Upload
kuruvilla-a-cherian
View
223
Download
0
Embed Size (px)
Citation preview
7/28/2019 Novel Approaches to Materials Synthesis and Processing with Microwaves
1/16
Festschrift Symposium for Professor Ted White, Chemical EngineeringUniversity of Queensland, Australia, December 2001
Novel Approaches to Materials Synthesis
and Processing with Microwaves
Kuruvilla A. Cherian*1, Arne J. Fliflet
2, Suman Ganguly
1
and Rustum Roy3
1Center for Remote Sensing Inc., Fairfax, VA 22030, USA
2Radiation and Particle Beam Generation Section, Code 6793
Naval Research Laboratory, Washington, DC 20375
3Materials Research Laboratory, The Pennsylvania State University,
University Park, PA 16801, USA
____________________________________________________________________
Use of microwaves for materials synthesis and processing is fast emerging as a viable
technological option offering specific advantages over several other conventional
methods. Novel synthesis routes for several technologically important materials and
sintering of various ceramic, and even powder metal, bodies have been successfully
demonstrated using 0.915 or 2.45 GHz radiation. 83 GHz quasi-optical Gyrotron
radiation offers novel and unique materials processing possibilities not possible with
the other frequencies. This paper presents some details of recent research &
development work utilizing these microwave frequencies.
_____________________________________________________________________
Introduction
Innovative approaches and new developments in materials synthesis and processing
have been spurred on by [1]:
*Author for correspondence; current address: Chief Scientist & Vice President of
Research, QQC Inc., 12825 Ford Road, Dearborn, MI 48126, USA
Email: [email protected]
7/28/2019 Novel Approaches to Materials Synthesis and Processing with Microwaves
2/16
a) need for new materials with unique properties (e.g. nano structured material formssuch as nano-particles, nano-fibers and nano-composites),
b) need for new and efficient routes to known materials, in known or new forms (e.g.
bulk and thin film forms of ultrahard phases such as diamond and diamond
films), and
c) need for new and improved technologies which are better, cheaper, faster and
greener (e.g. sintering, surface modification, etc).
Several approaches have been investigated to achieve these on a practical scale,
involving and exploiting unique characteristics of different types of electromagnetic
radiation. This article deals with novel approaches to materials synthesis and
processing using electromagnetic radiation in the microwave range: 0.915GHz,
2.45GHz & 83 GHz Gyrotron radiations.
Microwave Heating Characteristics
Microwaves are electromagnetic radiation with wavelengths in the 1 mm to 1 m range
in free space, or frequency between 300GHz to 300 MHz. 2.45 GHz microwaves are
currently used for a range of scientific, technological and industrial applications
including heating. There is a fundamental difference between microwave heating andconventional heating. In the microwave process, heating is a function of the material
being processed; depending upon the interacting material type, microwaves may be
transmitted, absorbed, or reflected. Heat is generated internally within the material
instead of originating from external heating sources.
Microwave characteristics that are advantageous for materials processing may be
summarized as follows:
a) Radiation Penetration and Heating
The depth of penetration in various materials depends on several factors, including
frequency of the radiation used and the dielectric properties of the material.
Generally, most ceramics absorb microwaves to varying degrees. The extent of
microwave coupling largely depends upon the dielectric properties of the material.
When microwaves penetrate and propagate through a dielectric material, the internal
electric field generated within the affected volume induces translational motions of
7/28/2019 Novel Approaches to Materials Synthesis and Processing with Microwaves
3/16
the free or bound charges (e.g. electrons or ions) and rotates charge complexes suchas dipoles. The resistance of these induced motions due to inertial, elastic, and
frictional forces cause losses and attenuate the electric field. As a consequence of
these losses, energy is transferred and volumetric heating occurs within the solid,
leading to inside-out heating or an inverse heating gradient with the interior of the
solid hotter than the outside. This enables rapid volumetric heating without surface
overheating, and various practical advantages such as removal of gases and binder
material from interior of porous materials, or enabling more efficient infiltration and
condensation of material into porous bodies.
b) Temperature Dependent Dielectric Losses and Accelerated Heating
The rate of temperature rise in a microwave field varies widely for different materials;
however, when this phenomenon occurs the heating rate is very fast since the energy
is transferred directly to the desired solid without the need of heating its environment
first. Since the effective heater in the microwave system is the solid being heated and
the heating is a function of its ability to couple with the microwave energy, the
heating rate is a function of this material property and the frequency of the radiation
used. For the same material, higher frequencies could provide higher heating rates
whereas lower frequencies have higher penetration. Many materials exhibit
acceleration of dielectric losses above a critical temperature. When uncontrolled this
could lead to thermal runaway but when controlled this could facilitate very rapid
bulk heating, which may be used to advantage in various processes like annealing,
calcining, firing, melting, sintering, etc.
c) Field Distribution Control and Localized Heating
Using specific applicators electric field distributions can be focused and controlled.
