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 Growth of Tartrate Crystals of 3d Series Elements by Silica Gel Methods: A Comprehensive Literature Review

Manisha Valvi^ab, Prashant Jagtap^a*, Hiralal Patil^b*

^aPSGVPM's Arts, Science and Commerce College, Shahada-425 409, (MS) India.

^bD.M.E.S Arts & Science College, Amalner-425 401, (MS) India.

*E-mail address: p22jagtap@gmail.com, hmp_2004@gmail.com

Abstract

This literature review examines the growth of tartrate crystals incorporating 3d transition-series elements using silica gel techniques. The silica gel method has emerged as a versatile and cost-effective approach for the growth of high-quality single crystals of sparingly soluble metal tartrates under ambient conditions. The surveyed literature demonstrates that silica gel growth enables fine control over nucleation and crystal growth kinetics through systematic variation of pH, gel density, reactant concentration, and diffusion parameters. Structural and physicochemical characterization using techniques such as XRD, FTIR, thermal analysis, and other spectroscopic methods has provided valuable insights into the structural, optical, thermal, magnetic, and dielectric properties of these materials. Reported applications include nonlinear optical devices, semiconductors, and advanced functional materials. Despite these advances, challenges remain in producing large, defect-free single crystals and in developing a comprehensive understanding of the underlying growth mechanisms.

Keywords:Silica gel growth; 3d transition metals; Metal tartrate crystals; Crystal growth optimization.

 

Introduction

Tartrate crystals of transition metal ions have attracted considerable scientific interest owing to their rich structural chemistry, intriguing physical properties, and potential applications in optoelectronics, nonlinear optics, and materials science. The 3d transition series elementsare known to form a wide range of coordination compounds with tartrate ligands, exhibiting remarkable structural diversity and functional behavior. Tartaric acid (2,3-dihydroxybutanedioic acid) is a naturally occurring organic acid containing two carboxyl and two hydroxyl functional groups, which enable it to act as a multidentate ligand and form stable chelated complexes with various metal ion[1].

The synthesis of high-quality single crystals of metal tartrates presents significant challenges due to their limited solubility in aqueous media and tendency toward rapid precipitation. Conventional solution growth methods often yield polycrystalline aggregates or poorly formed crystals unsuitable for detailed structural and physical property studies (Holmes 2002)[2]. The silica gel method, pioneered in the mid-20th century, has emerged as an elegant solution to these challenges[3–5]. This technique exploits the three-dimensional network structure of silica hydrogel to create a controlled diffusion environment that suppresses convection currents, reduces nucleation density, and promotes slow, uniform crystal growth at ambient temperatures (Nandreet al.,[6].

Over the past three decades, the silica gel technique has been widely employed for the growth of tartrate crystals of various 3d transition metals[7–9], producing crystals suitable for detailed structural, thermal, optical, and physicochemical characterization. The existing literature shows a predominant focus on copper, cobalt, iron, and manganese tartrate systems, whereas comparatively little attention has been devoted to the remaining 3d transition metals. This review consolidates current research on the growth methodologies, characterization techniques, and physicochemical properties of 3d metal tartrate crystals synthesized via silica gel methods, highlights existing gaps in the literature, and outlines potential directions for future investigations.

 

 

Synthesis Procedures and Experimental Parameters

a) Gel Preparation and Setting

The preparation of silica gel is a crucial initial step that strongly influences the quality, morphology, and growth behavior of the resulting crystals. In the standard procedure, an aqueous sodium metasilicate (water glass) solution is mixed with an acidic solution containing tartaric acid to induce gel formation. The specific gravity of the sodium metasilicate solution is typically controlled within the range of 1.03-1.06 g/cm³, with a value of 1.04 g g/cm³ (Satyanarayana et al., 1985)[4], most commonly employed, as reported by Nandre et al. (2015) [1].

