Special Issue "Carbonates"

A special issue of Crystals (ISSN 2073-4352). This special issue belongs to the section "Crystal Engineering".

Deadline for manuscript submissions: closed (15 June 2018)

Special Issue Editor

Guest Editor
Dr. Linda Pastero

Department of Earth Sciences, Interdepartmental Centre “Nanostructured Interfaces and Surfaces-NIS”, University of Torino, Italy
Website | E-Mail
Interests: crystal growth; epitaxy; surface; interface; calcite; gypsum; apatite; zeolite

Special Issue Information

Dear Colleagues,

Even though the study of the minerals belonging to the group of carbonates is a longstanding and sound out topic, its relevance remains unchanged, due to the countless implications for a wide range of disciplines, from mineralogy and geology to biology, medicine, and industry. Moreover, the study of the interactions between carbonates and other minerals, such as phosphates, or between carbonates and organics, may disclose new opportunities for understanding the mechanisms involved in natural phenomena, such as biomineralization.

The goal of this Special Issue on “Carbonates” is to provide a comprehensive overview about both the state-of-the-art and recent advances in crystal growth and characterization of carbonate phases, pointing out the mechanisms of growth, the interactions among phases, and the applications.

Scientists working in a wide range of disciplines are invited to contribute to this Special Issue.

The topics may include, but are not limited to, the following:

  • Natural and synthetic carbonates

  • Crystal growth of carbonates

  • Epitaxial relationships

  • Twinning

  • Bioinspired/biomimetic materials

  • Inorganic/organic self-organized materials (nacreous-like materials)

  • Inorganic complex systems (such as carbonate/phosphate for example)

  • Applications

The first round submission deadline: 30 November 2017

Dr. Linda Pastero
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All papers will be peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Crystals is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1200 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • carbonates

  • crystal growth

  • epitaxy

  • self-organized materials

  • bio-mineralogy

  • bio-inspired materials

  • bio-mimetic materials

  • environmental mineralogy

Published Papers (9 papers)

