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Polymer Degradation and Stability 96 (2011) 943e948

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Polymer Degradation and Stability
journal homepage: www.elsevier.com/locate/polydegstab

Thermal characterization of HCN polymers by TGeMS, TG, DTA and DSC methods
José L. de la Fuente a, *, Marta Ruiz-Bermejo b, César Menor-Salván b, Susana Osuna-Esteban b
a

Instituto Nacional de Técnica Aeroespacial “Esteban Terradas” (INTA), Carretera Torrejón-Ajalvir, Km. 4, E-28850 Torrejón de Ardoz, Madrid, Spain
Centro de Astrobiología [Consejo Superior de Investigaciones Científicas-Instituto Nacional de Técnica Aeroespacial “Esteban Terradas” (CSIC-INTA)],
Carretera Torrejón-Ajalvir, Km. 4, E-28850 Torrejón de Ardoz, Madrid, Spain

b

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 17 December 2010
Received in revised form
17 January 2011
Accepted 28 January 2011
Available online 22 February 2011

This paper presents a thermogravimetry (TG) study of hydrogen cyanide polymers, synthesized from the
reaction of equimolar aqueous solutions of sodium cyanide and ammonium chloride. Differential
thermal analysis (DTA) and differential scanning calorimetry (DSC) were also used to evaluate the
thermal behaviour of these black polymers, which play an important role in prebiotic chemistry. A
coupled TGemass spectrometer (MS) system allowed us to analyze the principal volatile thermal
decomposition and fragmentation products of the isolated HCN polymers under dynamic conditions and
an inert atmosphere. After dehydration, a multi-step decomposition occurred in this particular polymeric system, due to the release of ammonia, hydrogen cyanide (depolymerization reaction), isocyanic
acid (or cyanic acid) and formamide; these two latter species allow us identify bond connectivities.
Finally, data collected from TG experiments in an oxidative atmosphere showed significant differences at
higher temperatures, above 400  C. According to these results, the different techniques of thermal
analysis here applied have demonstrated to be an adequate methodology for the study and characterization of this complex macromolecular system, whose structure remains controversial even today.
Ó 2011 Elsevier Ltd. All rights reserved.

Keywords:
HCN polymers
Coupled TGeMS
Thermal decomposition
DSC
DTG

1. Introduction
Hydrogen cyanide (HCN) is a ubiquitous molecule in the
universe. HCN, whether as gas, a pure liquid, or in solution, polymerizes easily over a wide range of temperature and pressure in the
presence of amounts of a base catalyst to yield a dark complex solid,
known as “HCN polymers” [1e3]. In addition, recently HCN polymers have been synthesized from the thermal decomposition of
formamide [4].
The HCN polymers may be among the organic macromolecules
most readily formed within the solar system. The HCN polymers
could be the major component of the dark matter observed on
many bodies of the outer solar system including asteroids, moons,
planets and, especially, comets [5,6]. It has been also proposed that
the reddish haze (tholin) present in the atmosphere of Titan could
be analogous to HCN polymers [7].
Besides the interest in this polymeric system from a prebiotic
perspective, the HCN polymers can be used as a starting material
for the synthesis of carbon nitride materials, expected to have
unique mechanical properties such as wear, resistance coating and
hardness [8e18]. However, certain structural aspects of these HCN

* Corresponding author. Tel.: þ34 91 5206841; fax: þ34 91 5206611.
E-mail address: fuentegj@inta.es (J.L. de la Fuente).
0141-3910/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2011.01.033

polymers remain controversial, despite extensive efforts over the
last 50 years. Part of this is due to the various analytical techniques
different authors have used, part of it is due to the manner in which
the polymers were synthesized.
Thermogravimetry (TG) is one of the most commonly used
thermal analysis techniques for the characterization of both inorganic and organic materials, including polymers. It provides
quantitative results regarding the weight loss of a sample as
a function of temperature or time. Moreover, TG measurements
give basic information about the thermal properties of the material
and its composition. The derivative thermogravimetry (DTG) can be
used to investigate the differences between thermograms.
In recent years, multi-purpose thermal analysis coupled with
evolved gas analyzers has become very popular, as it can be used to
carry out further analysis of evolved gases during TG measurements; producing details of thermal decomposition processes,
which in turn facilitate estimation of sample structure and
composition. Regarding instrumentation, a great number of gas
detectors or analyzers have been utilized in evolved gas analysis
(EGA), being the most important analyzer Fourier transform
infrared (FTIR) spectrometers, and pre-eminently mass spectrometers (MS). Both methods can be used to record spectra repetitively,
thereby producing a time-dependent record of the composition of
the gas phase, from which EGA curves can be constructed for
selected species [19e22].

