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Energy
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Procedia120 (2017) 000–000
00 (2017) 417–423
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INFUB - 11th European Conference on Industrial Furnaces and Boilers, INFUB-11
INFUB - 11th European Conference on Industrial Furnaces and Boilers, INFUB-11
Investigations on container materials in high temperature
Investigations on container materials in high temperature
The 15th Internationalmicrowave Symposium applications
on District Heating and Cooling
microwave applications
Ralph Behrend
Assessing
a*
, Corina Dorn
the feasibility
a
, Volkerthe
of ausing Uhlig a
heat, Hartmut Krauseaa
demand-outdoor
Ralph Behrend a*
, Corina Dorn , Volker Uhlig a
, Hartmut Krause
temperature function for a long-term district heat demand forecast
TU Bergakademie Freiberg, Institute of Thermal Engineering, Gustav Zeuner-Straße 7, 09599 Freiberg
a

TU Bergakademie Freiberg, Institute of Thermal Engineering, Gustav Zeuner-Straße 7, 09599 Freiberg

a

Abstract I. Andrića,b,c*, A. Pinaa, P. Ferrãoa, J. Fournierb., B. Lacarrièrec, O. Le Correc

Abstract
a
Microwave heating
IN+ Center is a promising
for Innovation, technology
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and Policy temperature
Research - Institutomaterials
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Técnico, Av. Rovisco Pais 1,melting
1049-001 ofLisbon,
oxidic Portugal
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Microwave
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This paperproperties
comparesare themicrowave
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refractory as well
materials for asuse
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in microwave melting
stability.
applications Thiswith paper compares
a focus on boron thenitride.
suitability of some widely available refractory materials for use in microwave melting
applications with a focus on boron nitride.
Abstract
© 2017 The Authors. Published by Elsevier Ltd.
© 2017 The Authors. Published by Elsevier Ltd.
© 2017 The Authors.
Peer-review under Published by
responsibility of Elsevier Ltd. committee of INFUB-11.
Peer-review
District heatingundernetworks
responsibility of the
the organizing
are commonly organizing
addressedcommittee of INFUB-11
in the literature as one of the most effective solutions for decreasing the
Peer-review under responsibility of the organizing committee of INFUB-11.
greenhouse gas emissions from the building sector. These systems require high investments which are returned through the heat
Keywords: microwaves; high temperature; melting; refractory materials
sales. Due
Keywords: to the changed
microwaves; climate melting;
high temperature; conditions and building
refractory materials renovation policies, heat demand in the future could decrease,
prolonging the investment return period.
The main scope of this paper is to assess the feasibility of using the heat demand – outdoor temperature function for heat demand
1. Introduction
1.forecast. The district of Alvalade, located in Lisbon (Portugal), was used as a case study. The district is consisted of 665
Introduction
buildings that vary in both construction period and typology. Three weather scenarios (low, medium, high) and three district
The advantages
renovation scenariosofwere microwave
developedheating
(shallow, areintermediate,
very well known deep). To andestimate
result from the manner
the error, obtained of heatmaterial
demandheating by
values were
The
microwaves.advantagesThe of
main microwave
advantages heating
are rapidare very
and well
uniform known
heating. and result
Since
compared with results from a dynamic heat demand model, previously developed and validated by the authors. from
energy the
is manner
converted of material
rather than heating
transferred,by
microwaves.
heating rates The
as main
high as advantages
400 K/min are
are rapid
possible.and uniform
This resultsheating.
in Since
reduced energy
processing is converted
time
The results showed that when only weather change is considered, the margin of error could be acceptable for some applications and rather
decreased than transferred,
energy losses
heating
within
(the error rates
the in as highSome
process.
annual as 400
demand K/min
studies
was also
lower arethan
possible.
report20% This
improved
for all results
mechanical
weather inscenarios
reduced processing
properties time and
and lowered
considered). However, decreased
reaction
after energy
temperatures
introducing losses
[1].
renovation
within
Highthe
scenarios, process.
heating
the error Some
rates
value studies
becomealso
mayincreased up toreport
59.5%improved
problematic, mechanical
when materials
(depending properties
involved
on the weather and andable
lowered
arerenovation
not to reaction
withstand
scenarios temperatures
thermal
combination shocks.[1].
In
considered).
TheHigh
sintering heating
value orofceramicrates
slope may become
coefficient
burning, the problematic,
increased
heated on bodies
averagewhen materials
within
have totheendure involved
range of 3.8%
the areupnot
thermal able
toshock.
8% pertoFor
withstand
decade,
melting thermal
that shocks.
corresponds
applications, In
tothe
the
sintering
decrease in
refractory or ceramic
the
materialsnumber burning,
used of for thethe
heating heated
hours
container bodies
of 22-139h
have have
to during
toleratetothethermal
endure
heatingthe thermal
season
shock shock.onFor
as(depending
well. the melting
combination applications,
of weathertheand
renovationmaterials
refractory scenarios used considered).
for the On the other
container havehand, function thermal
to tolerate interceptshock
increased for 7.8-12.7% per decade (depending on the
as well.
coupled scenarios). The values suggested could be used to modify the function parameters for the scenarios considered, and
improve the accuracy of heat demand estimations.
* Corresponding author. Tel.: +49 3131 39-4341; fax: +49 3731 39-3942.
* E-mail
Corresponding
address:author. Tel.: +49 3131 39-4341; fax: +49 3731 39-3942.
ralph.behrend@iwtt.tu-freiberg.de
© E-mail
2017 The Authors.
address: Published by Elsevier Ltd.
ralph.behrend@iwtt.tu-freiberg.de
Peer-review under responsibility of the Scientific Committee of The 15th International Symposium on District Heating and
Cooling.

