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  • 1 Department of Chemical Organic Technology and Petrochemistry, Silesian University of Technology, B. Krzywoustego 4, 44-100, Gliwice, Poland
  • | 2 Department of Chemistry, Inorganic Technology and Fuels, Silesian University of Technology, B. Krzywoustego 6, 44-100, Gliwice, Poland
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Abstract

Thermogravimetric analysis of azo-peroxyesters revealed two decomposition stages on TG curves. Molecular nitrogen is released in the first stage and carbon dioxide in the second. Fitting the thermogravimetric data by means of the three-parameter model and a classic one based on an Arrhenius-type kinetic equation showed that the former approach satisfactorily describes the process within the wide range of the extent of decomposition. It was found that two coefficients of the three-parameter equation are related to the temperature of maximum reaction rate. One of the coefficients of the three-parameter equation is also related to the activation energy. The compounds investigated can be grouped with respect to their kinetic characteristics, structure and stage of decomposition.

Abstract

Thermogravimetric analysis of azo-peroxyesters revealed two decomposition stages on TG curves. Molecular nitrogen is released in the first stage and carbon dioxide in the second. Fitting the thermogravimetric data by means of the three-parameter model and a classic one based on an Arrhenius-type kinetic equation showed that the former approach satisfactorily describes the process within the wide range of the extent of decomposition. It was found that two coefficients of the three-parameter equation are related to the temperature of maximum reaction rate. One of the coefficients of the three-parameter equation is also related to the activation energy. The compounds investigated can be grouped with respect to their kinetic characteristics, structure and stage of decomposition.

Introduction

There are growing demands in different branches of industry for polymeric materials with customized physical and chemical properties. This has prompted investigations into new types of polymers and new polymerization techniques. It is difficult, however, to design homopolymeric materials with customized properties: it is much easier to design block or star-like copolymers, for example. To obtain such materials numerous polymerization techniques and different bi- and polyfunctional initiators are used. Such initiators contain two or more identical or different groups in their structure that can initiate polymerization according to radical or ionic mechanisms. In this way, block, linear and branched copolymers can be obtained [1].

Azo-peroxy compounds containing azo and peroxy groups (of different thermal and photochemical stability) in their structure are bifunctional initiators. These compounds can initiate polymerization at various copolymerization stages according to a free radical chain mechanism. The polymerization of various unsaturated monomers initiated by azo-peroxyesters has been tested [24].

The details of the synthesis of azo-peroxyesters by the reaction of sodium salts of organic hydroperoxides with acid chlorides, as well as investigations of their spectroscopic features and stability are given elsewhere [5]. On the other hand, peroxy and azo compounds have been analysed by isothermal and dynamic thermoanalytical methods [68]. These investigations enable the activation energies for decomposition, decomposition rate constants at different temperatures, and thermal ranges of decomposition to be determined. The kinetic data enables the conditions of polymerization under which these compounds are used as initiators to be established. Thermal analysis also supplies information on the safe storage and handling of the compounds [2]. We found that in the case of compounds containing both azo and peroxy groups it is more convenient to perform analyses under dynamic conditions with a constant rate of temperature increase [2].

Here we report the results of thermoanalytical investigations of compounds containing tert-butyl (t-Bu) and tert-amyl (t-Am) substituents and alkyl chains of different length between the azo and peroxy groups (Scheme 1).

Scheme 1
Scheme 1

The compounds investigated: 1 (n = 2, R = t-Bu), 2 (n = 3, R = t-Bu), 3 (n = 4, R = t-Bu), 4 (n = 2, R = t-Am), 5 (n = 3, R = t-Am), 6 (n = 4, R = t-Am)

Citation: Journal of Thermal Analysis and Calorimetry J Therm Anal Calorim 105, 3; 10.1007/s10973-011-1538-1

The results of DSC investigations of these compounds showed that in the first stage, at lower temperatures, azo groups decompose, while at higher temperatures, the peroxyester fragments break down [5]. N2 is released in the first stage and CO2 in the second (Scheme 2).