The concentration of tartaric acid is a critical parameter in silica gel preparation and is typically maintained within the range of 0.5-1.5 M (Quasim et al., 2008)[10]. Higher tartaric acid concentrations lead to lower pH values and more rapid gelation, whereas lower concentrations result in slower gelation and the formation of gels with different structural characteristics. Accordingly, the pH of the gel solution is carefully controlled, generally within the range of 3.0-5.5 (Jethva et al., 2016)[11], depending on the specific metal-tartrate system under investigation. For cobalt tartrate crystals, optimal growth has been reported at pH values between 3 and 5 (Nandre et al., 2015)[6], whereas copper tartrate systems typically employ pH values in the range of 4.0-5.0 (Patil et al., 2024)[[12].

The mixing procedure plays a crucial role in achieving uniform gel properties. Typically, the sodium metasilicate solution is added dropwise to the tartaric acid solution under continuous stirring to ensure homogeneous mixing and controlled gelation. The resulting mixture is then transferred into test tubes or other suitable crystallization vessels and allowed to set under undisturbed conditions. The gel setting time can vary from a few hours to several days, depending on factors such as pH and reactant concentrations; however, a setting period of 24-48 hours is most commonly employed, as reported by Nandre et al. (2015)[6].

After gelation, an aging period is typically introduced before the addition of the metal ion solution. This aging step allows the silica gel network to stabilize and strengthen, thereby improving its mechanical integrity and suitability for controlled crystal growth. Aging durations commonly range from 24 to 72 hours, with an optimal period of approximately 36 hours frequently reported (Nandre et al., 2015)[6]. During the aging process, the gel undergoes syneresis, characterized by network contraction and partial expulsion of solvent, which can influence the gel pore structure and, consequently, the nucleation and growth behavior of the resulting crystals (Jethva et al., 2014)[13].

b) Diffusion Methods

Two principal diffusion techniques are commonly employed for crystal growth in silica gel, namely single diffusion and double diffusion. The selection of an appropriate method depends on the specific metal-tartrate system under investigation as well as the desired crystal size, morphology, and growth kinetics.

Single Diffusion Method:The single diffusion method is the most widely employed technique for the growth of metal tartrate crystals in silica gel (Pandya et al., 2024)[14]. In this approach, tartaric acid is incorporated into the gel during its preparation, while the metal ion solution is introduced as a supernatant after the gel has set and undergone an aging period. The metal ions subsequently diffuse downward through the gel matrix and react with the tartrate ions immobilized within the gel, leading to controlled nucleation and crystal growth. This method has been successfully applied to the growth of cobalt tartrate (Nandre et al., 2015)[6], copper tartrate (Patil et al., 2024)[12], iron-manganese-cobalt ternary tartrate (Joshi et al., 2010)[15], and several other metal-tartrate systems[16–19].

Double Diffusion Method:In the double diffusion method, both reactants diffuse through the silica gel from opposite ends of the crystallization vessel. The gel is prepared without incorporating either reactant, and after gelation, separate solutions of the metal ion and the tartrate ion are introduced at opposite ends of the gel column. Crystal nucleation and growth occur in the region where the two diffusion fronts intersect.

The duration of crystal growth varies considerably depending on the specific metal-tartrate system and the targeted crystal size. Initial nucleation generally occurs within 24-72 hours following the addition of the supernatant solution, while visible crystals typically appear within 2-5 days. Subsequent crystal growth may continue for periods ranging from 1 to 4 weeks, with extended growth durations usually resulting in larger and better-developed crystals. In the case of cobalt tartrate, an optimal growth period of approximately two weeks has been reported (Nandre et al., 2015)[6].

Metal-Tartrate Systems: Synthesis and Properties

a) Pure Metal Tartarate Systems:

Yanes et al., (1996)[20]  describes the gel growth of manganese tartrate crystals and their structural and thermal characterization. IR analysis confirmed coordination of tartrate ions with Mn²⁺, while thermal studies showed stepwise dehydration followed by decomposition to manganese oxide. The results establish the formation, bonding nature, and decomposition behavior of hydrated manganese tartrate crystals.