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Research

Open AccessArticle Calcium Carbonate Polymorphs Growing in the Presence of Sericin: A New Composite Mimicking the Hierarchic Structure of Nacre
Crystals 2018, 8(7), 263; https://doi.org/10.3390/cryst8070263
Received: 28 May 2018 / Revised: 16 June 2018 / Accepted: 23 June 2018 / Published: 26 June 2018
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Abstract
Bioinspired self-assembled composite materials are appealing both for their industrial applications and importance in natural sciences, and represent a stimulating topic in the area of materials science, biology, and medicine. The function of the organic matrix has been studied from the biological, chemical,
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Bioinspired self-assembled composite materials are appealing both for their industrial applications and importance in natural sciences, and represent a stimulating topic in the area of materials science, biology, and medicine. The function of the organic matrix has been studied from the biological, chemical, crystallographic, and engineering point of view. Little attention has been paid to the effect of one of the two main components of the organic matrix, the sericin fraction, on the growth morphology of calcium carbonate polymorphs. In the present work, we address this issue experimentally, emphasizing the morphological effects of sericin on calcite and aragonite crystals, and on the formation of a sericin-aragonite-calcite self-assembled composite with a hierarchic structure comparable to that of natural nacre. Full article
(This article belongs to the Special Issue Carbonates)
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Open AccessArticle Experimental Value of the Specific Surface Energy of the Cleavage {10.4} Calcite Rhombohedron in the Presence of Its Saturated Aqueous Solution
Crystals 2018, 8(6), 238; https://doi.org/10.3390/cryst8060238
Received: 26 April 2018 / Revised: 20 May 2018 / Accepted: 28 May 2018 / Published: 30 May 2018
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Abstract
In this study, we describe a method to obtain experimental values of the surface energy of calcite. A zenithal imaging device was used to acquire pictures of droplets of CaCO3 saturated aqueous solution on the surface of a calcite crystal sample. Pictures
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In this study, we describe a method to obtain experimental values of the surface energy of calcite. A zenithal imaging device was used to acquire pictures of droplets of CaCO3 saturated aqueous solution on the surface of a calcite crystal sample. Pictures were used to measure the contact angle between the droplets and the {10.4} calcite surfaces. The method is discussed along with its geometrical ground, as well as the theoretical foundation of the contact angle calculation. A comparison is made with the literature data; a good agreement is found between our experimental values and those obtained from the more recent ab initio calculations. Full article
(This article belongs to the Special Issue Carbonates)
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Open AccessArticle Comparative Study on the Sand Bioconsolidation through Calcium Carbonate Precipitation by Sporosarcina pasteurii and Bacillus subtilis
Crystals 2018, 8(5), 189; https://doi.org/10.3390/cryst8050189
Received: 11 November 2017 / Revised: 20 March 2018 / Accepted: 21 April 2018 / Published: 27 April 2018
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Abstract
To investigate potential implications of microbial activity on sand bioconsolidation and subsurface environments, two ureolytic strains, Sporosarcina pasteurii and Bacillus subtilis were tested for the production of calcium carbonate (CaCO3). Laboratory experiments with monoculture S. pasteurii (column 1) and coculture S.
[...] Read more.
To investigate potential implications of microbial activity on sand bioconsolidation and subsurface environments, two ureolytic strains, Sporosarcina pasteurii and Bacillus subtilis were tested for the production of calcium carbonate (CaCO3). Laboratory experiments with monoculture S. pasteurii (column 1) and coculture S. pasteurii-B. subtilis (column 2) were conducted to determine urea and calcium chloride reactivity and volumetric carbonate formation. Both columns were able to consolidate sand, whereas, column 1 induced greater CaCO3 precipitation. X-ray diffraction (XRD) and scanning electron microscopy (SEM) showed two columns with different mineralogy with calcite, and vaterite formation. Column 1 showed rhombohedral and trigonal crystals morphology, whereas column 2 developed the prismatic calcite and the spherulite vaterite crystals might be due to the differences of the micro-environment caused by the urease expression of these bacterial species. These results indicate the possibility of using those crystals to cement loose sand whereas, highlighted the importance of combining these techniques to understand the geomicrobiology found in the subsurface environments. Full article
(This article belongs to the Special Issue Carbonates)
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Open AccessArticle The Carbonate Platform Model and Reservoirs’ Origins of the Callovian-Oxfordian Stage in the Amu Darya Basin, Turkmenistan
Crystals 2018, 8(2), 84; https://doi.org/10.3390/cryst8020084
Received: 21 November 2017 / Revised: 21 January 2018 / Accepted: 29 January 2018 / Published: 4 February 2018
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Abstract