Table 1 Experimental conditions. A coupled TGeMS system was used to analysis the principal species evolved during dynamic thermal decomposition or fragmentation processes for the HCN polymers synthesized. The polymers were prepared from solutions of equimolar amounts of ammonium chloride (NH4Cl) and sodium cyanide (NaCN) in pure water (MilliQ grade) at 1 M concentration. The results obtained from this thermal analysis provide useful information in drawing a correlation between their properties and chemical structure. and washed with distillate water (4) collecting black solids which were dried under reduced pressure. Elemental C. yields (calculated from the initial amount of carbon containing in the initial NaCN) and elemental analysis for the series of HCN black polymers synthesized. and the argon and oxygen flow rate was 100 ml/min. Heating rate was 10  C/min and the argon atmosphere. Fig. Our results are comparable to those reported by Eastman et al.4 3. involves a mass loss of around 9 wt%. Samples (w5 mg) were scanned at 10  C/min under dry nitrogen (100 ml/min). These spectra greatly resemble those reported in the literature for HCN polymers prepared under different experimental conditions [5. 1.9 40. Perkin Elmer DSC/TA7DX. Representative thermogravimetric curves are shown in Fig. However. and corresponds to the vaporization of moisture.8 41. a longer reaction time does not have a significant influence on the yield of these insoluble products (29  4%). Results and discussion The yield found in the polymerization reactions as well as the results of the elemental analysis for the “HCN polymers” obtained under the experimental conditions described above are shown in Table 1. in spite of the fact that they were obtained with different reaction times. de la Fuente et al. All solutions were heated at 38  C during the reaction time for comparative purposes with respect to our previous works about the formation of tholins under CH4 atmosphere [24e26].4 4. A differential scanning calorimetry (DSC. derivative thermogravimetry (DTG) and differential thermal analysis (DTA) measurements were preformed with a simultaneous thermal analyzer model Q600 of TA Instruments. Experimental section Three HCN polymer samples were synthesized using different reaction times. The degradation starts around 150  C and distributes over a broader temperature range. indicating that basically the same macrostructure is present in all of them (see Figs. main pyrolysis stage (150e500  C) and carbonization (>500  C). a systematic thermal degradation study stability of the HCN polymers has been carried out both in argon (thermal stability) and in oxygen (thermal-oxidative stability) atmosphere. 1a.28e30]. From this figure.5 36. The analytical and spectroscopic data. The temperature and heat flow were calibrated with common standards. The NH4Cl and NaCN were obtained from SigmaeAldrich. FTIR. [23]. of the HCN polymers synthesized are very similar. and one month without stirring. The first one. 2. (a) TG and (b) DTG curves for HCN polymer samples synthesized. The yields in this work were calculated from the initial amount of carbon contained in the initial NaCN. Polymer sample Reaction time (days) Yield (%) C (%) H (%) N (%) O (%) Empirical formula 1 2 3 3 10 30 25 27 33 36. For the elemental O analyses a LECO VTF-900 analyzer was used.944 J.5 36. differential thermal analysis (DTA) and differential scanning calorimetry (DSC) were also employed to evaluate different thermal features of these black polymers. model Thermostar QMS200 M3. to the desorption of water and to the possible emission of volatile organic compound.L. Thermogravimetry (TG). Samples were filtered using glass fibre filters after reactions.4 17. insoluble solid richer in oxygen was obtained.2 4. The solutions were left standing for three. The average sample weight was w10 mg. [27] for short reaction times (1e10 days). and 13C CP-MAS-NMR. 1 and 2 in reference [24]). The second stage. corresponds with 3. / Polymer Degradation and Stability 96 (2011) 943e948 In the present work. and to understand their decomposition mechanism. Thermogravimetric and DSC analysis The TG thermograms of HCN polymers were recorded under dynamic conditions from room temperature to 1000  C at a heating rate of 10  C/min and under argon atmosphere. which demonstrates the high degree of similarity between them.6 17. it is evident that the thermal degradation of all samples can be divided into three stages: drying stage (<150  C). between 25 and 150  C.2 C3H4N3O C3H4N3O C5H6N4O2 3. This initial step of weight loss at low temperatures indicates the hydrophilicity of the HCN polymers. Non-isothermal experiments were performed in the temperature range from 25 to 1000  C and at a heating rate of 10  C/min. As can be seen. with an electron-impact quadruple mass-selective detector. the thermal degradation of the different samples shows practically an identical behaviour.9 39. PC series with liquid nitrogen for low temperatures) was also used. such as indium. H and N analyses were performed using a LECO CHNS-932 elemental analyzer.2 19. For longer reaction times (30 days) a black. ten days. A coupled TGeMS system was used to make an analysis of principal species evolved during the dynamic thermal decomposition of fragmentation processes of all the polymers samples. elemental analysis. in a similar way to the one described by Borquez et al. .1. In addition. between 150 and 500  C.