Scheme 2
Scheme 2

Thermal decomposition pathways of azo-peroxyesters

Citation: Journal of Thermal Analysis and Calorimetry J Therm Anal Calorim 105, 3; 10.1007/s10973-011-1538-1

DSC analyses revealed that both stages are partially superimposed. Additionally the endothermic signal of melting overlaps with the signal of the first decomposition stage, which made the analysis difficult. That is why we used dynamic thermogravimetric analysis and complex kinetic analysis to describe the overall chemical changes during the decomposition of the compound investigated.

Experimental

The compounds investigated were synthesized as described elsewhere [5]. Thermogravimetric measurements were carried out using a Mettler Toledo TGA/SDTA-851 instrument under the following conditions: platinum crucible, sample mass 1–1.5 mg, heating rate 1–6 K min−1, N2 atmosphere (gas flow rate, 100 cm3 min−1).

Results

Examples of TG and DTG curves for the compounds investigated (13) are presented in Fig. 1. Two quite well-resolved decomposition stages are seen. N2 is released in the first stage, CO2 in the second. Analysis of mass loss on the basis of TG curves indicates that in the second stage volatile products other than CO2 are formed (the mass loss is greater than that predicted from the stoichiometry of the reactions shown in Scheme 2). The further mass loss (at higher temperatures) seen in TG curves is difficult to ascribe by any simple chemical process. The characteristic temperatures extracted from DTG curves, Ti and Tm, i.e. temperatures of the onset of decomposition and the maximum of the DTG peak, respectively, are presented in Table 1. Analysis of these characteristic temperatures indicates that decomposition of all samples occurs in a similar temperature range, from 357–364 K to 398–403 K, in the first stage and from 398–403 K to 450–453 K in the second stage. Compounds 46 generally decompose at somewhat lower temperatures than 13. This may be due to differences in their chemical structure—different R (Scheme 1).

Fig. 1
Fig. 1

TG and DTG curves for compounds 13: 1 (solid line), 2 (long dashed line), 3 (short dashed line) (for details see Scheme 1)

Citation: Journal of Thermal Analysis and Calorimetry J Therm Anal Calorim 105, 3; 10.1007/s10973-011-1538-1

Table 1

Characteristic temperatures of the thermal decomposition of azo-peroxyesters

Compound no.aFirst stagebSecond stageb
TiTmTiTm
1363 387 402 432 
2364 386 401 429 
3369 384 402 428 
4357 383 398 426 
5361 386 403 424 
6359 387 399 425 

For details see Scheme 1

Temperatures in K

Discussion

The thermal decomposition of azo-peroxyesters proceeds in two stages reflected by the two peaks on the TG curves. Methods based on Arrhenius-type kinetic equations are usually used to fit thermogravimetric data and to determine kinetic parameters [913]. These methods are widely applied in the case of dynamic measurements carried out at different heating rates. In this paper, the thermogravimetric data obtained at one heating rate was analysed with Arrhenius-type and three-parameter equations.

Arrhenius-type equation

The differential kinetic equation for dynamic conditions takes the form
1
where α the extent of reaction, T temperature, A pre-exponential factor, E activation energy, R gas constant, q heating rate (dT/dτ = const, τ time) and f(α) differential function reflecting the kinetic model of the process.
After integration of Eq. 1 one obtains
2
where g(α) the integral function representing the kinetic model of the process. We applied the Coats–Redfern approximation [14, 15] of the temperature integral in Eq. 2, which gives the following equations [16]
3
4

To obtain the kinetic parameters from Eq. 1, f(α) functions were selected using the criteria proposed in [17].

Average activation energies () were calculated for selected models from the relationship
5
where N the number of models and b the coefficient for the model (1 for F and R, 1/2 for A2, 1/3 for A3 and 2 for D).

The results are presented in Table 2. There are significant differences in E values for the first stage of decomposition. Moreover, both stages of decomposition are well described by the F1, A2 and A3 models, and that in the majority of cases the F1 model gives the best fit.

