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Kinetics of Formation and Crystal Structure Determination of Sr4Al6O12SO4

Abstract

The sulphoaluminate of strontium, Sr4Al6O12SO4, was synthesized by solid state reaction from mixture of SrCO3, Al2O3 and SrSO4 (3:3:1 molar ratio) as pellets. The kinetics of formation has been studied in the range of temperature between 850ºC and 1100ºC using quantitative X-ray powder diffraction data (XRD) analysis. Likewise, at room temperature, the crystal structure was determined from conventional X-ray powder diffraction data using direct methods and it was refined by the Rietveld method. The kinetics mechanisms that showed the best fit, were identified as geometrical contraction at grain boundary (R1.1) and nucleation and growing by energy law (P1.1). The activation energy values obtained were 145.47KJmol-1 (R1.1) and 151.35KJmol-1 (P1.1), respectively. The resulting crystal structure was orthorhombic type (a: 13.32802Å, b: 13.34430Å and c: 9.38704Å). The observed adjustment parameters were RB: 0.0985, Rwp: 0.137, Rp: 0.0925 and Chi2: 1.94.

Keywords:
Solid state reaction; Kinetic study; Crystal structure; Rietveld method


1. Introduction

Reactions between solids are diverse, determinants being i) the thermodynamic conditions, ii) structural conditions and iii) reaction mechanisms governing the process. The Knowledge of the kinetic mechanisms that characterize a solid state reaction is essential for the control of a process, critical issue in the development of new products11 Quesada Gonzalez O, Torres GE, Llópiz JC. Termogravimetría de alta resolución: Estudio cinético de la deshidratación térmica del cloruro de bario dihidratado. Revista Cubana de Química. 2002;14(1):44-50.. However, there are few mathematical descriptions which provide suitable bases for prediction and interpretation of such reactions. On the other hand, knowledge of the crystal structure of any material is a fundamental requirement to understand and control the properties22 Esteve Cano VJ, ed. El Método de Rietveld. 2ª ed. Castellón: Universitat Jaume I; 2014.. In recent decades they have seen a considerable increase in the development of the structure determination from powder diffraction data33 Harris KD, Tremayne M, Kariuki BM. Contemporary Advances in the Use of Powder X-Ray Diffraction for Structure Determination. Angewandte Chemie (International ed. in English). 2001;40(9):1626-1651.

4 Tremayne M. The impact of powder diffraction on the structural characterization of organic crystalline materials. Philosophical Transactions. Series A, Mathematical, Physical, and Engineering Sciences. 2004;362(1825):2691-2707.
-55 McCusker LB, von Dreele RB, Cox DE, Louër D, Scardi P. Rietveld refinement guidelines. Journal of Applied Crystallography. 1999;32:36-50.. An example is the Rietveld method, computational program whose objective is the refining of crystal structures using the technique of least squares by adjusting the patterns (experimental and calculated)22 Esteve Cano VJ, ed. El Método de Rietveld. 2ª ed. Castellón: Universitat Jaume I; 2014.. Due to the above and knowing that the information about the compounds formed within the system SrO-Al2O3-SrSO4 is low (only synthesis at high temperature, some physical and chemical properties of Sr4Al6O12SO4 were reported)66 Gilioli C, Massazza F, Pezzuoli M. A new compound: Strontium sulphoaluminate and its relationships with calcium sulphoaluminate. Cement and Concrete Research. 1971;1(6):621-629.

7 Brenchley ME, Weller MT. Synthesis and structure of sulfide aluminate sodalites. Journal of Materials Chemistry. 1992;2(10):1003-1005.

8 Rodríguez-García JA, Rocha-Rangel E, Torres-Torres J, Almanza-Robles JM. Synthesis by a solid state reaction of the Sr4Al6O12SO4 compound. Journal of Ceramic Processing Research. 2011;12(3):310-313.

9 Rodríguez-García JA, Rocha-Rangel E, Almanza-Robles JM, Torres-Torres J, Leal Cruz AL, Munive GT. Chemical interaction of Sr4Al6O12SO4 with liquid aluminum alloys. In: Sing JP, Bansal NP, Goto T, Lamon J, Choi SR, Mahmoud MM, et al., eds. Processing and Properties of Advanced Ceramics and Composites IV: Ceramic Transactions, Volume 234. Hoboken: Willey; 2012. p. 21-27.
-1010 Rodríguez-García JA, Rocha-Rangel E, López Hernández J, Hernández-Bocanegra A, Leal-Cruz A, Almanza-Robles J, et al. Physical properties of the Sr4Al6O12SO4 ceramic compound. Wulfenia Journal. 2014;21(2):420-427. as an integral part of the synthesis and characterization of strontium sulfoaluminate, Sr4Al6O12SO4, this paper presents i) the kinetic study of the formation from quantitative data best fit against kinetic models by solid state reaction and ii) the crystal structure at room temperature through the refining of X-ray diffraction patterns using the Rietveld method.