respectively. However.093 0. At these high temperatures the cleavage of the polymer chain can originate. and the samples lost a maximum of ca. are in good agreement with the DTA and DTG peaks found (the small differences are due to the technique considered). A more significant change due to thermal degradation takes place from the third peak.133 818 807 815 0. dW/dT. for the three samples are collected in Table 2. the first one around 260  C and the last one appears between 334 and 371  C. and it also happens on a large range of temperature with a plateau form. At the second stage.084 0.J. and a following broad peak (extended between 155 and 530  C) centred around 280  C. This second broad MS peak presents the same profile than the third major signal for m/z ¼ 16 (NHþ 2 ). The profiles for m/z ¼ 42 (NCOþ) and m/z ¼ 30 (NOþ) show the same tendencies due to their ion fragmentation.1 81. other significant components are released from the polymer such as: hydrogen cyanide. and continues with a main degradation at the last stage. obtained to the lowest reaction time. where the first endothermic peaks are clearly observed at 90 and 255  C. DTA curve for an HCN polymer sample. 50% of weight. thus for the sample 1. and finally one last shoulder around 810  C. reflect decomposition.103 0. Fig. which is attributed to OHþ or/and ammonia NHþ 3 . for example. with maximum rates of forming centred at 90  C (probably for OHþ). with a signal at m/z ¼ 17. 1b illustrates more clearly the small differences in the thermal decomposition behaviour of the three samples. 18. These DTG curves are shown in Fig. and formamide HCONH2. Polymer sample Tmax1 ( C) dW1/dT (wt%/ C) Tmax2 ( C) dW2/dT (wt%/ C) Tmax3 ( C) dW3/dT (wt%/ C) Tmax4 ( C) dW4/dT (wt%/ C) Tmax5 ( C) dW5/dT (wt%/ C) 1 2 3 68. probably resulted from the desertion of water and/or organic volatile material as it was mentioned before. 4 compares the ion current curve for the main thermal decomposition gases for an HCN polymer sample under study. 675 and 885  C. 1b. In this inert atmosphere major signals are observed in the range 50e550  C with an MS peak for H2Oþ (with m/z ¼ 18) that appeared at 85  C (these data coincide with loss observed on TG curves and DSC data).0102 0. the formation of NCeC^CHþ (m/z ¼ 51) and NCeCH]CHeþ (m/z ¼ 52) type structures. The temperatures of the DTG maxima with the corresponding rates of weight loss. In addition to the mentioned products. with a peak of maximum loss weight between 651 and 668  C. the char residue is another characteristic of these HCN polymers. the gaseous species can be mainly due to the tar cracking of the HCN polymer main chain. / Polymer Degradation and Stability 96 (2011) 943e948 945 peak at 80 is attributed to the evaporation of absorbed water.148 0. a mass loss of about 25 wt%. This last step is the major thermal decomposition stage. 43 and 45. dW/dT.0 78. The HCN evolution (thermal depolymerization) with m/z ¼ 26 for CNþ and 27 for HCNþ. DTG maxima with the corresponding rates of weight loss. The release of formamide is followed with the profile of m/z ¼ 45 and 44 (CONHþ 2 ).089 . As is shown in this figure. The second major signal corresponds with m/z ¼ 17. 13 and 12. 3 (as an example) presents the ion current for m/z detected in the MS versus temperature for the sample 2 (identical results were obtained for the other samples). Finally.085 0. the release of gases contributing to m/z ¼ 43. 27. 17 and 15% for the samples 1e3. Fig. HCN. with a very broad endotherm between 300 and 950  C. respectively (Table 1). The first derivatives of thermograms were calculated to highlight the inflection points that indicate thermal transitions. starts at 120  C and takes place over all the temperature range under study. observing TGeMS profiles for the m/z ¼ 51 and 52 and probably with ion fragmentations producing a signal on the profiles of m/ z ¼ 24. 2. at temperatures above 550  C.101 0.L. isocyanic acid and Table 2 Characteristic temperatures for the thermal decomposition of synthesized HCN black polymers in argon atmosphere. 3.126 0. At 1000  C.087 0. Heating rate was 10  C/min and the argon atmosphere. being equal to 13. Dynamic measurements were carried out in argon atmosphere. de la Fuente et al.083 334 368 371 0. This broad stage may therefore be rationalized to be a composite of two thermal events as described below. the intensity order of MS signal is m/z ¼ 18 (8.082 651 653 668 0. The three samples follow globally the same stages of pyrolysis. The final stage occurs between approximately 500 and 1000  C. The DSC thermograms of the samples run in nitrogen atmosphere. Fig. H2O and NH3. The DTA thermogram under argon of HCN polymer samples under study exhibits different stages according with the previous DTG analysis. where a deconvolution of one of these curves into an individual Gaussian peak has been made assuming a linear background over the temperature range of the fitting. as is shown in Fig. isocyanic acid HeN]C]O (or cyanic acid HeOeCN). associated to isocyanic acid (or cyanic acid). The shape of the main peaks of mass spectrometry resembles those of DTG curves. a double peak observed. ammonia. and the rest of the observed peaks. at 265. some small differences appear. begins at 150  C. where two peaks around 255 and 400  C can be observed.2.5$109) > 17 (2$109) > 27 (5$1010) > 43 (15$1012) > 45 (<1012).094 0.093 252 260 259 0. These profiles are very similar to those ion currents corresponding to Cþ and CHþ with m/z ¼ 12 and 13. On the other hand. its first three maxima decomposition rates take place at slightly lower temperatures than the polymer samples prepared with longer reaction times. Mass spectrometric thermal analysis Fig. This indicates the majority of thermal decomposable components in the HCN polymers can release H2O. The first DTG peak appears at 80  C. 2.1 0. The first and well defined endothermic MS coupled with TG system has been used to study volatile species of thermal decomposition and fragmentation processes for all HCN polymer samples obtained.