Nandre et al., (2012)[21]reported the gel growth of zinc tartrate crystals under optimized conditions and their structural and optical characterization. SEM revealed plate-like, layer-by-layer morphology, while EDAX confirmed zinc incorporation. UV-Visible analysis showed high transparency above 300 nm and a band gap of 4.35 eV, indicating suitability for nonlinear optical applications.

Mathivanan et al., (2014)[22] reported the first successful growth of cobalt tartrate pentahydrate crystals in silica gel via a simple reaction between tartaric acid embedded in the gel and diffusing cobalt nitrate, producing dark brown spherulitic crystals within 3-4 weeks. Due to the ability of tartrate compounds to exhibit notable dielectric, piezoelectric, and nonlinear optical properties, cobalt tartrate crystals are considered promising materials for applications in semiconductor devices, optical components, and related advanced electronic technologies.

Ariponnammal et al., (2014)[23] grew cobalt tartrate trihydrate crystals by slow evaporation and confirmed a monoclinic (P2₁) structure with octahedral Co²⁺ coordination. Optical (band gap ~4.68 eV), thermal, and dielectric studies supported good stability, and SHG efficiency comparable to KDP indicated promising nonlinear optical applications.

Fukami et al., (2022)[24] investigated the growth, structure, and thermal behavior of FeC₄H₄O₆·2.5H₂O crystals prepared by the gel method. Structural details were obtained from single-crystal or powder XRD analysis, while thermal studies examined dehydration and decomposition processes. The presence of 2.5 water molecules per formula unit confirms a hydrated structure, with lattice water contributing to crystal packing and stability.

Patil et al., (2024)[12] reported the growth of copper tartrate single crystals via the single diffusion method in silica gel. The gel medium was prepared using tartaric acid at pH 4.5-5.0 and sodium metasilicate of specific gravity 1.04 g/cm³. A 0.5-1.0 M copper sulfate solution was used as the supernatant.The crystals exhibited a monoclinic structure with unit cell parameters:a = 5.47 Å, b = 11.76 Å, c = 9.20 Å. The crystals were blue-green and optically transparent. Thermal analysis indicated stability up to ~100 °C, followed by multistage decomposition ultimately yielding CuO at higher temperatures.

b) Doped metal Tartrate Systems:

Several studies have explored the modification of metal tartrate crystals through controlled doping with other metal ions.

Suthar et al., (2006)[25] investigated Mn(II)-doped calcium L-tartrate crystals and showed that manganese doping alters the physicochemical characteristics of the host crystal, illustrating the broader applicability of 3d transition metal ion doping in metal tartrate systems.

Mathivanan et al., (2013)[26] reported the gel growth of pure and copper-doped iron tartrate crystals and compares their structural, magnetic, and thermal properties. EDAX confirmed Cu²⁺ incorporation into the lattice, while XRD showed an orthorhombic structure with increased unit cell volume after doping. Magnetic studies revealed a shift from diamagnetic behavior in pure crystals to paramagnetic behavior in doped crystals. Thermal analysis confirmed hydrated structures and slight changes in decomposition behavior due to copper substitution.

Bachhav et al., (2014)[27] reported the growth of cobalt-doped barium tartrate crystals using the silica gel method, demonstrating that cobalt incorporation into the host lattice significantly modifies crystal properties and highlights the adaptability of gel growth techniques for doped systems.

Pradeepkumar et al., (2020)[28] investigated Co(II)-doped copper tartrate single crystals grown in silica gel and examined the influence of light radiation on their properties. Incorporation of cobalt ions altered the optical and thermal characteristics of the host copper tartrate lattice, while exposure to light radiation further modified the crystal behavior. These findings indicate that controlled doping combined with external stimuli can tailor material properties, highlighting potential applications in photonic and optoelectronic devices.

Similarly, Savitha et al., (2022)[29]successfully synthesized and characterized pure and Co-doped PPLT single crystals, highlighting the significant improvements in their structural, optical, dielectric, and nonlinear optical properties due to Co-doping. The findings suggest that Co-doped PPLT is a promising material for various advanced optical and electronic applications, particularly in the realm of third-order nonlinear optics.