The Calloviane-Oxfordian carbonates in the northeastern Amu Darya Basin of southeastern Turkmenistan are composed of medium- to thick-bedded, mostly grainy limestones with various skeletal (bivalves, brachiopods, echinoderms, foraminifera, corals, and sponge) and non-skeletal grains (intraclasts, ooids and peloids). Two facies zones, six standard
[...] Read more.
The Calloviane-Oxfordian carbonates in the northeastern Amu Darya Basin of southeastern Turkmenistan are composed of medium- to thick-bedded, mostly grainy limestones with various skeletal (bivalves, brachiopods, echinoderms, foraminifera, corals, and sponge) and non-skeletal grains (intraclasts, ooids and peloids). Two facies zones, six standard facies belts and some microfacies types were recognized, and sedimentary model “carbonate ramp-rimmed platform” was proposed and established that can be compared with the classical carbonate sedimentary models. In this model, favorable reservoirs not only developed in the intraplatform shoal of open platform, or reef and shoal on the platform margin, but also in the patch reefs, shoal and mound facies on the upper slope. The reservoir’s pore space is dominated by intergranular and intragranular pores and fissure-pore reservoirs exist with medium porosity and medium to low permeability. Sedimentary facies and diagenetic dissolution are the key controlling factors for the development of high-quality reservoirs. Full article
(This article belongs to the Special Issue Carbonates)
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Open AccessArticle Electrocrystallization of CaCO3 Crystals Obtained through Phosphorylated Chitin
Crystals 2018, 8(2), 82; https://doi.org/10.3390/cryst8020082
Received: 22 December 2017 / Revised: 31 January 2018 / Accepted: 2 February 2018 / Published: 3 February 2018
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Abstract
A phosphorylated chitin (Chi-P) derivative was synthesized and its chemical structure was verified with Fourier-transform infrared spectroscopy (FTIR), elemental analysis, and thermogravimetric techniques (TGA). The influence of Chi-P used as a solid template through in vitro electrocrystallization (EC) supported on an indium zinc
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A phosphorylated chitin (Chi-P) derivative was synthesized and its chemical structure was verified with Fourier-transform infrared spectroscopy (FTIR), elemental analysis, and thermogravimetric techniques (TGA). The influence of Chi-P used as a solid template through in vitro electrocrystallization (EC) supported on an indium zinc oxide (ITO) surface on the growth of calcium carbonate (CaCO3) was studied. CaCO3 crystals through EC essays were also compared with crystals obtained with the gas diffusion (GD) method. Scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDS), chronopotentiometry, Raman, and powder X-ray diffractometry (XRD) characterized all resultant inorganic particles. Our findings revealed that the EC method selectively controlled the coexistence of truncate calcite and the metastable phase of vaterite. The crystals’ morphology reflects the electrostatic interaction of phosphate moieties from Chi-P onto CaCO3 crystals through both EC and GD crystallization methods. We believe that the EC method represents a viable electrochemical approach for studying different inorganic minerals and could be useful as an in vitro classical crystallization method for the design of advanced inorganic materials with desirable shapes and properties. Full article
(This article belongs to the Special Issue Carbonates)
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Open AccessArticle Effect of Alginate from Chilean Lessonia nigrescens and MWCNTs on CaCO3 Crystallization by Classical and Non-Classical Methods
Crystals 2018, 8(2), 69; https://doi.org/10.3390/cryst8020069
Received: 23 December 2017 / Revised: 27 January 2018 / Accepted: 29 January 2018 / Published: 31 January 2018
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Abstract
In our crystallization experiments, the influence of alginate from Chilean Lessonia nigrescens and functionalized multi-walled carbon nanotubes (MWCNTs) was tested through electrocrystallization (EC) and gas diffusion (GD) methods on the crystal growth of calcium carbonate (CaCO3) and their possible stabilization of
[...] Read more.
In our crystallization experiments, the influence of alginate from Chilean Lessonia nigrescens and functionalized multi-walled carbon nanotubes (MWCNTs) was tested through electrocrystallization (EC) and gas diffusion (GD) methods on the crystal growth of calcium carbonate (CaCO3) and their possible stabilization of proto-structures in amorphous CaCO3 (ACC) state through pre-nucleation clusters (PNC) essays with automatic potentiometric titrations were performed. CaCO3 crystals obtained in the in vitro above-mentioned crystallization systems were characterized by scanning electron microscope (SEM), energy-dispersive X-ray spectrometry (EDS) and powder X-ray diffractometer (XRD). Our experimental findings showed that ALG and functionalized MWCNTs stabilized truncated and agglomerated vaterite-like particles through GD and EC methods. While, on the other hand, we obtained qualitative information about induction or inhibition of CaCO3 nucleation that was provided by potentiometric titrations. Full article
(This article belongs to the Special Issue Carbonates)
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Open AccessArticle CO2 Capture and Crystallization of Ammonia Bicarbonate in a Lab-Scale Scrubber
Crystals 2018, 8(1), 39; https://doi.org/10.3390/cryst8010039
Received: 21 November 2017 / Revised: 9 January 2018 / Accepted: 12 January 2018 / Published: 16 January 2018
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Abstract
