Thermal degradation of organic additives used in colloidal shaping of ceramics investigated by the coupled DTA/TG/MS analysis
Thermal degradation of organic additives used in colloidal shaping of ceramics investigated by the coupled DTA/TG/MS analysis
Paulina Wiecinska 0
0 Faculty of Chemistry, Warsaw University of Technology , 3 Noakowskiego St., 00-664 Warsaw , Poland
The paper presents the analysis of thermal decomposition of selected organic additives, which are commonly used in shaping of ceramic materials by colloidal methods. Shaping of ceramics requires using different additives which then are burned out during sintering process. For this reason, the knowledge about thermal degradation of organics used, as well as decomposition products, seems to be very important from the application point of view. The analyzed substances were as follows: diammonium hydrocitrate, citric acid, ammonium salt of acrylic polymer, L-ascorbic acid, N,N,N0,N0-tetramethylethylenediamine, and ammonium persulfate. The thermal analysis has been done on the apparatus coupled with mass spectrometer what allowed to observe what types of gasses are released to the atmosphere during heating. The obtained results showed important differences in thermal degradation of organic additives. It was possible to determine at what temperature regions harmful gases like N2O, NO2, or SO2 are released from the organics and which additives can be treated as environmentally friendly.
Fabrication of advanced ceramic materials requires the use
of various organic additives which facilitate shaping
process of non-plastic ceramic powders. The appropriate
& Paulina Wiecinska
selection of additives is especially important in case of
colloidal processing , in methods like: slip casting ,
gelcasting [3, 4], tape casting , and mechanical foaming
. The number of different organics needed in a shaping
process ranges from two to eight. The organic substances
can play the role of dispersing agents which stabilize
suspensions [7–9], binders which hold particles together ,
plasticizers which give elasticity , foaming agents
which allow to obtain porous materials , monomers
 together with activators  and initiators of
polymerization  which allow to create polymeric network
around non-plastic particles, etc. Organic additives are
subsequently burned out during sintering process. They are
indispensible in shaping step but must be then eliminated in
order to obtain pure ceramic phase . Organic
substances thermally decompose during heating, and as a
result different gases are released into the atmosphere.
Information about temperature range of organics
degradation is very useful in elaboration of sintering conditions,
such as heating rate or dwell time. Two violent releases of
gases from ceramic samples can lead to their deformation
or cracking. The very useful tools which allow to
determine the thermal degradation characteristics of substances
during decomposition are DTA/TG and DSC analyses
[17–20]. Additionally, coupling of the DTA apparatus with
mass spectrometer makes it possible to analyze type of
gases released to the atmosphere .
The author has chosen six organic additives, commonly
used in colloidal shaping of ceramics in order to examine
their behavior during thermal heating. The analyzed
substances were as follows: diammonium hydrocitrate, citric
acid, Dispex A-40 (ammonium salt of an acrylic polymer
in water), N,N,N0,N0-tetramethylethylenediamine,
L-ascorbic acid, and ammonium persulfate. In the previous paper,
thermal decomposition of selected organic monomers used
in gelcasting process was reported . This paper
develops the topic of thermal degradation of substances
commonly used in colloidal shaping of ceramics.
Materials and experimental procedure
Six organic substances have been chosen for the analysis.
The first three chemicals are commonly used as dispersing
agents which allow to obtain time-stable and low-viscosity
ceramic suspensions. The dispersants used were as follows:
diammonium hydrocitrate, citric acid, and Dispex A-40 (an
ammonium salt of an acrylic polymer in water.). The next
(TEMED) and L-ascorbic acid—are the activators of
radical polymerization, commonly used in shaping of ceramics
by gelcasting method. The last analyzed compound was
ammonium persulfate which is a water-soluble initiator of
radical polymerization, also used in gelcasting. The
chemical formulae of analyzed substances is shown in
DTA/TG measurements were carried out by using
Netzsch STA 449C coupled with quadrupole mass
spectrometer Netzsch QMS 403C. The heating rate was 5 C min-1,
and the final temperature was 1000 C. The measurements
were performed in the constant flow of two gases: argon—
10 mL min-1 (protective gas) and synthetic air (75:25
N2:O2)—60 mL min-1. The sample placed in the crucible
contained 300 mg of high-purity alpha alumina (TM-DAR
from Tamei Chemicals, Japan) and 15 mg of analyzed
organic additive. Alumina which was non-reactive during
heating prevented sticking of melted organics to crucible
walls. Mass spectrometer was set to detect certain m/z
values and is listed in Table 2. Value 100 % corresponds to the
main m/z value characteristic for a certain compound in the
mass spectrum. In order to confirm the presence of given
substance, the second m/z value had to be detected by the
spectrometer. The intensity of the second peak in the mass
spectrum is related to the main m/z value of the compound.