Patil et al., (2024)[12] reported the growth of cadmium-doped copper tartrate crystals using the silica gel method. Powder X-ray diffraction analysis revealed a monoclinic structure with lattice parameters a = 5.47 Å, b = 11.76 Å, c = 9.20 Å, and a unit cell volume of 621.02 Å. Cadmium incorporation influenced crystal morphology and size, demonstrating that dopant ions can significantly affect structural and growth characteristics. The study primarily focused on structural and compositional analysis.

c) TernaryMetal Tartrate Systems:

Joshi et al., (2010)[15]reported the growth of Fe-Mn-Co ternary levo-tartrate crystals by the silica gel single diffusion method . EDAX revealed compositional deviations due to preferential partitioning (iron enrichment), while powder XRD confirmed crystallinity with evidence of extra phases. FTIR verified tartrate coordination and metal-oxygen bonding. TGA showed ~2.4-2.5 hydration water molecules followed by decomposition to mixed oxides, with activation energies between 67-85 kJ·mol^-1. Dielectric studies indicated frequency-dependent behavior, and VSM measurements confirmed paramagnetic nature, demonstrating strong composition-dependent structural, thermal, and magnetic properties.

Joshi et al., (2013)[30]further succeccfully studied the growth of Fe-Ni-Mn ternary levo-tartrate crystals by the silica gel method. XRD and FTIR confirmed crystalline hydrated structures, TGA showed stepwise dehydration and oxide formation, and magnetic measurements indicated paramagnetic behavior. Dielectric studies revealed frequency-dependent properties, demonstrating that metal substitution effectively tunes the material’s physicochemical characteristics.

Tandel et al., (2025)[31] reported the growth of strontium–magnesium–zinc ternary levo-tartrate (SrMgZnT) crystals by the single diffusion silica gel method at ambient temperature. The crystals exhibited orthorhombic morphology with layer-by-layer growth, and EDX confirmed the incorporation of Sr, Mg, and Zn, though Mg content was low due to its lower solubility. TGA showed a four-stage decomposition pattern, with SrMgZnT displaying higher thermal stability (355 K) than pure SrT (339 K). Kinetic analysis indicated higher activation energy for the ternary crystal, confirming improved thermal stability due to Mg and Zn doping.

Conclusion

This comprehensive literature review has examined the growth of tartrate crystals of 3d transition series elements using silica gel methods, synthesizing findings from highly relevant studies published over the past three decades. The silica gel technique has proven to be a versatile, cost-effective approach for growing high-quality crystals of sparingly soluble metal tartrates under ambient conditions. The method exploits the three-dimensional gel network to create a controlled diffusion environment that suppresses convection, reduces nucleation density, and promotes uniform crystal growth.The silica gel method for growing metal tartrate crystals represents a mature but still evolving field with significant potential for both fundamental research and technological applications. Continued systematic investigation, guided by the insights and recommendations presented in this review, will advance understanding of these fascinating materials and enable realization of their full potential.

 

 

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16.      Dhikale MD, Shitole SJ, Nahire SB, Chavan AR. Electric conductivity study of silica gel grown pure and Cu doped Fe tartrate crystals. J Gujarat Res Society. 2019;21(14):1574-81.

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29.      Savitha K, Saravanan K. Growth and characterizations of pure and co doped piperazinium L-tartrate single crystals (PPLT) single crystals: optical and NLO properties. J Cryst Growth. 2022;582:126529.

30.      Joshi SJ, Tank KP, Parekh BB, Joshi MJ. FT-IR and thermal studies of iron–nickel–manganese ternary levo-tartrate crystals. J Therm Anal Calorim. 2013;112(2):761-6.

31.      Tandel NH, Patel IB. Synthesis and Characterization of Strontium Tartrate Pentahydrate and Strontium-Magnesium-Zinc Ternary Levo-Tartrate Hexahydrate Crystals. Bulgarian Journal of Physics. 2025;52(3).

 

 

 

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