1876-6102
Keywords:©Heat
2017demand;
The Authors. Published
Forecast; bychange
Climate Elsevier Ltd.
1876-6102
Peer-review©under
2017responsibility
The Authors. of
Published by Elsevier
the organizing Ltd. of INFUB-11.
committee
Peer-review under responsibility of the organizing committee of INFUB-11.

1876-6102 © 2017 The Authors. Published by Elsevier Ltd.

Peer-review under responsibility of the Scientific Committee of The 15th International Symposium on District Heating and Cooling.
1876-6102 © 2017 The Authors. Published by Elsevier Ltd.
Peer-review under responsibility of the organizing committee of INFUB-11
10.1016/j.egypro.2017.07.191
418
2 Ralph Ralph Behrend
Behrend et al. / Energy
et al./ Energy Procedia
Procedia 120000–000
00 (2017) (2017) 417–423

Nomenclature

εr relative permittivity
εr’ permittivity
εr’’ loss factor
ε0 vacuum permittivity
λ0 wavelength in vacuum
Dp penetration depth
E electric field strength
f frequency
V volume

Generally, there are two ways to design a microwave heating process: Heating the material directly or heating a
susceptor that heats the material to be processed. This paper focuses on the identification of affordable container
materials with suitable properties for direct melting with microwaves.
Nowadays, several research groups are working on microwave heated melting furnaces for oxidic materials and
even metals [1, 2]. Microwaves are electromagnetic waves with frequencies between 300 MHz and 300 GHz. For
most heating applications, the ISM-frequencies (Industrial, Scientific and Medical) around 915 MHz, 2.45 GHz and
5.8 GHz are used. The 915 MHz and the 2.45 GHz ranges are preferred for applications with high power demand [1].
The dielectric properties of a material, especially the relative permittivity εr determine how well microwaves can
heat the material. Relative permittivity is a complex number and is usually written as

 r   r   r, (1)

where the real part describes the ability of a material to store an electromagnetic field and the imaginary part
describes the ability to convert energy to heat. The imaginary part is often referred to as loss factor. Permittivity is a
function of frequency and temperature. Minor impurities affect the permittivity of a material. Depending on the
material and the impurities, this effect may reach an order of magnitudes. Materials with very low loss factors are
called “microwave transparent” [3].
For engineering purposes, two aspects are of paramount importance: Transferred power to the goods P and the
penetration depth Dp. P can be calculated using the dielectric heating equation [3]:

