Microwave synthesis

DARIUSZ BOGDAL
ALEKSANDER PROCIAK

Microwave synthesis
of polymeric materials
Scale up and commercial aspects
ABSTRACT processing, including improved product uniformity,
reduced extrusion-line length, reduced scrap, and
Polymer technology forms one of the largest areas of improved cleanliness and environmental sustainability
application of microwave technology, and the methods compared with steam autoclaves, hot air, slat batch, or
and procedures used therein are among the most fluid bed heating processes (9).
developed in chemistry. The purpose of the paper is to In the seventies, the technology of microwave heat-drawing
provide a brief story of the application of microwaves in was developed for the manufacture of high-modulus
polymer processing together with some considerations of polymeric materials. Many other applications of microwave
commercial aspects, which can divided into two heating were introduced including the rapid bonding of
segments i.e. industrial applications and instruments for polymeric films, sheets, and various components, fast
laboratory uses. curing of thermosettings resins. While in eighties
microwave technology revealed almost simultaneously in
polymer and organic chemistry an outstanding potential to
INTRODUCTION cause strong acceleration and/or selective promotion of a
number of chemical processes (10).
Microwave processing of materials is a relatively new Recently, microwave technology applied to polymer
technology that provides novel approaches for enhancing processing, and particularly to the polymerization process
of the material properties (1). has become a subject of a great deal of academic and
Since the late sixties microwave irradiation has been industrial research with a number of scientific and patent
employed to synthesis and process polymeric materials literature being generated (10-13). Microwave
exploiting the rapid heating and melting of neat and technology has become widely accepted and a popular
mineral-filled plastics for a number of purposes such as unconventional technology in polymer chemistry as an
fast curing of thermosetting resins and composites, alternative to, and often improvement on, conventional
polymerization of vinyl monomers, rapid drying of heating. This statement is clearly evident from the annual
aqueous solutions or dispersion of polymers and resins, number of publications on microwave-assisted polymer
heat drawing of polymer rods and tubings (2). For chemistry as growing rapidly with more than 600
example, microwave irradiation was applied to curing of publications up to the end of 2004 (Figure 1) (12).
epoxy resins (3), and the use of microwave irradiation for
bulk polymerization of dental materials was also reported
(4). In turn, emulsion polymerization of various vinyl DISCUSSION
monomers has been described for the radio and
microwave frequency range (5). Industrial microwave processing has never achieved the
A remarkable achievement of the late sixties was the success of domestic microwave appliances in which speed
application of microwave irradiation for the continuous and convenience of reheating (not cooking) were
vulcanization of extruder rubbers and the discontinuous powerful driving forces for consumers. By contrast, in
vulcanization of moulded rubber 1984, the whole of the food industry
articles (6-8). The microwave assisted used microwave units with a total
vulcanization of rubber compounds that power output of only 19 MW of
has been used industrially since the microwave heating units installed
seventies, is the most important worldwide (14). In absolute terms, the
application of microwave heating to 19 MW of industrial microwave power
polymeric materials in terms of number were equivalent to 32 thousand 600
of installed plants. For example, in W domestic microwave ovens, which is
1992 microwave vulcanization of derisory by comparison to the ca. 7
extruded rubber weather stripping for million units in domestic service in
the automotive and construction 1984 in the US; at the time the highest
industries has found commercial growth rate in the electric domestic
application over 600 installations appliances sector (15).
worldwide (7). Microwave processing Figure 1. Number of publications on On the other hand, the use of
offered rubber processors significant microwave-assisted polymerizations microwave heating in an industrial
advantages over conventional sorted by year. scope usually has quite different