It is worth to mention that m/z values 14, 16, 32, although
useful in determination of the presence of ammonia or NOx,
have not been taken into consideration because they refer
also to N2 and O2, which constantly flow through the
apparatus. The analysis was performed in the oxidizing
atmosphere; therefore, the analyzed gases were the products
of complete oxidation. Ammonia was supposed to appear
during heating of TEMED and ammonium persulfate.
Results and discussion
Figure 1 presents DTA/TG/DTG curves of diammonium
hydrocitrate (DAC) thermal degradation. The total mass
loss was 100 % what indicates that the whole DAC has
decomposed, as expected. Mass loss is observed until ca.
659 C. DAC decomposition goes in few stages according
Table 1 Organic additives used in the research
Role in colloidal shaping
Citric acid (Sigma-Aldrich, anhydrous, C99.5 %)
Diammonium hydrocitrate (POCh, Poland, puriss)
Dispex A-40 (BASF)
L-ascorbic acid (Sigma-Aldrich, reagent grade)
N,N,N0,N0-tetramethylethylenediamine, TEMED (Fluka, [98 %)
Ammonium persulfate (Sigma-Aldrich, C98 %)
Table 2 m/z values and their intensities for the analyzed gases
to TG curve. Two peaks are visible on DTA curve, the
endothermic peak with the minimum at 185 C and the
wide exothermic peak with the maximum at 542 C. More
information of MS curves is shown in Fig. 2. Course of
curves of m/z values 17 and 18 is similar what indicates
that they correspond to H2O. There is one maximum on MS
18 at 189 C which overlap with endothermic peak on
DTA at 185 C, what indicates on dehydration process.
The presence of CO2 is confirmed by m/z values 12 and 44.
There is the increase in the intensities of MS 44 and 12
signals with the maxima at 217 and 552 C, what indicates
on the decomposition of citrate ion. MS signals 30 and 46
correspond to NO2; here again two maxima at temperatures
188 and 548 C are observed. They indicate the oxidation
of ammonium groups to NO2. The maxima on MS 44 and
30 overlap with the maximum on DTA curve and is
connected with 31 % mass loss. Hence, degradation of
diammonium hydrocitrate proceeds in two main steps and
ends at ca. 659 C. The main products of decomposition in
the oxidizing atmosphere are: H2O, CO2 and NO2.
Figure 3 shows DTA/TG/DTG curves of citric acid
(CA) thermal degradation. The total mass loss was 100 %
TEMED 58 (100 %) 42 (7 %)
what indicates that the whole CA has decomposed. Mass
loss is observed until ca. 501 C, and therefore,
decomposition of CA ends 158 C lower than DAC. Two main
stages of CA degradation are observed; the first stage till
233 C connected with 81 % mass loss and the second
stage till 501 C with 19 % mass loss. The first stage of
decomposition is connected with high increase in
intensities of all MS signals, that is 12, 17, 18, and 44 which
corresponds to H2O and CO2 (Fig. 4). The first peak on MS
18 is wider than on MS 44 what together with the
endothermic peak on DTA with the minimum at 162 C
can be ascribed to the dehydration process and partial
decomposition of hydrocarbon chain. The next DTA
endothermic peak with the minimum at 213 C can be the
result of the overlap of two effects: further dehydration
(what indicate MS 17 and 18) and decomposition of
hydrocarbon chain with the release of CO2 (what indicate
MS 12 and 44). Then, further degradation of chain
proceeds what is observed as a wide exothermic peak on DTA
with the maximum at 458 C, a small peak on MS 18 with
the maximum at 361 C and two peaks of smaller
intensities on MS 44 with maxima at 370 and 452 C.
Fig. 1 DTA/TG/DTG curves of diammonium hydrocitrate
Fig. 2 MS analysis of diammonium hydrocitrate during heating
Fig. 3 DTA/TG/DTG of citric acid
Comparing the obtained results with the available
literature, it can be underlined that the decomposition of citric
acid is not a single-step process. The measurements
performed in argon atmosphere allowed Wyrzykowski et al.
 to propose the thermal transformation pattern of the
citric acid showing the intermediate products, such as
trans-aconitic acid and citraconic anhydride. It was
summarized that thermal decomposition is a complex
process leading through dehydration and decarboxylation.
