
- Relatively straightforward setup compared to some chemical approaches.
Challenges
- Lower yields compared to chemical reduction routes.
- Requires specialized equipment and expertise.
- Potential oxidation or formation of silver oxide phases if oxygen is present (Tseng et al., 2018).
4. Hybrid Approaches: Integrating Arc Discharge with Other Methods
The complexity and limitations of single-route synthesis have motivated the development of hybrid methods. By coupling arc discharge with chemical or biological strategies, researchers aim to capitalize on the benefits of each, thereby achieving better control over AgNP features.
4.1 Arc Discharge + Chemical Reduction
Following arc discharge in an inert medium, partially formed nanoparticles can be transferred into a chemical solution where reducing and capping agents further refine size and shape (Bouafia et al., 2021). This two-step method can enhance yield and tailor functional groups on the nanoparticle surface without compromising purity. For instance, PVP or citrate can be introduced in a post-discharge processing step, preventing agglomeration while harnessing the initial purity of physically generated AgNPs.
4.2 Arc Discharge + Biological Synthesis
Researchers have experimented with subjecting arc-discharge-generated silver to microbial or plant extract processes, effectively bridging physical and green synthesis. The idea is to combine the high-purity advantage of plasma-based production with the natural capping and reduced toxicity of biological media (Khanna, Kaur, & Goyal, 2019). For example, arc-generated silver seeds could be placed in a fungal or algal culture, where enzymatic components reduce any remaining ionic species and functionalize the nanoparticles with bioactive molecules.
4.3 Arc Discharge + Electrochemical Treatment
Some investigations explore using arc discharge to pre-form silver colloids in an electrolyte solution, followed by an electrochemical step that modulates oxidation states or polydispersity (Kumar et al., 2016). This synergy can yield specialized nanostructures, such as core-shell morphologies or dendritic assemblies, by exploiting electrode potentials.
4.4 Advantages of Hybrid Routes
- Enhanced Uniformity: Physical pre-synthesis sets a baseline size distribution, followed by a secondary refining or functionalization step (Naganthran et al., 2022).
- In Situ Functionalization: Biological or chemical agents can attach onto nascent silver surfaces, imparting targeted properties like improved stability or biocompatibility (Miyazawa et al., 2021).
- Resource Efficiency: Hybrid methods can sometimes lower chemical consumption, especially if the first step (arc discharge) produces minimal byproducts (Zhang et al., 2017).
5. Mechanisms of Nanoparticle Formation
Irrespective of the synthetic route, certain fundamental mechanisms underlie AgNP formation. Understanding these phenomena is vital for controlling particle size, shape, and distribution.
5.1 Nucleation and Growth Phases
In classical nucleation theory, the reduction of silver ions (or vapor condensation in physical methods) leads to critical nuclei, which then grow via diffusion of silver monomers to their surfaces (Iravani et al., 2014). Rapid nucleation tends to form many small, uniform particles, while slower nucleation and growth can yield larger, polydisperse nanoparticles (Malik et al., 2012).
5.2 Ostwald Ripening
Ostwald ripening occurs when small particles dissolve, and their material redeposits onto larger particles, driven by minimization of total surface energy (Dondi et al., 2012). This process can cause a shift in the size distribution over time, highlighting the importance of stabilizers or capping agents to prevent excessive ripening (Bouafia et al., 2021).
5.3 Recrystallization and Phase Transitions
In high-temperature methods like arc discharge, partial oxidation can generate silver oxide (Ag_2O or AgO). Subsequent cooling or chemical reduction can revert these phases to metallic silver (Li et al., 2020). Phase boundaries and crystallographic defects often act as nucleation sites for continued nanoparticle growth.
5.4 Role of Surfactants and Capping Agents
Surfactants and capping molecules bind to nanoparticle surfaces, modulating interfacial energies and preventing aggregation (Miyazawa et al., 2021). Common capping agents include PVP, citrate, and various proteins or polysaccharides in biological systems (Miyazawa et al., 2021; Mukherjee et al., 2001). Their choice and concentration profoundly impact particle size, shape, and colloidal stability (Munkhbayar et al., 2013).
6. Characterization Techniques
Comprehensive characterization verifies the successful synthesis of AgNPs and determines their suitability for specific applications. Each method offers distinct insights into nanoparticle structure, surface chemistry, and performance.
6.1 Microscopy
- Transmission Electron Microscopy (TEM): Provides high-resolution images to measure particle diameter, shape, and crystallinity. Arc-discharge AgNPs frequently display near-spherical morphologies (Ashkarran, 2010).