2. Experimental Procedure

The research was conducted in three stages; in the first stage the preparation and characterization of the samples are presented, in the second stage a study was performed to establish the kinetic of formation of Sr4Al6O12SO4 in the SrO-Al2O3-SrSO4 system and the third stage the crystal structure of the same strontium compound was determined.

2.1 Preparation and characterization of samples

Stoichiometric mixture of Al2O3, SrCO3 and SrSO4 (3:3:1 ratio molar) were accurately weighed and homogenized for 4 hours in plastic jar with acetone and alumina balls on spinning rolls. The mixtures was dried in a furnace at 100ºC for 24 hours. After drying the mixture was ground in a mortar to disintegrate agglomerates. Disk pellets (20mm of diameter and 3mm thick), were made for each mixture by uniaxial pressing using at steel die. Press loading of 100MPa was used for all experiments. The samples were introduced into high alumina crucibles and were heat treated from 800 to 1400ºC with isotherms of 4, 6, 8 and 10 hours, with a heating-cooling rate of 10ºCmin-1 and without the use of a special gas to generate an enveloping atmosphere. To avoid possible chemical reactions between the samples and the crucibles, the dicks pellets were placed inside the crucible on a powder layer of the same stoichiometric mixture (previously described) and then covered with the same stoichiometric powder mixture before placing the alumina cap on the crucible. Subsequently, samples were analyzed by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). The samples analyzed by SEM (Philips XL30/ESEM) were cross sectioned and grinded using SiC grinding media from 80 to 2400 grit size. Then the samples were polished using a 1µm diamond paste and treated to remove impurities in ultrasonic bath. Morphology of the phases present in each reaction step, were observed and semi-quantitative analysis (EDS) was performed. The samples analyzed by XRD, previously ground in a mortar until a fine grain size was obtained (30gr). In this way, randomly orientated samples were prepared to avoid preferred orientation. The X-ray diffractometer used (Philips TW-3040) with a monochromatic Cu-Kα radiation operating voltage of 50KV and a current of 30mA. At room temperature, a scanning speed of 0.10º2θmin-1 and a step size of 0.02º were used to examine the samples in the range 10-80º2θ. The crystalline phases were identified by means of the PAN-ICSD database version 2013-1.

2.2 Kinetic study

Kinetic models governing the formation of Sr4Al6O12SO4 by solid state reaction in the SrO-Al2O3-SrSO4 system were determined. The main objectives of kinetic study were i) identifying the kinetic model(s) that describe the formation of products and ii) determining the influence of temperature on the reaction rate. In both cases it was necessary to know the full extent of the reaction, that is, progressive changes from reactants to products in a given time. Such changes, known as reacted fraction11 Quesada Gonzalez O, Torres GE, Llópiz JC. Termogravimetría de alta resolución: Estudio cinético de la deshidratación térmica del cloruro de bario dihidratado. Revista Cubana de Química. 2002;14(1):44-50., were calculated by using Equation 1:

(1) α = m 0 m t m 0 m f

Were mo is the initial amount of product, mt is the amount of product at time t and mf is the final amount of product. The amounts of all the reaction products (strontium compounds) formed during the reactions steps were determined by quantitative X-ray powder diffraction data analysis, using the Sietronics Traces 3.0 software and were plotted as reacted fraction versus time. The basic equation that defines the reaction rate is11 Quesada Gonzalez O, Torres GE, Llópiz JC. Termogravimetría de alta resolución: Estudio cinético de la deshidratación térmica del cloruro de bario dihidratado. Revista Cubana de Química. 2002;14(1):44-50.:

(2) α t = A exp E a RT f α

Where α represents the reacted fraction (0 < α < 1) in the solid reactant during the course of the reaction, A is the Arrhenius pre-exponential factor, T is the temperature of the reaction, f(α) is the kinetic function and depends on the reaction mechanism, Ea is the activation energy for the reaction and R is the gas constant. If the reaction rate is constant, applying the logarithm and rearranging the equation:

(3) ln f α = E a RT + ln C A

Considering that the term ln (C/A) is constant, by plotting f(α) against 1/T for various functions, it is possible to determine the kinetic model(s) describing the mechanism through which the reaction occurs, using the method of adjustment functions11 Quesada Gonzalez O, Torres GE, Llópiz JC. Termogravimetría de alta resolución: Estudio cinético de la deshidratación térmica del cloruro de bario dihidratado. Revista Cubana de Química. 2002;14(1):44-50.. Namely, the experimental curves were compared with ideal curves, these second obtained from the introduction of fraction reacted values in different kinetics models for solid state reaction reported in the literature, being determined kinetic model(s) have greater adjustment functions1111 Brown ME, ed. Handbook of Thermal Analysis and Calorimetry. Amsterdam: Elsevier Science B.V.; 1998. 691 p.. Kinetic phenomena were observed in the samples analyzed by SEM in each reaction step.

2.3 Crystalline structure determination

The crystal structure of Sr4Al6O12SO4 was determined. The structure and microstructure features of the prepared samples were obtained from X-ray powders diffraction data of the same heat treated at 1400ºC with 4 hours isotherm. The measured angular range, the step size and counting times were selected to ensure enough resolution (the step size should be at least, 1/10 of the fwhms) and statistics. The structural refinements were carried out by the Rietveld method using the Fullprof program22 Esteve Cano VJ, ed. El Método de Rietveld. 2ª ed. Castellón: Universitat Jaume I; 2014.; in some cases, a severe microstructural contribution to the profile must be considered. The background intensities were fitted to a polynomial function with ten adjustable parameters. A phenomenological approach was applied using a capability of the program which allows some of the peaks to be described by their own breadths and shapes, as well as small displacements from their positions calculated from the average unit cell. Prior to the structure refinements, a pattern matching without structural model was performed. This procedure allows obtaining suitable profile parameters, including the breadths, shapes and displacements of those reflections with relevant microstructural contributions. An overall isotropic thermal factor (ITF) was used for all the atoms in the structure. The fitting process was finished when convergence is reached.

3. Results and Discussion

3.1 Kinetic study

The kinetic of formation of strontium sulphoaluminate, Sr4Al6O12SO4, within the system SrO-Al2O3-SrSO4 was studied. Figure 1 shows the quantitative X-ray powder diffraction data analysis for all samples were heat treated in the temperature range from 850 to 1100ºC and different isotherms.

Figure 1
Formation of strontium compounds and starting reagents, quantified by X-ray powder diffraction data for samples of the 3Al2O3:3SrCO3:SrSO4 mixture, heat treated at several temperatures and isotherms.

As shown in Figure 1, as strontium compounds are produced the three starting reagents, SrCO3, SrSO4 and Al2O3, remaining quantity decreases, strontium sulfate only remains to the final stage of the reaction. With the process of decomposition of the strontium carbonate in oxide (starts at low temperatures), results in the formation of strontium compounds. At all six temperatures studied, Sr4Al6O12SO4 was formed (result of the reaction between SrO, SrSO4 and Al2O3) and its amount increases gradually with increasing temperature and time. Likewise, the presence of two strontium aluminates, Sr3Al2O6 and SrAl2O4, as intermediate phases were formed (reaction between SrO and Al2O3) initially and persisted until the reaction to form Sr4Al6O12SO4 was nearly complete. Sr3Al2O6 was formed at 850ºC, reached a maximum at 950ºC with 10 hours isotherms and subsequently decreased. Meanwhile, SrAl2O4 was formed at 1000ºC and its amount increases gradually with increasing temperature and time, reached a maximum at 1100ºC with 6 hours isotherms. In the case of this type of aluminate (SrAl2O4), its formation has been previously explained: at temperatures lower than the transformation temperature of SrCO3 from orthorhombic to hexagonal (<920ºC), the formation of strontium compounds is attributed to the interfacial reaction between SrCO3 and alumina. Conversely, at temperatures higher that 920ºC, the solid-state reaction is dominated by the diffusion of Al+3 ions into the SrCO3 lattice1212 Chang YL, Hsiang HI, Liang MT. Phase Evolution During Formation of SrAl2O4 from SrCO3 and a-Al2O3/AlOOH. Journal of the American Ceramic Society. 2007;90(9):2759-2765.-1313 Rojas-Hernandez RE, Rubio-Marcos F, Gonçalves RH, Rodriguez MA, Véron E, Allix M, et al. Original Synthetic Route To Obtain a SrAl2O4 Phosphor by the Molten Salt Method: Insights into the Reaction Mechanism and Enhancement of the Persistent Luminescence. Inorganic Chemistry. 2015;54(20):9896-9907.. At 1100ºC these strontium aluminates, Sr3Al2O6 and SrAl2O4, reacted with SrSO4 to form Sr4Al6O12SO4. To supplement the results, at 1150ºC with 4 hours isotherm, the main identified phase was Sr4Al6O12SO4. This indicated that the formation of this compound is complete at 1150ºC. The amount of Sr4Al6O12SO4 formed at several temperatures is plotted as fraction reacted, α, as a function of time in Figure 2.