P  2f r 0 E V
2
(2)

where f is frequency, ε0 is vacuum permittivity, E is electric field strength and V is the volume of the heated body.
The penetration depth is defined as the point where the power flux in the material reaches 1/e of its surface value. It
can be calculated by
0 1
Dp  
2  2 r  2 0, 5
   r   (3)
1      1
   r  


where λ0 is the wavelength in vacuum [3].

1.1. Melting oxidic materials with microwaves

Directly resulting from Eq. (2) and (3), microwave melting processes require a container material that is microwave
transparent. Another property needed is high thermal shock resistance – in laboratory trials heating rates as high as 36
K/s have been observed. Due to the formation possibility of hot spots during melting, these temperature increases
occur locally, thereby increasing the stress on the refractory.
 Ralph Behrend et al. / Energy Procedia 120 (2017) 417–423 419
Ralph Behrend et al./ Energy Procedia 00 (2017) 000–000 3

Furthermore, the material needs to be chemically stable and resistant against abrasion and should not be infiltrated
by the melt. Considering a glass melting process, the material has to be stable for temperatures up to 1400 °C and
withstand the corrosive behavior of glass melt. Additionally, if a continuous process is considered, the refractory has
to withstand the highly abrasive behavior of a high viscosity fluid and a three-phase boundary.

1.2. Microwave transparent materials

For engineering microwave applications, a variety of microwave transparent materials are known. Common
materials are PTFE (Polytetrafluoroethylene), alumina based ceramics, corundum or fused quartz.
PTFE has many advantages in microwave applications, mainly because of its very low loss factor and easy
machinability. It is, however, very dangerous to use in high temperature applications. Fused quartz or borosilicate
glasses are also very common microwave-suited refractory materials. High purity fused quartz is even practicable for
high temperature applications, owing to the high melting temperature. However, a SiO2 based container material will
be dissolved quickly in molten glass.
Alumina based ceramics and especially corundum are stable at high temperatures, chemically inert and exhibit very
good microwave transparency. Their resistance to thermal shock is generally considered to be sufficient.
Boron nitride and silicon nitride are not so common materials for microwave applications. Both exhibit a very good
transparency to microwaves, a very good thermal shock resistance and high chemical stability.
Since PTFE and fused quartz should be disregarded in microwave melting applications, the following sections
compare corundum and boron nitride.

2. Experimental setup

Two sets of experiments were conducted. Tubes made from corundum and hot pressed boron nitride were heated
in a conventional furnace and then quenched in water to study thermal shock resistance. A second set of tubes was
used to melt oxidic materials in a microwave heated smelter.
The tubes were heated with a rate of 200 K/h to temperatures ranging from 600 °C to 1600 °C. The tubes were
then removed from the furnace and put into water with a temperature of about 20 °C. After cooling, they were visually
examined in order to detect cracks and other surface changes. Tubes were treated with ink in order to make cracks
more visible. Diameter and wall thickness were measured using a caliper. All tubes have been weighted in order to
detect mass loss. The properties of the tubes used for thermal shock experiments are noted in Table 1.