- Scanning Electron Microscopy (SEM): Useful for examining surface topography and film morphologies in large-area samples (Zhang et al., 2017). Coupled with energy-dispersive X-ray (EDX) analysis, SEM confirms elemental composition.
6.2 Spectroscopy
- UV–Vis Spectroscopy: Detects the surface plasmon resonance (SPR) peak of AgNPs, typically around 400 nm (Mallick et al., 2004). Shifts in peak position or intensity can reveal changes in particle size or aggregation.
- X-ray Diffraction (XRD): Identifies metallic silver’s face-centered cubic (fcc) structure via characteristic Bragg peaks (Abou El-Nour et al., 2010).
- Fourier-Transform Infrared Spectroscopy (FTIR): Detects the presence of capping agents or bioorganic layers adsorbed on AgNP surfaces (Naveed et al., 2022).
6.3 Particle Size and Surface Properties
- Dynamic Light Scattering (DLS): Offers average hydrodynamic size and polydispersity index in colloidal solutions (Gudikandula & Charya Maringanti, 2016).
- Zeta Potential: Evaluates surface charge, which directly impacts colloidal stability (Li et al., 2020). Highly positive or negative values generally denote stable suspensions.
6.4 Advanced Techniques
- Thermogravimetric Analysis (TGA): Useful for determining the organic content (e.g., capping agents) on AgNPs (Miyazawa et al., 2021).
- X-ray Photoelectron Spectroscopy (XPS): Identifies oxidation states of silver and other elements present on nanoparticle surfaces (Bouafia et al., 2021).
- Atomic Force Microscopy (AFM): Explores surface topography at the nanoscale, beneficial for thin films loaded with AgNPs.
7. Applications and Emerging Directions
7.1 Electronic Devices and Conductive Inks
Silver has the highest electrical conductivity among metals, making AgNPs attractive for printed electronics, flexible circuits, and solar cells (Bouafia et al., 2021; Zhang et al., 2017). Arc-discharge-generated nanoparticles offer excellent purity, an essential requirement for low-resistivity conductive inks. Post-synthesis modifications—such as sintering at mild temperatures—enable the formation of conductive paths in flexible substrates, including polymer foils and textiles (Wongrat et al., 2019).
7.2 Antimicrobial Coatings and Textiles
AgNPs are widely recognized for their broad-spectrum antimicrobial properties, which disrupt microbial membrane integrity and metabolic pathways (Naqvi et al., 2013). Incorporating them into coatings and textile fibers offers a protective barrier against bacterial and fungal growth. Green- or microbially-synthesized AgNPs may reduce toxicity concerns in medical textiles and wound dressings, while arc-discharge synthesis can ensure minimal chemical contaminants (Shivaji, Madhu, & Singh, 2011).
7.3 Biomedical and Therapeutic Applications
7.3.1 Drug Delivery
Functionalizing AgNP surfaces with polymers, drugs, or targeting ligands enables localized therapeutic delivery (Naganthran et al., 2022). The high surface area and adjustable surface chemistry make AgNPs ideal carriers for anticancer and antimicrobial agents.
7.3.2 Biosensing
AgNPs exhibit strong localized surface plasmon resonance (LSPR), useful for biosensor platforms that detect proteins, nucleic acids, or small molecules (Eckhardt et al., 2013). Hybrid arc-discharge methods can fine-tune the LSPR peak position and enhance detection sensitivity.
7.4 Environmental Remediation
Silver nanoparticles can degrade a variety of organic pollutants via photocatalysis or advanced oxidation processes (Li et al., 2020). For instance, doping silver into composite photocatalysts such as Ag_2O/Bi_5O_7I improves bisphenol A degradation under UV–Vis–NIR light (Li et al., 2020). Moreover, AgNPs embedded in membranes can purify water by combining filtration with antimicrobial action (Naumenko et al., 2013).
7.5 Catalysis and Chemical Conversions
AgNPs act as efficient catalysts in oxidation, reduction, and coupling reactions, partly due to their large surface area and active facets (Tseng et al., 2018). For example, in the oxidation of various organic substrates, arc-discharge-produced silver nanoparticles demonstrate high catalytic turnover frequencies. This is beneficial for industrial-scale chemical processes where robust, clean catalysts are needed.