Figure 2
Kinetics models fit for the fraction formed of Sr4Al6O12SO4 as function of temperature and time.

This amount always increased with increase in temperature and the reaction approached completion at the highest temperatures. Shows the two models that had the best fit compared with the results. These two models corresponded to R1.1 (geometrical contraction at grain boundary, 1 - (1 - α)1/n and P1.1 (nucleation and growth by the energy law, α1/n). The value of "n" in both models was varied from 1 to 3 and the best fit was found to be 1.1 for each one. The kinetics study always gives an approximation of the phenomenon that is occurring; in this case both models can explain the kinetics formation of strontium compound Sr4Al6O12SO4. For the R1.1 model it can be observed that the values of fraction formed did not fit exactly with the model for the curve at 1100ºC. On the other hand for 1100ºC the model P1.1, fits accurately with experimental data. An analysis of Figure 1, can help to explain the influence of both model in the kinetics of Sr4Al6O12SO4 formation. At low temperatures 800 to 950ºC, the amount of SrCO3 decreased considerably. This decreased in the amount of strontium carbonate indicates a rapid decomposition of SrCO3 in the sample volume, to form SrO available to react with Al2O3 and SrSO4 to form the strontium sulphoaluminate Sr4Al6O12SO4. This process presents a fast and dense initial nucleation at constant speed through all or some crystalline phases, due to the formation of interface reaction zones (low values fraction reacted), with diffusive effects and geometrical contraction. At high temperatures (high values of fraction reacted) reaction zones (active interface) is increased, producing a greater number of nuclei in conjunction with the growth of these to form the total product volumer. Figure 3 shows micrographs of typical samples of 3Al2O3:3SrCO3:SrSO4 mixture, heat treated from 800 to 1150ºC with 4h isotherm, to observe the kinetic mechanisms governing the formation of Sr4Al6O12SO4.

Figure 3
Micrographs of typical samples of 3Al2O3:3SrCO3:SrSO4 mixture, heat treated from 800 to 1150ºC with 4h isotherm. A: 800ºC, B: 900ºC, C: 1000ºC, D: 1100ºC, E and F: 1150ºC.

In Figure 3A nuclei of SrO (1) were identified into the sectioned particles of SrCO3 (2), according to EDS analysis. In Figure 3B the amount of strontium oxide (dark zone) were increased and even, from blowing to form nuclei within the same area of SrO. This process of decomposition of SrCO3 to SrO is carried out throughout the volume of the sample at constant speed, with the dimensioning the crystal grain boundary. Porosity is also present due to the generation of CO2 and grains geometric suffer contraction, as explained by the kinetic mechanism R1.1. In Figure 3C the strontium oxide reacts with alumina present in the system to give rise to two aluminates was observed, the SrAl2O4 (4) and Sr3Al2O6 (5) according to EDS analysis. The latter with a spherical morphology and both are reacting strontium sulfate, SrSO4 (3). In Figure 3D nucleation of Sr4Al6O12SO4 (6) was observed within particles corresponding to SrAl2O4 (4), according to the analysis of EDS, as explained by the kinetic mechanism P1.1. The growth of these nuclei are shown in Figure 3E where particles are identified corresponding to Sr4Al6O12SO4 (6), according to the analysis of EDS and as explained by the kinetic mechanism P1.1. Figure 3F is a magnification of a particle to observe the formation of agglomerates of microspheres for the Sr4Al6O12SO4 (6), according to the analysis of EDS. Figure 4 shows the curves of ln K versus 1/T for both kinetic models. From this curves it was determined that the activation energy for the R1.1 and P1.1 models was 145.47KJmol-1 and 151.37KJmol-1, respectively.