Table 1: Properties of tubes used for thermal shock experiments

Tube properties Corundum Boron nitride

Outer diameter 40 mm 40 mm
Wall thickness 4 mm 3 mm
Length 112 mm 110 mm
Initial mass 203,48 g 80,5 g

Table 2: Properties of tubes used for melting experiments

Tube properties Corundum Boron nitride

Outer diameter 50 mm 54 mm
Wall thickness 4 mm 3 mm
Length 120 mm 120 mm
420 Ralph Behrend et al. / Energy Procedia 120 (2017) 417–423
4 Ralph Behrend et al./ Energy Procedia 00 (2017) 000–000

For the melting application the tubes have been installed in a mono mode cavity and insulated from the cavity walls
by high temperature insulation wool with high alumina content. The tubes were then filled with raw material and
heated by microwave. Microwave power was then increased stepwise from 500 W up to 3000 W or until melting
occurred.
The tubes were afterwards inspected visually and cleaned. Diameter and wall thickness were measured by caliper.
Tube mass could not be measured, since molten material remained at the tube walls. Properties of tubes used for
melting experiments are recorded in Table 2.
The dielectric properties of boron nitride were measured using a cavity perturbation approach described
elsewhere [4].

3. Results and assessment

Figure 2 shows the boron nitride tubes after heating to a designated temperature and quenching in water. It is clearly
visible that no cracks were induced at all tested temperatures. However, for temperatures above 900 °C (Figure 2 c),
d), e)) the surface of the tubes displayed tiny bubbles of a hard substance. It can easily be seen that bubbles increase
in size and decrease in number with higher temperatures. At 1600 °C, the bubbles seem to diminish and a serious
degradation of the tube surface was observed (Figure 2, f)). This coincides with a higher mass loss.
Table 3 shows the changes in diameter and wall thickness after heating. Clearly, diameter and wall thickness are
not measurably influenced by temperatures up to 1400 °C. However, an increasing mass loss can be noted for
temperatures above 900 °C.
Figure 1 shows a corundum tube after heating to 1000 °C and quenching in water. Cracks of varying size and length
can be seen all over the surface. However, the tube itself was intact. Even higher temperature gradients before
quenching would not lead to a complete failure of tube integrity. For corundum tubes, no mass loss or shrinkage was
measured, as expected.
Experiments with the melting setup using corundum tubes were not successful. With the exception of a minority
of samples all tubes revealed large cracks and leakage of molten material. Figure 1 illustrates a typical case. Note that
compared to the left hand side the cracks are larger and less branched. The tube is held together by the solidified glass
and is structurally defect.

Table 3: Diameter, wall thickness and mass loss of bornon nitride tubes after heating and quenching

Temperature [°C] Diameter [mm] Wall thickness [mm] Mass loss[%]

900 40.0 3.0 0
1000 40.0 3.0 1.41
1100 40.0 3.0 2.18
1400 40.0 3.0 5.78
1600 39.3 2.4 17.86

a b

Fig. 1. (a) Corundum tube after heating to 1000 °C and quenching; (b) Cracks in a corundum tube after microwave heated melting.
 Ralph Behrend et al./ Energy Procedia 00 (2017) 000–000 5
Ralph Behrend et al. / Energy Procedia 120 (2017) 417–423 421

Fig. 2. Pictures of boron nitride tubes after heating with 200 K/h temperature ramp and 20-minute soak time and quenching in water at room
temperature. (a) 20 °C; (b) 900 °C; (c) 1000 °C; (d) 1100 °C; (e) 1400 °C; (f) 1600°C

Experiments with boron nitride were more successful, Figure 3 shows boron nitride tubes after one and several
melting campaigns. Subfigure b) shares the part of the tube that is closest to the magnetron. Effects of high temperature
similar to Figure 2 d) are clearly visible. The degradation effects shown in Figure 2 are also visible in subfigures c)
and d) of Figure 3. Note that the scratch marks were caused during removal of the tube from the cavity.
In order to verify that the effects of higher temperature on boron nitride are not connected to heating effects in the
container material itself the dielectric properties of boron nitride were measured. Samples of material identical to the
tube material were obtained and measured. The results are shown in Figure 4. It is clearly visible that after an increase
between 500 °C and 700 °C the dielectric properties do not change much at higher temperatures and the loss factor
remains relatively low, compared to the heated material inside of the tube. This is consistent with the data shown by
Westphal and Sils [5]. However, the data shown there indicate that binding agents strongly influence the dielectric
behavior of boron nitride. Therefore, materials with low content of binding agents perform better
422 Ralph Behrend et al. / Energy Procedia 120 (2017) 417–423
6 Ralph Behrend et al./ Energy Procedia 00 (2017) 000–000

Fig. 3. Boron nitride tubes after one and after several melting campaigns. (a) one melting campaign, cold side; (b) one melting campaign,
magnetron side; (c) several melting campaigns, cold site; (d) several melting campaigns, magnetron side.