8. Safety, Toxicity, and Regulatory Concerns
8.1 Ecotoxicology and Human Health
Despite their favorable properties, AgNPs raise concerns about potential toxicity to aquatic life, soil biota, and human health (Miyazawa et al., 2021). At the nanoscale, silver can more readily cross biological barriers, leading to oxidative stress, DNA damage, and protein denaturation in cells (Mukherjee et al., 2001). The dissolution of AgNPs into Ag^+ ions further intensifies their toxicity profile.
8.2 Strategies for Mitigation
- Surface Modification: Biocompatible coatings (e.g., polysaccharides, proteins, or PEG) can reduce ion release and mitigate cytotoxicity (Nandagouda, Speth, & Varma, 2011).
- Green Synthesis: Biological routes minimize hazardous chemicals, and resultant nanoparticles are often more biocompatible (Mustapha et al., 2022).
- Lifecycle Assessment: Evaluating the environmental impact from raw materials to end-of-life ensures more responsible manufacturing and disposal (Kapoor et al., 2021).
8.3 Regulatory Landscape
Regulatory bodies like the U.S. Environmental Protection Agency (EPA) and the European Chemicals Agency (ECHA) have begun addressing nano-specific risk assessments. However, frameworks for consistent labeling, standardized test protocols, and permissible exposure limits are still evolving (Eckhardt et al., 2013). For commercial products containing AgNPs, data on nanoparticle release, accumulation, and long-term effects are increasingly required.
9. Future Perspectives and Challenges
9.1 Scale-Up Considerations
While arc discharge and many other methods effectively produce silver nanoparticles at laboratory scales, scaling up to industrial levels requires overcoming issues related to cost, reproducibility, and environmental safety (Zhang et al., 2017). Continuous-flow reactors, automated monitoring, and real-time characterization might streamline large-scale production without compromising quality.
9.2 Advanced Functionalization
Increasingly sophisticated surface modifications are emerging, including ligand exchange, multi-metallic alloying, and doping (Bouafia et al., 2021). These refinements can drastically improve properties like catalytic selectivity, antimicrobial potency, or optical tunability, opening up new frontiers in nanomedicine and electronics.
9.3 Ångstrom-Scale Particles
A breakthrough avenue lies in producing sub-nanometer “Ångstrom-scale” silver clusters. These ultra-small structures can exhibit quantum confinement effects and unique plasmonic behavior (Wang et al., 2019). Exploring hybrid or arc-based methods to generate such particles promises even broader applications, particularly in fields like photonics and precision oncology.
9.4 Combinatorial Green Routes
As sustainability gains prominence, researchers are investigating ways to merge arc discharge with green synthesis. A potential approach is employing algae or bacterial cultures in the arc discharge medium, harnessing biological molecules for capping or in situ functionalization. This synergy could address safety, environmental, and functionalization challenges simultaneously (Khanna et al., 2019).
9.5 Regulatory Harmonization
A globally consistent regulatory framework remains a pressing challenge. Harmonizing definitions, test protocols, and labeling requirements for nanosilver products will facilitate responsible innovation while safeguarding public health and ecosystems (Eckhardt et al., 2013). Partnerships among academia, industry, and government agencies are essential for shaping policies that keep pace with rapid technological developments.
10. Conclusion
Arc discharge stands out as a robust physical route for synthesizing silver nanoparticles, offering high purity and the potential for unique particle characteristics. Yet, no single approach satisfies all demands for cost, scalability, versatility, and eco-friendliness. Consequently, hybrid strategies that combine arc discharge with chemical or biological methods are increasingly explored to balance purity, yield, and functionalization. This synergy has led to notable breakthroughs in tailoring size, morphology, and surface chemistry, which is crucial for applications spanning electronics, catalysis, and biomedicine.
Nevertheless, significant challenges remain. Achieving industrial-scale production without compromising nanoparticle quality or harming the environment requires continued process optimization and real-time monitoring systems. Meanwhile, evolving regulatory frameworks must address potential nanoparticle toxicity throughout their lifecycle, from synthesis to disposal. Arc discharge—once considered a specialized niche—now anchors many of these ongoing efforts, revealing itself as a versatile platform that can be adapted and merged with other methods to push the boundaries of what silver nanoparticles can achieve.
Whether in designing the next generation of antiviral coatings, developing highly conductive inks for flexible electronics, or creating advanced therapeutic vehicles for targeted drug delivery, AgNP research is poised to make substantial contributions. Ongoing advancements in arc discharge technologies and hybrid approaches pave the way for safer, more effective, and more sustainable silver nanomaterials.
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