Figure 4
Activation energy curves for the two models involve in the formation of Sr4Al6O12SO4 strontium compound.

3.2 Crystal structure

Structural refinement process was divided into three stages. Firstly, the size and shape of the unit cell was determined through the refining of diffraction patterns with the Rietveld method (using the Fullproof program). Second, as it is a compound with unknown crystal system, the unit cell parameters such as; Miller indices and numbers of atoms were determined analytically1414 Cullity BD. Elements of X-Ray Diffraction. 2nd ed. Reading: Addison-Wesley; 1978.. Finally, the positions of the atoms inside the unit cell were determined with the Rietveld method (using the Fullproof program). A prerequisite in order to begin with the structural determination of any compound is the verification of the purity of the sample. Figure 5 shows the X-ray diffraction patterns for samples heat treated from 1200 to 1500ºC with 4 hours isotherm (the right side shows a typical SEM micrograph of Sr4Al6O12SO4 compound).

Figure 5
On the left patterns of X-ray diffraction of samples head treated at different temperatures with an isotherm of 4 hours. •: Sr4Al6O12SO4. On the right shows a typical SEM micrograph of Sr4Al6O12SO4 compound.

The stability of the compound is observed up to 1500ºC since only the peaks corresponding to the Sr4Al6O12SO4, are recorded without variation at intensities. Thus, the diffraction pattern employed for the structural determination was the heat treated at 1400ºC with an isotherm of 4 hours. Recalling that the Fullprof program needs input crystallographic data to begin refining, crystal system, space group and atomic positions of the Ca4Al6O12SO4 were considered as initial variables1515 Calos NJ, Kennard CHL, Whittaker AK, Davis RL. Structure of calcium aluminate sulfate Ca4Al6O12S. Journal of Solid State Chemistry. 1995;119(1):1-7.. Figure 6 shows the first and last stage of fitting of the X-ray diffraction patterns corresponding to Sr4Al6O12SO4 compound, where the evolutionary process of the method used is observed.

Figure 6
First (A) and last (B) stage of refining diffraction patterns, where the evolutionary process of the method used is observed.

For the first refining (6A) a value of convergence 105 was obtained. This is reflected in the low fit between the experimental pattern (red spots) and the calculated pattern (solid black line), reflecting higher intensity peaks in the differential curve (solid blue line). In the last stage of refining (6B) the value of Chi2 was of 1.94, reflecting this in the good fit between experimental and calculated pattern and low intensity peaks in the differential curve (Yobs - Ycal). Considering the numbers of peak of the diffraction pattern as well as the crystal system that is refining (Orthorhombic), the results are acceptable. Figure 7 presents a scheme of the crystal structure of Sr4Al6O12SO4 strontium compound and crystallographic data.

Figure 7
Representative scheme of the strontium compound (Sr4Al6O12SO4) crystal structure and crystallographic data.

Yellow spheres represent oxygen atoms (80), red spheres represent atoms of strontium (20), with spheres represent atoms of aluminum (30) and purple spheres represent atoms of sulfur (5). Tetrahedron are formed with sulfur and oxygen atoms. Atomic coordinates within the unit cell of the elements present in the compound are presented in Table 1.

Table 1
Atomic coordinates of elements present in the Sr4Al6O12SO4 compound.

4. Conclusions

  • The crystal structure of the Sr4Al6O12SO4 compound was determined using the Rietveld method. The shape of the unit cell is Orthorhombic, with next reticular parameters: a = 13.32802Å, b = 13.34430Å and c = 9.38704Å, the volume of cell is 1669.51414Å33 Harris KD, Tremayne M, Kariuki BM. Contemporary Advances in the Use of Powder X-Ray Diffraction for Structure Determination. Angewandte Chemie (International ed. in English). 2001;40(9):1626-1651. and has Pcc2 space group. The number of atoms within the unit cell was determined, existing 80 atoms of oxygen, 30 atoms of aluminum, 20 atoms of strontium and 5 atoms of sulphur. The atomic positions within unit cell were determined using the Fullproof, FOX and CARINE computational programs.