This could help localize very high field strengths, offering a host of possibilities
including heating selected regions between two material to facilitate bonding, brazing
or welding, etc. Single mode systems, or high frequency Gyrotron systems with
quasi-optical beam characteristics, are more useful for these applications. The
generation of microwave assisted plasmas for sintering or chemical vapor deposition
is another intensely investigated possibility. Single mode systems are useful for
microwave plasma applications.
7/28/2019 Novel Approaches to Materials Synthesis and Processing with Microwaves
4/16
d) Material Dependent Selective HeatingDifferent materials exhibit different degrees of coupling with microwaves. The
differential coupling characteristics can be used to advantage in various types of
processing. The strong microwave absorption characteristic of water, for example, is
exploited in food processing, drying or dehydrating several types of materials.
Similarly, selective microwave absorption and heating characteristics of specific
components may be exploited to advantage in processing asphalt, rubber and other
composite materials.
e) Self-limiting Heating.
In cases where one constituent phase of a composite materials system is selectively
heated, a phase change of the specific phase into a non microwave-absorbing phase as
a result of the processing could lead to cessation of heating and thus be self-limiting.
This characteristic could be used to advantage in the synthesis of certain phases that
are non-microwave absorbers, from starting phases that are microwave absorbers.
Microwave Processing Set-Ups
These characteristics outlined above can be used to advantage for the synthesis and
processing of a variety of materials. Several types of microwaves systems arepresently available and these include single mode and multi mode cavities and
travelling wave applicators, besides a variety of radio frequency and induction heating
systems. These could offer considerable flexibility in processing and also enable
tailoring of processes for specific materials synthesis and product processing. Several
reputed research groups worldwide have seized upon this opportunity, and detailed
reports of the varying degrees of successes obtained have been reported. [1-4].
The most commonly used systems for materials processing at present use 2.45
GHz radiation for which the microwave power sources are readily available. Since
lower frequencies offer greater depth of penetration, 0.915 GHz radiation has been
found beneficial for certain larger bulk materials processing applications. Typical
0.915 and 2.45 GHz microwave processing set-ups at the Penn State Materials
Research Laboratory (MRL) are shown schematically in figs. 1a & b. These normally
operate in air but adaptations have been made to operate in special atmospheres as
7/28/2019 Novel Approaches to Materials Synthesis and Processing with Microwaves
5/16
well. Using these or similar set-ups, a host of useful materials and material systemshave been synthesized and/or processed. These include sintering of WC+Co and other
superhard material composites for tool applications. It was found, depending on the
Figure 1a & b. Schematic of 0.915 and 2.45GHz microwave processing systems at
Penn State MRL
precursor characteristics and processing regime adopted, that microwave processing
could yield better mechanical properties than those conventionally processed, fine and
uniform microstructure (~1 micron grains) with very little grain growth and nearly
7/28/2019 Novel Approaches to Materials Synthesis and Processing with Microwaves
6/16
full density achieved without addition of grain growth inhibitors. Typical processparameters could include sintering at 1250-1320
oC for 10-30 minutes. Materials
synthesis utilizing reduced oxide precursors was another successful area, and this
include BaTiO3 (BT), Pb(Zr 0.52 Ti 0.48)O3 (PZT), Ba3(MgTa2)O9 (BMT), etc. Lesser
processing times and temperatures result in less loss of volatile components such as
Pb compounds [1]. Other notable results include synthesis of sub-micron diameter
Si3N4, [5], fabrication of transparent ceramics through minimization of grain growth
[1], etc. Fig. 2 shows some examples of components processed with microwaves at
Penn State MRL.