Table 2

Average activation energies and pre-exponential factors obtained by fitting thermogravimetric data for azo-peroxyesters with an Arrhenius-type equation

Compound no.aFirst stagebSecond stageb
/kJ mol−1r2 > 0.98/kJ mol−1r2 > 0.98
1188 17.1F1, A2, A3182 13.0F1, A2, A3
2169 14.1F1, A2, A3195 14.8F1, A2, A3
3223 22.3F1, A2, A3188 14.0F1, A2, A3
4153 11.7F1, A2, A3183 13.4F1, A2, A3
5150 11.2F1, A2, A3180 13.0F1, A2, A3
6143 10.1F1, A2, A3175 12.2F1, A2, A3

For details see Scheme 1

values were calculated using Eq. 5; values were calculated by replacing E with ln A in Eq. 5; r2 represents the determination coefficient

The results indicate the existence of the isokinetic effect—a linear relationship between the logarithm of the pre-exponential factor and the activation energy (Fig. 2) [18]. The straight lines resulting from the approximation have the following analytical forms
6
7
Fig. 2
Fig. 2

Isokinetic effect in the thermal decomposition of azo-peroxyesters (numbers indicate the compounds investigated—for details see Scheme 1)

Citation: Journal of Thermal Analysis and Calorimetry J Therm Anal Calorim 105, 3; 10.1007/s10973-011-1538-1

In Fig. 2 the points related to compounds 13 are placed on the left-hand side, whereas those corresponding to compounds 46 are on the right-hand side. In the first stage of the decomposition, the points representing compounds 13 and 46 are more widely separated than in the second stage. Values of E (175–195 kJ mol−1) for the second stage (CO2 removal) are similar to those found for other organic compounds [19, 20], but are lower than the ones determined for the decomposition of calcium carbonate [9].

Three-parameter equation

Following [17] we applied the three-parameter model to the TG curve fitting, which links the extent of reaction (α) with temperature (T) without the integral g(α). The model is represented by the equation [21]
8
where a0, a1 and a2 are characteristic coefficients related to the kinetics and thermodynamics of the thermal decomposition.

The three-parameter equation arising from the van’t Hoff’s isobar enables the dissociation enthalpy to be determined, since it is proportional to (where αeq and Teq denote the extent of reaction and temperature, respectively, under equilibrium conditions) [22]. It was found that a2 changes linearly with changes of both a0 and a1 [2326]. Figure 3 shows one of these dependences for the compounds investigated.

Fig. 3
Fig. 3

Relationships between coefficients in the three-parameter equation (numbers indicate the compounds investigated—for details see Scheme 1)

Citation: Journal of Thermal Analysis and Calorimetry J Therm Anal Calorim 105, 3; 10.1007/s10973-011-1538-1

The differentiation and transformation of Eq. 8 yields the relationship for the relative rate (r) expressed by the formula [26]
9
Further transformation of Eq. 9 produces relationship 10 determining the zero-order temperature profile [24]
10
In the kinetic analysis we also applied the relationships 11 and 12 that we derived earlier [27]
11
And
12
where rm represents the maximum reaction rate.
By combining Eqs. 11 and 12 one obtains a relationship that links coefficients a1 and a2 with the temperature of the maximum reaction rate
13

Plots of reaction rate (r) versus temperature (T) are presented in Fig. 4. Their linear sections correspond to a quite wide range of α values from 0.2 to 0.9 for the first stage and from 0.05 to 0.9 for the second one. This follows previous findings, which show that it is more convenient to apply the relative rate of thermal decomposition than the hitherto used DTG data (Fig. 1). Values of a1, a2, Tm (calculated from Eq. 12) and ΔTm for both decomposition stages are presented in Table 3. If we take relationship 9 into account, we see that an increase in a2 also leads to an increase in reaction rate (r) in terms of dα/dT, but not always in terms of dα/dτ, which is considered to be the primary formula for the determination of r [28]. According to our investigations, a0 and a1 increase when a2 does so. Calculated values of Tm are generally higher than its measured values, although both sets of values correspond quite well to each other. This implies that our approach is reliable.