Fig. 4. Dielectric properties of hot pressed boron nitride samples similar to tube materials

Literature data for dielectric properties of corundum [5] show a steep increase in loss factor and therefore energy
absorption for corundum when exceeding temperatures of 800 °C. This might explain the discrepancy between thermal
shock experiments and melting experiments. Corundum tubes with higher purity or other modifications of Al2O3 might
perform better, as indicated by literature data.

4. Conclusion

Most conventional microwave transparent materials are unsuitable for high temperature melting applications.
Special requirements such as microwave transparency, chemical and mechanical stability and thermal shock resistance
reduce the list of available materials to a few high-performance ceramics. Economic concerns have to be taken into
 Ralph Behrend et al. / Energy Procedia 120 (2017) 417–423 423
Ralph Behrend et al./ Energy Procedia 00 (2017) 000–000 7

account when choosing such materials and the more expensive alternatives have to have a significant advantage over
the cheaper ones.
Within this paper, corundum and hot pressed boron nitride were assessed as possible container materials for high
temperature microwave melting of oxidic materials. Experiments assessing the thermal shock resistance of both
materials were carried out. Furthermore, both materials were tested under real microwave heated melting conditions.
Dielectric parameters of both materials were compared through own measurements and literature data in order to
validate and explain the differences between measured thermal shock resistance and the melting trials.
It was shown that corundum demonstrates superior performance under oxidizing conditions, while hot pressed
boron nitride starts to degrade at temperatures above 1000 °C. While this effect is not critical for temperatures below
1100 °C, the degradation effects become critical at temperatures of about 1600 °C.
However, while the measured thermal shock resistance of corundum seemed sufficient from the tests, it proved
insufficient under real microwave melting conditions. Boron nitride exhibited no cracks, but the degradation effects
already observed in the thermal shock experiments were observed again. Nevertheless, it was still possible to reuse
one boron nitride tube several times for melting, while corundum tubes were destroyed.
From our experiments, we conclude that hot pressed boron nitride is a cost efficient alternative to more expensive
materials like pyrolytic boron nitride or silicon nitride. Further research should investigate the long term stability of
hot pressed boron nitride and ways of increasing the lifetime of such tubes. Furthermore, other alternatives such as
aluminium nitride need to be investigated.

Acknowledgement

This work was supported by the project DAPhNE (Development of adaptive ProductioN systems for Eco-efficient
firing processes). The project has received funding from the European Union Seventh Framework Programme
(FP7/2007-2013) under grant agreement n° 314636.

References

[1] Agrawal D. Microwave processing of ceramics. Current Opinion in Solid State & Materials Science 1998; 3:480-485
[2 Hara K, Hayashi M, Sato M, Nagata K. Continuous pig iron making by microwave heating with 12.5 kW at 2.45 GHz. Journal of Microwave
Power and Electromagnetic Energy 2011; 45(3):137-147
[3] Meredith R. Engineers’ Handbook of industrial microwave heating. London: The institution of electrical engineers; 1998
[4] Hahn S; Dornich K; Reichmann M; Walter G. Contactless Measurement of the Dielectric Parameters of Ceramic Materials for Microwave
Processing. Ceramic Forum International 2010; 87(5):E43-46
[5] Westphal W, Sils A. Dielectric Constant and Loss Data, Technical Report AFML-TR-72-39. National Technical Information Service; 1972