A lab-scale bubble-column scrubber is used to capture CO2 gas and produce ammonia bicarbonate (ABC) using aqueous ammonia as an absorbent under a constant pH and temperature. The CO2 concentration is adjusted by mixing N2 and CO2 in the
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A lab-scale bubble-column scrubber is used to capture CO2 gas and produce ammonia bicarbonate (ABC) using aqueous ammonia as an absorbent under a constant pH and temperature. The CO2 concentration is adjusted by mixing N2 and CO2 in the range of 15–60 vol % at 55 °C. The process variables are the pH of the solution, temperature, gas-flow rate and the concentration of gas. The effects of the process variables on the removal efficiency (E), absorption rate (RA) and overall mass-transfer coefficient (KGa) were explored. A multiple-tube mass balance model was used to determine RA and KGa, in which RA and KGa were in the range of 2.14 × 10−4–1.09 × 10−3 mol/(s·L) and 0.0136–0.5669 1/s, respectively. Results found that, RA showed an obvious increase with the increase in pH, inlet gas concentration and gas temperature, while KGa decreased with an increase in inlet gas concentration. Using linear regression, an empirical expression for KGa/E was obtained. On the other hand, ammonia bicarbonate crystals could be produced at a pH of 9.5 when the gas concentration was higher than 30% and γ (=Fg/FA, the gas-liquid molar flow rate ratio) ≥ 1.5. Full article
(This article belongs to the Special Issue Carbonates)
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Open AccessArticle Hydrophobic Calcium Carbonate for Cement Surface
Crystals 2017, 7(12), 371; https://doi.org/10.3390/cryst7120371
Received: 14 November 2017 / Revised: 6 December 2017 / Accepted: 8 December 2017 / Published: 11 December 2017
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Abstract
This report describes a novel way to generate a highly effective hydrophobic cement surface via a carbonation route using sodium stearate. Carbonation reaction was carried out at different temperatures to investigate the hydrophobicity and morphology of the calcium carbonate formed with this process.
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This report describes a novel way to generate a highly effective hydrophobic cement surface via a carbonation route using sodium stearate. Carbonation reaction was carried out at different temperatures to investigate the hydrophobicity and morphology of the calcium carbonate formed with this process. With increasing temperatures, the particles changed from irregular shapes to more uniform rod-like structures and then aggregated to form a plate-like formation. The contact angle against water was found to increase with increasing temperature; after 90 °C there was no further increase. The maximum contact angle of 129° was obtained at the temperature of 60 °C. It was also found that carbonation increased the micro hardness of the cement material. The micro hardness was found to be dependent on the morphology of the CaCO3 particles. The rod like structures which caused increased mineral filler produced a material with enhanced strength. The 13C cross polarization magic-angle spinning NMR spectra gave plausible explanation of the interaction of organic-inorganic moieties. Full article
(This article belongs to the Special Issue Carbonates)
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Open AccessArticle Crystallization of Calcium Carbonate in Alginate and Xanthan Hydrogels
Crystals 2017, 7(12), 355; https://doi.org/10.3390/cryst7120355
Received: 20 September 2017 / Revised: 21 November 2017 / Accepted: 27 November 2017 / Published: 30 November 2017
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Abstract
Calcium carbonate polymorphs were crystallized in alginate and xanthan hydrogels in which a degree of entanglement was altered by the polysaccharide concentration. Both hydrogels contain functional groups (COOH and OH) attached at diverse proportions on saccharide units. In all systems, the precipitation process
[...] Read more.
Calcium carbonate polymorphs were crystallized in alginate and xanthan hydrogels in which a degree of entanglement was altered by the polysaccharide concentration. Both hydrogels contain functional groups (COOH and OH) attached at diverse proportions on saccharide units. In all systems, the precipitation process was initiated simultaneously with gelation, by the fast mixing of the calcium and carbonate solutions, which contain the polysaccharide molecules at respective concentrations. The initial supersaturation was adjusted to be relatively high in order to ensure the conditions suitable for nucleation of all CaCO3 polymorphs and amorphous phase(s). In the model systems (no polysaccharide), a mixture of calcite, vaterite and amorphous calcium carbonate initially precipitated, but after short time only calcite remained. In the presence of xanthan hydrogels, precipitation of either, calcite single crystals, porous polyhedral aggregates, or calcite/vaterite mixtures were observed after five days of ageing, because of different degrees of gel entanglement. At the highest xanthan concentrations applied, the vaterite content was significantly higher. In the alginate hydrogels, calcite microcrystalline aggregates, rosette-like and/or stuck-like monocrystals and vaterite/calcite mixtures precipitated as well. Time resolved crystallization experiments performed in alginate hydrogels indicated the initial formation of a mixture of calcite, vaterite and amorphous calcium carbonate, which transformed to calcite after 24 h of ageing. Full article
(This article belongs to the Special Issue Carbonates)
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