Reda  examined the thermal stability of selected
antioxidants, including citric acid and ascorbic acid. His
measurements were performed under the following
conditions: heating rate of 20 C min-1 in an atmosphere of
synthetic air, flow of 70 mL min-1 at a temperature range
361.0 °C 369.7 °C
Fig. 4 MS analysis of citric acid during heating
of 25–600 C. According to his measurements,
decomposition of citric acid starts above 160 C, culminating at
around 220 C, what is in a good agreement with the
results presented in this paper. Moreover, in case of
ascorbic acid, decomposition of the antioxidant starts at
around 190 C what again is the similar result to that
obtained within the measurements described below.
Thermal analysis of citric acid degradation gives the
important information that the main step of decomposition
which is connected with the release of high quantities of
gases goes till ca. 233 C. For this reason, it is preferable to
conduct the sintering process of ceramic samples prepared
with the use of citric acid with a low heating rate (for
example 1 C min-1) at low temperatures. Too fast heating
till 233 C may result in rapid release of cumulated gases
and therefore crack appearance in the ceramic body.
Sintering of ceramic samples at different heating rates has
been already examined by author; the obtained results
showed that heating rate equaling 5 C min-1 resulted in
the creation of pores in the sample, what was observed on
the SEM images .
Figure 5 shows DTA/TG/DTG curves of thermal
degradation of an ammonium salt of an acrylic polymer in
water (Dispex A-40). The total mass loss was 99 % what
indicates that the whole Dispex A-40 has decomposed.
Mass loss is observed until ca. 599 C. Several stages of
Dispex degradation are observed. The first stage till 131 C
is connected with 56 % mass loss, and then two stages till
187 and 291 C with ca. 6 % mass loss are observed. The
last two stages of thermal decomposition till temperatures
392 and 599 C are connected with 14 and 16 % mass loss,
respectively. The first stage of decomposition is connected
with DTA endothermic peak with the minimum at 118 C
and MS signals 17, 18 (H2O) and 12, 44 (CO2) (Fig. 6).
The assumption that CO2 not N2O is released at this stage
of decomposition is based on the fact that there is a visible
peak on MS 12, while MS 30 curve is flat. The increase in
MS 30 signal is observed at 160 C, but the presence of MS
46 signal indicates that NO2 is released at higher
temperatures. It must be also mentioned that in case of ammonium
salt of an acrylic polymer, ammonia is released from the
compound at low temperatures, and for this reason, mass
loss on TG curve is observed from the very beginning of
the analysis. As explained later for ammonium persulfate
decomposition, it is difficult to distinguish NH3 in the
conditions of the measurement. At temperature 196 C, the
peaks on MS curves 18 and 17 accompanied by 6 % mass
loss are observed what can be ascribed to dehydration of
the sample. The next decomposition stages are connected
with two exothermic peaks on DTA at 379 and 540 C,
accompanied by the increase in MS signals 12, 18, 30, 44,
and 46. This indicates that during decomposition of Dispex
A-40 at temperature range 291–599 C, H2O, CO2, and
NO2 are released to the atmosphere. The stepped mass loss
and the presence of a few maxima on MS curves indicate
that thermal decomposition of the polymeric chains
proceeds gradually. According to the literature, in case of
thermal degradation of acrylic polymers in nitrogen
atmosphere, the major decomposition products comes from
main chain scission, giving monomers, dimers, saturated
Fig. 5 DTA/TG/DTG of dispex A-40
Fig. 6 MS analysis of dispex A-40 during heating
diesters, and trimers. The light products of decomposition
include also carbon dioxide and water . In case of the
research carried out in air atmosphere, the oxidation of
intermediate products proceeds and light gases are
The most commonly used system for initiating of
polymerization reaction in ceramic technology is a redox
system. It is based on two substances, activator (catalyst)
and initiator, where due to redox reaction free radicals are
created which initiate the polymerization process. In
scientific literature, the most commonly used redox system in
ceramic processing is
N,N,N0,N0-tetramethylethylenediamine (TEMED) and ammonium persulfate (APS) [26, 27].