Figure 2. Various kinds of WC/Co parts sintered through 2.45GHz microwaveprocessing at Penn State MRL
Novel Approaches and Results with 2.45GHz radiation
Reduced Oxide Precursor Microwave Synthesis
In the area of microwave-assisted materials synthesis, it was found that pre-reduction
of oxide phases could yield highly microwave absorptive precursor materials which
could enhance reaction kinetics dramatically. The creation of a defect structure
7/28/2019 Novel Approaches to Materials Synthesis and Processing with Microwaves
7/16
apparently makes microwave coupling more efficient at room temperatures. Forexample, conventional methods for the synthesis of technologically important oxides
such as BaTiO3 (BT), Pb(Zr0.52Ti0.48)O3 (PZT) and Ba3 (MgTa2)O9 (BMT) require
temperatures in the range of 900-1400oC with several hours of soaking time. Pure
stoichiometric metal oxides such as TiO2 and Ta2O5 do not couple with microwaves
efficiently unless heated to temperatures >1000oC where they become dielectrically
lossy. Partial reduction of these phases to oxygen defective states such as TiO2-x and
Ta2O5-x radically enhances their ability to absorb microwave energy at lower and near
room temperatures. By using such pre-reduced precursor oxides, BaTiO3 (BT), Pb(Zr
0.52 Ti 0.48)O3 (PZT), Ba3 (MgTa2)O9 (BMT) could be synthesized at amazingly lower
temperatures, between 300-900oC in 5-12 minutes! This concept of reduced oxides
causing better microwave coupling has also been extended to densification by
sintering. An example is that of titania, where 98% density was achieved in 40
minutes, compared to 3 hours through conventional heating [1].
Microwave Hydrothermal Processing
A novel variation in processing approach is the development of the microwave
hydrothermal apparatus, initially used for rapid dissolution of rock and other samples
for chemical analysis. The Penn State MRL group has successfully used this for new
materials synthesis studies. Rapid and convenient precipitation of 1-micron metal
powders from ethylene glycol solutions and a wide variety of synthesis in oxide and
silicate systems were studied [1]. The microwave hydrothermal process have yielded
at least two new phases and, besides, has been found to be a powerful tool to
synthesize a range of useful materials such as ferrites, ferroelectrics, etc. Reaction
times were found to be lowered substantially and reaction times by nearly an order of
magnitude, compared to not only dry conditions but also non-microwave
hydrothermal conditions as well.
Full Sintering of Powdered Metal Bodies
A very novel and significant result achieved recently was sintering of powdered metal
bodies [6]. Bulk metals reflect microwaves and thus are not heated significantly in a
microwave field. Nevertheless in a powdered and unsintered form, all metals alloys
and intermetallics are reported to couple and heat up in a microwave field efficiently
7/28/2019 Novel Approaches to Materials Synthesis and Processing with Microwaves
8/16
and effectively to yield well-sintered bodies with improved mechanical properties.Examples include PM green bodies of various metals and alloys (Fe-Ni-C and Fe-Cu-
C) sintered in a microwave field with total time cycle ~90 min for sintering
temperatures 1100-1300oC and soaking period varying from 5 to 60 minutes. Physical
properties, such as density, hardness and modulus of rupture were reported to be
better than those prepared through conventional routes. The ability to sinter metals
with microwaves should be beneficial in the preparation of high-performance metal
parts needed in many industries, the automotive industry for example.
Novel Approaches with 83 GHz Gyrotron Radiation
We have seen above that advanced materials processing technologies using
microwaves offer several advantages over conventional methods; the frequency most
commonly being investigated has been the conventional 2.45 GHz. Efforts have been
underway to use these microwaves for numerous materials processing applications at
various laboratories worldwide (see references in [1]). With the realization of the
frequency dependence of microwave-material interaction characteristics, other
processing approaches employing different frequencies have assumed greater
importance. For larger bulk processing, 0.915 GHz has been found to have certainadvantages over 2.45 GHz. For technologies involving extremely fast heating and
surface processing, however, higher frequencies offer unique advantages.
Gyrotron radiation is a microwave beam with a wavelength from one to 10 mm.
This is a new, concentrated beam source of energy and has broad, unique applicability
in the processing of various materials such as ceramics, composites, organics,
polymers, and semiconductors, and chemical synthesis. This beam is generated by a
Gyrotron, which is a generator of high-power concentrated electromagnetic radiation.
There are no other devices in existence today that can generate this specific
wavelength at power levels high enough for materials processing. The Gyrotron was
developed almost simultaneously in Russia and the U.S. and today all nuclear centers
throughout the world use Gyrotron devices in their fusion synthesis units, but
generally for this application only. The novel 83 GHz microwave beam produced by a
Gyrotron, with quasi-optical beam characteristics, offers unique advantages in
7/28/2019 Novel Approaches to Materials Synthesis and Processing with Microwaves
9/16
materials processing over conventional 2.45 GHz microwaves. Higher frequencieshave different material interaction characteristics that could be exploited for unique
materials processing advantages.