so that the last studies about the structure of this polymeric system. the recent work of Cataldo and co-worker [31]. On the other hand. where the major pyrolytic reaction products were identified as CO2.L. HCN. is consistent with the presence of amide groups in these HCN polymers. where these authors analyze HCN polymers obtained from thermal decomposition of formamide. 3. the pyrolytic formation of some of these products. and they find in their pyrolysis a large amount of gaseous HCN in a wide range of temperatures together with ammonia and isocyanic acid. and pyridine [32]. heating at 10  C/min in argon atmosphere. de la Fuente et al. as for example polyamides based on cyanoimidazoles as has been welldescribed by Thurber and Rasmussen [33]. On the other hand. propose a polyaminoimidazole as the main chain for HCN polymers [30].32]. CH3CN.31. On one hand. These results are in agreement with the scarce data of the literature concerning the thermal decomposition of the system under study [7. performed Mamajanov and Herzfeld and based on solid state NMR. such as formamide and isocyanic acid.946 J. Ion intensity curves for an HCN polymer sample. HCONH2. H2O. / Polymer Degradation and Stability 96 (2011) 943e948 Fig. the pioneering study of Ferris et al. The hydrophilic character of these HCN polymers demonstrated in this paper is also a feature of other well-known polymers. formamide. The presence . This fact is very relevant.