Nevertheless, there appears information concerning the use
of L-ascorbic acid (L-AA) instead of harmful TEMED .
For these reasons, the presented below diagrams concern
the thermal analysis of TEMED, L-AA and APS
decomposition. The TG curve presented in Fig. 7 indicates that
the total degradation of TEMED proceeds till 135 C, and
the mass loss begins at room temperature. The degradation
is connected with the release of several gaseous products
which have been detected by mass spectrometer (Fig. 8).
There is only one peak visible on each MS curve at
temperature ca. 131 C. The m/z values detected by mass
spectrometer are as follows: 17, 18 (H2O), 12, 44 (CO2),
30, 46 (NO2), and 58, 42 (TEMED). MS 58 and 42 may
indicate on the release of TEMED vapors. Moreover, m/
z 17 can correspond to NH3, but as in the case of DAC and
APS, the confirmation of this statement is not obvious in
the conditions of the measurement. The analysis showed
that thermal decomposition of TEMED is the one-stage
rapid process connected with the release of high amounts
of gaseous products. This information is very important
from technological point of view because during both
polymerization and drying of ceramic samples, TEMED
can begin to decompose at temperatures below 100 C.
Figure 9 shows DTA/TG/DTG curves of L-ascorbic acid
(L-AA) thermal degradation. The total mass loss was
100 % what as in case of previous substances indicates that
the whole acid has decomposed. Mass loss is observed until
ca. 574 C. Three main stages of L-AA degradation are
observed; the first stage till 232 C connected with 32 %
mass loss, the second stage till 346 C with 28 % mass
loss, and the third stage till 574 C with 40 % mass loss.
Fig. 7 DTA/TG/DTG of N,N,N0,N0-tetramethylethylenediamine
The highest intensities of MS signals (of m/z values 12, 17,
18 and 44) are observed in temperature range 217–221 C
and are connected with the DTA endothermic peak at
202 C (Fig. 10). This can indicate on dehydration process
and partial decomposition of the compound. Then the
intensities of MS signals slightly decrease, but still H2O
and CO2 are released from the sample. Two exothermic
maxima can be observed at 343 C (MS 18 and 44) and at
504 C (MS 44). The course of DTA curve overlap with
the MS 12 and 44 curves in temperature range 232–574 C
what indicates the gradual decomposition of ring and
aliphatic substituent. It is worth to compare the products of
thermal degradation of two activators of polymerization,
which are TEMED and L-AA. Due to the chemical
constitution of TEMED, NO2 and probably ammonia are
released during its burnout, while L-AA is environmentally
friendly compound, and only CO2 and H2O are the gaseous
products which go to the atmosphere.
The last analyzed compound was ammonium persulfate
(APS). Plots of DTA/TG/DTG and MS are presented in
Figs. 11 and 12. Here, thermal degradation is a much more
complicated process than in case of previous substances.
The total mass loss was 99 % what indicates that the whole
salt has decomposed. However, mass loss is observed till
920 C, which is ca. 400 C higher than in case of other
analyzed compounds. The thermally activated
decomposition of persulfate ion leads to the formation of sulfate
radical ion , which then can be oxidized to SO2, as
shown on MS spectra. In parallel, ammonia may be
released at lower temperatures, but then oxidation process
Fig. 8 MS analysis of N,N,N0,N0-tetramethylethylenediamine during heating
Fig. 9 DTA/TG/DTG of L-ascorbic acid
begins and as a result NO2 appears. At the beginning, three
decomposition steps, accompanied by a small mass loss,
are observed. The first stage till 202 C with 7 % mass loss
is connected with DTA exothermic peak. In this
temperature region, MS signals of m/z values 44 and 30 are
observed (maxima at 192 and 223 C). In case of APS,
m/z value 44 may correspond to N2O. The second
characteristic mass for nitrogen monoxide is 30, but this mass
corresponds also to NO2. It is therefore probable that N2O
is the product of thermal degradation of APS, but in air
atmosphere, it oxidizes to NO2. No peaks on MS 18 are
observed in this temperature. The little peak on MS 18 at
99 C can be ascribed to moisture evaporation from the
sample. The second stage of APS decomposition till
304 C with 3 % mass loss is also connected with DTA
exothermic peak, but here mass spectrometer detected m/
Fig. 10 MS analysis of L-ascorbic acid during heating
Fig. 11 DTA/TG/DTG of ammonium persulfate
z values 18, 44, and 30 which can be ascribed to H2O, N2O,
and NO2. The third stage of APS degradation till 369 C
with 9 % mass loss is connected with DTA endothermic
peak. According to mass spectrometer, H2O and NO2 seem