Fig. 4
Fig. 4

Relationship of r versus T for compound 1 (for details see Scheme 1)

Citation: Journal of Thermal Analysis and Calorimetry J Therm Anal Calorim 105, 3; 10.1007/s10973-011-1538-1

Table 3

Coefficients obtained from the fitting of thermogravimetric data with the three-parameter equation

Compound no.aFirst stagebSecond stageb
a1 × 103a2r2TmΔTma1 × 103a2r2TmΔTm
1462 1155 0.940387 0.5333 739 0.982432 2.3
2361 904 0.916386 0.4449 1010 0.971429 2.2
3488 1215 0.929384 6.0418 939 0.969428 2.5
4329 822 0.907383 3.5502 1140 0.991426 0.8
5334 833 0.915386 1.1484 1100 0.985424 2.9
6323 804 0.901387 0.8449 1020 0.985425 1.8

Values a1, Tm(calculated) and ΔTm are in K; values of a1 and a2 were obtained by fitting Eq. 8 to thermogravimetric data; values of Tm (calculated) were derived by using Eq. 13; ΔTm = Tm (calculated) − Tm (measured)

Values of a2 are relatively high: 804–1215 for the first stage of thermal decomposition and 739–1140 for the second. They are typical of chemical processes rather than physical ones [17]. The rate of mass loss after these two stages can be obtained from relationship 10, which appears to be formally a zero-order activationless process [24].

Relations between a2 and E can be grouped on the basis of differences in the structures of the compounds (13 and 46) and the stages of decomposition (Fig. 5). Linear trends are observed for a given group of compounds and stage of the process. This may indicate that chemical structure is the main factor affecting the kinetic characteristics of thermal decomposition.

Fig. 5
Fig. 5

Dependence of a2 coefficient versus activation energy (E) for azo-peroxyesters (numbers indicate the compounds investigated—for details see Scheme 1)

Citation: Journal of Thermal Analysis and Calorimetry J Therm Anal Calorim 105, 3; 10.1007/s10973-011-1538-1

Conclusions

The thermal decomposition of azo-peroxyesters proceeds in two stages—N2 is released in the first and CO2 in the second. The mass loss seen on the TG curves indicates that after the second stage other volatile products are evolved (the mass loss is greater than that predicted from the stoichiometry of the reactions shown in Scheme 2).

The fitting of non-isothermal thermogravimetric data obtained at one heating rate using an Arrhenius-type kinetic equation provided an opportunity to determine the basic kinetic characteristics of the decomposition of azo-peroxyesters. The isokinetic effect due to the chemical similarity of the samples was found to have occurred. The kinetic characteristics obtained by this approach do not discriminate the compounds investigated.

The three-parameter model fits the thermogravimetric data linearly within a wide range of the extent of decomposition. This follows previous findings, which showed that the relative rate of thermal decomposition is more convenient than the hitherto used DTG data. The results indicate that a0 and a1 increase as a2 does so. Furthermore, the temperature of the maximum rate of decomposition is linked to a1 and a2. The predicted temperatures at which the rate of decomposition is a maximum correlate well with values of this quantity determined directly from DTG curves.

The results of this research confirm that the three-parameter model is more useful and convenient than the classical methods based on Arrhenius-type equations in the kinetic analysis of thermal decomposition processes.

References

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    • Search Google Scholar
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    • Export Citation
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    • Search Google Scholar
    • Export Citation
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    • Search Google Scholar
    • Export Citation
  • 21. Mianowski, A. Thermal dissociation in dynamic conditions by modeling thermogravimetric curves using the logarithm of conversion degree. J Therm Anal Calorim. 2000;59:747762. .