  • The kinetics of formation of Sr4Al6O12SO4 is controlled by two models, R1.1 (geometrical contraction at grain boundary, 1 - (1 - α)1/n and P1.1 (nucleation and growth by the energy law, α1/n). The activation energies for these models were 145.47KJmol-1 and 151.37KJmol-1, respectively. It was identified the formation of Sr3Al2O6 and SrAl2O4 as intermediate phases. The formation of Sr4Al6O12SO4 occurred at low temperature as 1150ºC.

5. Acknowledgments

Authors would like to thank to National Coucil of Science and Technology of México (CONACyT) for financial support for the development of this work as well as the processing laboratories and characterization of CINVESTAV-Saltillo and UPV for the technical support.

6. References

  • 1
    Quesada Gonzalez O, Torres GE, Llópiz JC. Termogravimetría de alta resolución: Estudio cinético de la deshidratación térmica del cloruro de bario dihidratado. Revista Cubana de Química 2002;14(1):44-50.
  • 2
    Esteve Cano VJ, ed. El Método de Rietveld 2ª ed. Castellón: Universitat Jaume I; 2014.
  • 3
    Harris KD, Tremayne M, Kariuki BM. Contemporary Advances in the Use of Powder X-Ray Diffraction for Structure Determination. Angewandte Chemie (International ed. in English) 2001;40(9):1626-1651.
  • 4
    Tremayne M. The impact of powder diffraction on the structural characterization of organic crystalline materials. Philosophical Transactions. Series A, Mathematical, Physical, and Engineering Sciences 2004;362(1825):2691-2707.
  • 5
    McCusker LB, von Dreele RB, Cox DE, Louër D, Scardi P. Rietveld refinement guidelines. Journal of Applied Crystallography 1999;32:36-50.
  • 6
    Gilioli C, Massazza F, Pezzuoli M. A new compound: Strontium sulphoaluminate and its relationships with calcium sulphoaluminate. Cement and Concrete Research 1971;1(6):621-629.
  • 7
    Brenchley ME, Weller MT. Synthesis and structure of sulfide aluminate sodalites. Journal of Materials Chemistry 1992;2(10):1003-1005.
  • 8
    Rodríguez-García JA, Rocha-Rangel E, Torres-Torres J, Almanza-Robles JM. Synthesis by a solid state reaction of the Sr4Al6O12SO4 compound. Journal of Ceramic Processing Research 2011;12(3):310-313.
  • 9
    Rodríguez-García JA, Rocha-Rangel E, Almanza-Robles JM, Torres-Torres J, Leal Cruz AL, Munive GT. Chemical interaction of Sr4Al6O12SO4 with liquid aluminum alloys. In: Sing JP, Bansal NP, Goto T, Lamon J, Choi SR, Mahmoud MM, et al., eds. Processing and Properties of Advanced Ceramics and Composites IV: Ceramic Transactions, Volume 234 Hoboken: Willey; 2012. p. 21-27.
  • 10
    Rodríguez-García JA, Rocha-Rangel E, López Hernández J, Hernández-Bocanegra A, Leal-Cruz A, Almanza-Robles J, et al. Physical properties of the Sr4Al6O12SO4 ceramic compound. Wulfenia Journal 2014;21(2):420-427.
  • 11
    Brown ME, ed. Handbook of Thermal Analysis and Calorimetry Amsterdam: Elsevier Science B.V.; 1998. 691 p.
  • 12
    Chang YL, Hsiang HI, Liang MT. Phase Evolution During Formation of SrAl2O4 from SrCO3 and a-Al2O3/AlOOH. Journal of the American Ceramic Society 2007;90(9):2759-2765.
  • 13
    Rojas-Hernandez RE, Rubio-Marcos F, Gonçalves RH, Rodriguez MA, Véron E, Allix M, et al. Original Synthetic Route To Obtain a SrAl2O4 Phosphor by the Molten Salt Method: Insights into the Reaction Mechanism and Enhancement of the Persistent Luminescence. Inorganic Chemistry 2015;54(20):9896-9907.
  • 14
    Cullity BD. Elements of X-Ray Diffraction 2nd ed. Reading: Addison-Wesley; 1978.
  • 15
    Calos NJ, Kennard CHL, Whittaker AK, Davis RL. Structure of calcium aluminate sulfate Ca4Al6O12S. Journal of Solid State Chemistry 1995;119(1):1-7.

Publication Dates

  • Publication in this collection
    09 Feb 2017
  • Date of issue
    Dec 2016

History

  • Received
    03 Sept 2016
  • Reviewed
    28 Nov 2016
  • Accepted
    27 Dec 2016
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