to be the dominant gases, while concentration of N2O is
smaller. It must be noticed that MS signal 17 in this region
has slightly higher intensity than MS 18. It might mean that
NH3 is released; nevertheless, it is difficult to confirm it in
these measurement conditions. The second characteristic
m/z value for ammonia is 16, but this is also the m/z of O2,
and the flow of air was 60 mL min-1. It means that the
intensity of MS 16 is about two orders of magnitude higher
than MS 17 or 18, what makes it impossible to distinguish
any changes on MS 16 connected with eventual release of
Fig. 12 MS analysis of ammonium persulfate during heating
501.0 °C 574.0 °C
Fig. 13 TG curves of all investigated substances
NH3. Running the experiment in non-oxidizing atmosphere
would lead to completely different decomposition
mechanism, and different gaseous products would be released,
what might be very interesting form scientific point of view
but non-applicable in case of conventional sintering of
ceramics. The next decomposition stage appears in
temperature 545 C with 25 % mass loss. Here, the intensities
of many MS signals are increased: 12, 17, 18, 30, 46, 48,
and 64, what can be ascribed to the following gases: H2O
(and HN3), N2O, NO2, and SO2. The dominant gaseous
product is SO2. The increase in the temperature till 920 C
results in the decrease in most of the gaseous products, but
the presence of SO2 is still observed which means that
oxidation of sulfate ions present in APS requires high
energy. According to TG, the mass loss within temperature
range 575–1000 C is 56 %. It means that the main
degradation stage occurs at high temperature. This is again
the very important information in case of sintering of
ceramic samples prepared with the use of APS. It seems
that in case of ceramic samples prepared with the use of
APS, heating rate should be low till 920 C in order to
avoid cracks. In fact, the quantities of APS used in
colloidal shaping of ceramics usually amount to
0.01–0.3 mass% with respect to ceramic powder. For this
reason, the risk that cracks would appear as a result of the
release of high amounts of gases during APS
decomposition is small. Therefore, sintering conditions for samples
containing APS should be matched individually depending
on shaping method and APS concentration. Finally, it
seems that gaseous products released to the atmosphere
during thermal degradation of APS are the most harmful in
comparison with other analyzed substances. On the other
hand, APS is not as irritant as for example TEMED. It must
be then summarized that both toxicity of a compound and
its thermal decomposition should be taken into account
when environmental aspects are concerned.
Figure 13 presents cumulative diagram of TG curves of
all investigated substances. It can be concluded that the
fastest thermal decomposition was observed for TEMED.
Nevertheless, both TEMED and Dispex A-40 has begun to
decompose at room temperature. The other four substances
required raised temperature in order to start to decompose.
Diammonioum hydrocitrate starts to decompose at 168 C,
but the process ends at 659 C which means that among
investigated substances, DAC is the second, after
ammonium persulfate, long-degradable substance. Citric acid
decomposes quite fast, in temperature range 177–501 C.
L-ascorbic acid remains stable till 197 C, and its thermal
decompositions ends at 574 C. The longest and the most
complicated thermal degradation was observed for
ammonium persulfate; TG curve indicates mass loss till
Thermal decomposition of six selected organic additives,
which are commonly used in shaping of ceramic materials
by colloidal methods have been performed. Three
dispersing agents, two activators, and one initiator of radical
polymerization have been analyzed. The fastest thermal
decomposition was observed for TEMED (activator of
polymerization). The process has begun at room
temperature and ended at 135 C. According to MS analysis,
decomposition was followed by the release of H2O, CO2,
NO2, and probably NH3. The multi-step thermal
decomposition process was observed for ammonium persulfate
with the release of H2O, N2O, NO2 and SO2. The most
environmentally friendly substances in terms of gases
released to the atmosphere were citric and L-ascorbic acids.
Here, the mass spectrometer has detected m/z values only
for H2O and CO2. Thus, the couple of DTA/TG with mass
spectrometry is a very useful tool for analysis of thermal
decomposition of different substances.
Acknowledgements This work has been financially supported by
the National Science Centre of Poland (Grant No. 2014/15/D/ST5/
Open Access This article is distributed under the terms of the
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