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    • Search Google Scholar
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    • Search Google Scholar
    • Export Citation
  • 24. Mianowski, A, Bigda, R, Zymla, V. Study on kinetics of combustion of brick-shaped carbonaceous materials. J Therm Anal Calorim. 2006;84:563574. .

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    • Search Google Scholar
    • Export Citation
  • 25. Mianowski, A, Blazewicz, S, Robak, Z. Analysis of the carbonization and formation of coal tar pitch mesophase under dynamic conditions. Carbon. 2003;41:24132424. .

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    • Search Google Scholar
    • Export Citation
  • 26. Mianowski, A. Analysis of the thermokinetics under dynamic conditions by relative rate of thermal decomposition. J Therm Anal Calorim. 2001;63:765776. .

    • Crossref
    • Search Google Scholar
    • Export Citation
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  • 1. Bernaerts, KV, Du Prez, FE. Dual/heterofunctional initiators for the combination of mechanistically distinct polymerization techniques. Prog Polym Sci. 2006;31:671722. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 2. Pabin-Szafko, B, Wisniewska, E, Hefczyc, B, Zawadiak, J. New azo-peroxidic initiators in the radical polymerization of styrene and methyl methacrylate. Eur Polym J. 2009;45:14761484. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 3. Czech, Z, Butwin, A, Hefczyc, B, Zawadiak, J. Radical initiators and their influence on the viscosity and molecular weight of acrylic polymers applied in pressure-sensitive adhesives. Polimery. 2009;54:283287.

    • Search Google Scholar
    • Export Citation
  • 4. Czech, Z, Butwin, A, Herko, E, Hefczyc, B, Zawadiak, J. Novel azo-peresters radical initiators used for the synthesis of acrylic pressure-sensitive adhesives. eXPRESS Polym Lett. 2008;2:277283. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 5. Zawadiak, J, Hefczyc, B, Janeczek, H, Kowalczuk, M. Synthesis and thermal properties of azo-peroxyesters. Monatsch Chem. 2009;140:303308. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 6. Severini, F, Gallo, R. DSC study of thermal decomposition of peroxide and azo derivative mixtures in the presence of LDPE. J Therm Anal Calorim. 1987;32:11891200. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 7. Cheikhalard, T, Tighzert, L, Pascault, P. Thermal decomposition of some azo initiators. Influence of chemical structure. Angew Makromol Chem. 1998;256:4959. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 8. Severini, F, Gallo, R. Differential scanning calorimetry study of the thermal decomposition of peroxides in the absence of a solvent. J Therm Anal Calorim. 1985;30:841847. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 9. Brown, ME, Maciejewski, M, Vyazovkin, S, Nomen, R, Sempere, J, Burnham, A, Opfermann, J, Strey, R, Anderson, HL, Kemmler, A, Keuleers, R, Janssens, J, Desseyn, HO, Li, Ch-R, Tang, TB, Roduit, B, Malek, J, Mitsuhashi, T. Computational aspects of kinetic analysis.: Part A. The ICTAC kinetics project—data, methods and results. Thermochim Acta. 2000;355:125143. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 10. Maciejewski, M. Computational aspects of kinetic analysis.: Part B. The ICTAC Kinetics Project—the decomposition kinetics of calcium carbonate revisited, or some tips on survival in the kinetic minefield. Thermochim Acta. 2000;355:145154. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 11. Vyazovkin, S. Computational aspects of kinetic analysis.: Part C. The ICTAC Kinetics Project—the light at the end of the tunnel?. Thermochim Acta. 2000;355:155163. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 12. Burnham, AK. Computational aspects of kinetic analysis.: Part D. The ICTAC Kinetics Project—multi-thermal-history model-fitting methods and their relation to isoconversional methods. Thermochim Acta. 2000;355:165170. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 13. Roduit, B. Computational aspects of kinetic analysis.: Part E. The ICTAC Kinetics Project—numerical techniques and kinetics of solid state processes. Thermochim Acta. 2000;355:171180. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 14. Coats, AW, Redfern, JP. Kinetic parameters from thermogravimetric data. Nature. 1964;201:6869. .