30 chimica oggi • Chemistry Today • Vol 25 nr 3 • May/June 2007

Microwave synthesis
requirements compared to the As it was stated at the
application in a research beginning, the microwave
environment. The biggest assisted vulcanization of
differences are the rubber compounds is the
motivations of the project and most important application of
magnitude of the equipment. microwave heating to
While the motivation to use polymeric materials in terms
microwaves in a research of number of installed plants.
application may be manifold, At the moment, the
ranging from fundamental microwave equipment
research to finding new Figure 2. Diagram of microwave line for vulcanization of rubber. manufacturers offer single-
applications, the industrial mode as well as multi-mode
intention for using microwaves or other new technology is microwave ovens, which are designed for automobile
usually only a single one – profit. Therefore, the industrial type profile and big industrial type profiles, respectively.
project is limited to giving answers to two questions. At Present implementation are characterized by the 3-10 kW
first the question if it is possible to use microwaves for the applied power, shifting velocity in range 0.75-45 m/min.
intended process, and second, if the first question was Treated profile ca. 50 x 50 mm passes the 3 m long
answered with yes, the question if it is more profitable to microwave chamber followed by hot-air 7 m long space
use microwaves for the process than the existing and cooling section of approximately 4 m. Result
technology (16). processing capacity is about 500 kg/h. Control of the
In fact, microwaves do not provide a universal solution to process and especially the extent of installed microwave
all problems but should be considered whenever all other output heat is typically 1 kW per approximately 30 kg of
processes fail to solve an industrial problem, when their the product per hour (Figure 2) (17).
unique advantages can offer considerable savings as For processing of polymeric materials and composites a
compared to other existing processes. Since magnetron number of industrial microwave equipment manufacturers
efficiencies are between 50-72 percent for 2.45 GHz offer equipment for the production of continuous cast-
compared to 80 to 87 percent for 922 or 915 MHz, a resin components, in which the microwave unit (3.6 kW
necessary but not sufficient condition then is that the or 7.2 kW) processes high-viscosity resins systems with
product to be treated must be of high value, so that the flow rates up to 5.0 kg/min. The control system provides
cost of microwave treatment can be justified. The study of easy integration into other and/or existing systems.
efficiency should also include a detail analysis of the Several furnaces can be switched in cascades to achieve
conventional process, of which the user often has a very an increase in temperature difference between feeding
vague idea (15). flow and drain flow and/or an increase in the flow
Thus, the processes characteristics that have been quantity of the medium to be treated. A microwave flow
suggested as potentially attractive for microwave heater is available which can also be applied in other
processing are (9): fields, e.g. food industry, plastic and chemical industry.
– the size or thickness of the material should be large There is microwave continuous heating chamber for glass
– the cost of the material should be high fiber cables, glass fiber reinforced plastics, and reinforced
– improvements in properties obtainable from optical fibers 0.8 / 1.6 / 2.4 kW (18).
microwave processing are significant There are also available continuous microwave belt
– plant space is limited furnaces, in which the microwave generators are
– electricity is cheap arranged in a spiral around the longitudinal axis of the
– minimizing handling is advantageous cylindrical chamber to achieve a more uniform energy
distribution. The conveyor belt passes over floor plates
From this very simplified overview it becomes clear why which are fitted with secondary radiators to provide a
the results of a research project are not much use for an higher microwave concentration. The furnaces can be
industrial project of even the same topic. Although much operated with a microwave power output of up to 200
of the process understanding a research project generates kW. The power control system allows each magnetron to
is not required for the average industrial project, it should be switched on and off if necessary, which offers the
nevertheless be possible to come to at least the same advantage that power consumption is reduced compared
result as the industrial project. The other big difference to continuous power control. Size of channel opening is
between a research project and an industrial one is the adapted to a process (Figure 3) (18).
size and power of the used microwave test unit (16). A new industrial microwave system HEPHAISTOS-CA2
Therefore, it is worth mentioning what equipment is (High Electromagnetic Power Heating Autoclaveless
already available industrially and for laboratory uses. Injected STructures Oven System) for curing of carbon
fibre reinforced plastics is being developed (19). The
system is especially optimized for processes like injection
molding or curing of that matrix and a modular system
technology in connection with “autoclave” fabrication
processes.
The second segment on the microwave chemistry market
is for instruments for laboratory use in chemical synthesis
and analysis that targets customers in academic working
groups and laboratories in the chemical, pharmaceutical
and biochemical industries. The intention of all
manufacturers as well as users is to extend the dimensions
of product capacity. Thus, most research in the field of
chemical synthesis has recently been focused on scaling
up of chemical reactions using microwave irradiation.
Figure 3. Continuous microwave belt furnace.
Manufacturers of microwave instruments have devised

32 chimica oggi • Chemistry Today • Vol 25 nr 3 • May/June 2007

 Microwave synthesis
CONCLUSIONS

In summary, there are fundamental differences in the

heating mechanism during material processing in thermal
and microwave fields. Microwave energy, in contrast to
thermal heating, is supplied directly to a large volume,
thus avoiding the thermal lags associated with conduction
and/or convection. Consequently, temperature gradients
and the excessive heat build-up during thermal
processing could be reduced by a microwave power
control. Thus, a comparison of thermal and microwave
processing assumes a new dimension when the
temperature distribution inside the sample is considered,
Figure 4. Continuous microwave reactor with rotating quartz and that is where the scientific challenge lies. Regardless
tube (Politechnika Krakowska). of the type of activation (thermal) or kind of microwave
effects (non-thermal) (26), microwave energy has its won
means of scaling up the yield of both single-mode and advantages which are still waiting to be fully understood
multi-mode microwave reactors. Based on the patents and applied for chemical process.
publications granted to date in this field, it is evident that
research is still in a nascent stage (20). The detailed
descriptions of such instruments can be found in the REFERENCES AND NOTES
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An overview of microwave equipment manufacturers was
presented recently (25). It can be seen that many DARIUSZ BOGDAL*, ALEKSANDER PROCIAK
companies that specialize in microwave power will build
microwave equipment to customer specification, and *Corresponding author
some will assist with design and processing issues. Chair of Polymer Chemistry and Technology
However, industry must have some understanding of how Politechnika Krakowska
microwaves interact and heat materials and what the ul. Warszawska 24
limitations are before its potential can adapted. Krakow, 31-155, Poland

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