5a and b shows the TG and DTG curves. between 400 and 600  C (versus 500 and 1000  C in argon). which is now quite narrow. Heating rate was 10  C/ min and the oxygen atmosphere. 3. de la Fuente et al. until temperature around 400  C. Fig. urea could be one of these side products. where the HCN polymers present higher stability in argon than in an oxygen atmosphere at higher temperatures. therefore their thermal stability is not essentially influenced by the reaction time used in their syntheses. and in this case it appears at lower temperatures. it is unaffected by the change of the atmosphere. Fig. Therefore. At the second stage. however it is thermally unstable. Thus for example. (a) TG and (b) DTG curves for an HCN polymer sample. 540  C. 27. it is not observed in the presence of oxygen. but not decisive. This fact suggests that these peaks. it is very illustrative the clear change at the third decomposition stage. caused by the presence of water and/or volatile compounds is shifted to lower temperatures.35]. it is also important to note that pyrolysis of these HCN polymers releases gaseous hydrogen cyanide. However. do not arise from the thermally weak structures sensitive to oxidation. which correspond to the main pyrolysis stage. Besides.37]. isocyanic acid and formamide in a wide temperature range. it is noticeable the great difference observed from ca.J. Thus. Thus the presence of oxygen diminishes the stability of the macrostructure of the HCN polymer. they can simply be side products. The thermal degradation of . 5. DTA. the quantitative comparison of MS signals of different samples and components is not performed in this paper. some of these molecules (as well as other oligomers from them) could not be thermal decomposition products. the DTG maximum is observed around 660  C. Below this temperature the oxygen notably decreases the stability of the HCN polymers. The HCN polymers thermal-oxidative degradation has a different behaviour than in argon degradation. In this range of temperatures decompositionecarbonization reactions normally take place. and leads to intense thermo-oxidation processes. 42 and 44 for an HCN polymer sample. formed during the polymerization reaction. respectively. the TG analyses of all HCN polymers under oxidative atmosphere provide no residues. and characterized by FTIR and solid state NMR for a study of their thermal properties using different analytical techniques such as TG. However. heating at 10  C/min in argon atmosphere. It is also determined by different ionized energies of the distinct gas species. A detailed analysis of the curves allow us to conclude that the two first degradation stages. The first DTG peak. / Polymer Degradation and Stability 96 (2011) 943e948 947 Fig.3. 400  C. (a) DTG curve and (b) MS signal comparison of m/z ¼ 17.L. In an inert atmosphere. and now appears around 50  C in the thermo-oxidative degradation. are not apparently affected by the type of environment under study. The dW/dT values of this peak significantly increase under oxygen atmosphere. and trapped on the polymeric matrix. Conclusions Various samples of HCN polymers were synthesized from the reaction of equimolar amounts of NaCN and NH4Cl in water. It should be mentioned that the intensity of m/z signal in this technique is related to the amount of species. 4. the second of DTG peaks. which appear as a shoulder around 815  C in argon. 18. for an HCN polymer sample degraded in argon and oxygen environments from room temperature to 1000  C. The TG curves showed that the mass loss percentages for the decomposition were practically the same for each sample. where two separated DTG maxima under argon flux can be registered. forming ammonia and cyanic acid (or isocyanic acid) in a simple decomposition reaction [36. Effect of oxygen on the thermal decomposition The effect of the oxygen on the thermal degradation of the HCN polymers was also analyzed. 4. as this figure clearly shows. This means that the oxygen accelerated the mass loss of this polymer through oxidation. On the other hand. of secondary amide groups has been established by solid state NMR in HCN polymers obtained from equimolar amounts of H13CN and HC15N by Matthews and co-workers [34. DSC and TGeMS. In addition.

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