  • 15. Coats, AW, Redfern, JP. Kinetic parameters from thermogravimetric data. II. J Polym Sci Part B: Polym Lett. 1965;3:917920. .

  • 16. Mianowski, A, Radko, T. Evaluation of the solutions of a standard kinetic equation for non-isothermal conditions. Thermochim Acta. 1992;204:281293. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 17. Mianowski, A, Siudyga, T. Influence of sample preparation on thermal decomposition of wasted polyolefins–oil mixtures. J Therm Anal Calorim. 2008;92:543552. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 18. Mianowski, A, Bigda, R. The Kissinger law and isokinetic effect: Part II. Experimental analysis. J Therm Anal Calorim. 2004;75:355372. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 19. Criado, JM, Gonzalez, M, Malek, J, Ortega, A. The effect of the CO2 pressure on the thermal decomposition kinetics of calcium carbonate. Thermochim Acta. 1995;254:121127. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 20. Britt PF , Buchanan AC, Eskay TP, Mungall WS. Mechanistic investigations into the decarboxylation of aromatic carboxylic acids. American Chemical Society National Meeting, New Orleans, LA, August 22–26, 1999.

    • Search Google Scholar
    • Export Citation
  • 21. Mianowski, A. Thermal dissociation in dynamic conditions by modeling thermogravimetric curves using the logarithm of conversion degree. J Therm Anal Calorim. 2000;59:747762. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 22. Šesták, J. Heat, thermal analysis and society. Hradec Králové: Nucleus HK; 2004.

  • 23. Mianowski, A, Bigda, R. Thermodynamic interpretation of three-parametric equation: Part I. New form of equation. J Therm Anal Calorim. 2003;74:423432. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 24. Mianowski, A, Bigda, R, Zymla, V. Study on kinetics of combustion of brick-shaped carbonaceous materials. J Therm Anal Calorim. 2006;84:563574. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 25. Mianowski, A, Blazewicz, S, Robak, Z. Analysis of the carbonization and formation of coal tar pitch mesophase under dynamic conditions. Carbon. 2003;41:24132424. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 26. Mianowski, A. Analysis of the thermokinetics under dynamic conditions by relative rate of thermal decomposition. J Therm Anal Calorim. 2001;63:765776. .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 27. Mianowski, A. Consequences of Holba-Šesták equation. J Therm Anal Calorim. 2009;96:507513. .

  • 28. Holba, P, Šesták, J. Kinetics with regard to the equilibrium of process studied by non-isothermal techniques. Z Physik Chem Neue Folge. 1972;80:120.

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  • Impact Factor (2019): 2.731
  • Scimago Journal Rank (2019): 0.415
  • SJR Hirsch-Index (2019): 87
  • SJR Quartile Score (2019): Q3 Condensed Matter Physics
  • SJR Quartile Score (2019): Q3 Physical and Theoretical Chemistry
  • Impact Factor (2018): 2.471
  • Scimago Journal Rank (2018): 0.634
  • SJR Hirsch-Index (2018): 78
  • SJR Quartile Score (2018): Q2 Condensed Matter Physics
  • SJR Quartile Score (2018): Q2 Physical and Theoretical Chemistry

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Journal of Thermal Analysis and Calorimetry
Language English
Size A4
Year of
Foundation
1969
Volumes
per Year
4
Issues
per Year
24
Founder Akadémiai Kiadó
Founder's
Address
H-1117 Budapest, Hungary 1516 Budapest, PO Box 245.
Publisher Akadémiai Kiadó
Springer Nature Switzerland AG
Publisher's
Address
H-1117 Budapest, Hungary 1516 Budapest, PO Box 245.
CH-6330 Cham, Switzerland Gewerbestrasse 11.
Responsible
Publisher
Chief Executive Officer, Akadémiai Kiadó
ISSN 1388-6150 (Print)
ISSN 1588-2926 (Online)

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