Figure 3. Gyrotron Beam Energy Source for Materials Processing
Fig 3 shows some of the Gyrotron beam characteristics. The unique advantages of
83 GHz Gyrotron microwaves are:
1. Quasi-optical beam characteristics that enable it to be focussed, spread, rastered
or directed on to specific parts of sample being processed
2. Efficient heating source for non-metallic materials: extremely rapid heating to
melting points in seconds or fraction of a second
3. Heating depth in mm to cm range: extremely useful dimensions for industrial
processing
4. Selective heating of materials: non absorbing material components not heated
unnecessarily during processing
. To exploit this for materials research, design and construction of a novel high
frequency (83 GHz) Gyrotron materials processing facility was necessary. The
combined efforts and resources of the Center for Remote Sensing (CRS), Inc., VA
and the Naval Research Laboratory (NRL) in Washington carried out this complex
7/28/2019 Novel Approaches to Materials Synthesis and Processing with Microwaves
10/16
task. A program in HF microwave ceramic processing based on Gyrotron sources wasinitiated in 1995 at NRL, with the initial focus of the program being on bulk sintering
of nano-crystalline ceramics. In 1998, the resources of the NRL program and an ONR
Phase II SBIR grant awarded to CRS Inc. helped to establish a new 15kW CW 83
GHz Gyrotron beam facility. The facility was intended to be made available to
various commercial and Government users for test and development of new
techniques and processes.
Fig. 4a shows the schematic, and Fig. 4b the actual set up, of this Gyrotron beam
material processing facility. The millimeter wave radiation source is a CW Gaussian
beam generated by an industrial Gyrotron manufactured by Gycom, Ltd., operating at
83 GHz and power output up to 15 kW. This materials-processing facility is designed
to undertake various R & D activities to exploit the unique Gyrotron microwave (mm
wave) interaction characteristics with materials, to develop new or better processing
technologies. Application areas include coating of materials, soldering and brazing,
polymer treatments, semiconductor processing, ceramic processing and materials
synthesis.
Figure 4a. Schematic of the Gyrotron Processing Facility at the Naval ResearchLaboratory, Washington
7/28/2019 Novel Approaches to Materials Synthesis and Processing with Microwaves
11/16
Figure 4b. The Gyrotron Beam Material Processing Facility at the Naval Research
Laboratory, Washington
Some of the specific materials processing possibilities with Gyrotron radiation
which have been identified may be summarized as follows:
Coating of materials
Coating of metallic objects (e.g. oil and gas pipelines, chemical equipment) with
polymer (polyethylene, Teflon, polypropylene and other nonpolar polymers) for
better corrosion resistance, with excellent adhesion.
Ceramic glaze on firebricks, with wide transition zone, strong adhesion, high
resistance to thermal shock.
Steel casting ladle linings, gates and pipes, with excellent performance conditions
under cyclical mechanical and thermal loads.
Metal surface hardening of metals, tool steels, etc. by high temperature surface
diffusion of hardening component and with lower overall internal heating.
Metallization of dielectric materials, PCB manufacture using thick film
technology instead of etching: copper on fiberglass laminate substrates possible
7/28/2019 Novel Approaches to Materials Synthesis and Processing with Microwaves
12/16
with substrate temperatures rising to only 60-80C, fast copper fusing on ceramicsubstrates with excellent adhesion, without need for shielding gasses.
Soldering and brazing
Fast brazing of diamonds and cBN to metal tools; use of high temperature brazes
for increased mechanical bonding properties, without destructive phase
transformations.
Low pressure compaction of diamonds and cBN, using high temperature brazes
and without phase transformations.
Joining of ceramic articles and fabrication of complex shapes using high
temperature brazes; preferential heating of joint enable use of brazes with melting
points higher than the materials being joined.
Polymer treatment
Hermetical sealing of electronic components by selective and rapid heating of
polymers.
Manufacture of fiberglass reinforced polymer laminate sheets without use of
polymer solvents and large drying furnaces.
Manufacture of reinforced polymer structures with rotational symmetry, without
air bubble entrapment.Semiconductor processing
Homogenization of semiconductors, active dopants, form ohmic contacts, etc. by
selective fast diffusion processes under Gyrotron radiation.
Ceramic processing
Faster sintering process for ceramics with fine microstructure and UV/optical/IR
transparency.
Materials synthesis
More efficient synthesis routes for specific phases exploiting selective absorption
characteristics of materials to Gyrotron radiation.
Penn State MRL, CRS Inc. and NRL have been collaborating at various levels in
developing this new technology for practical applications.
7/28/2019 Novel Approaches to Materials Synthesis and Processing with Microwaves
13/16
Figure 5. SiOx fibers synthesized through 83 GHz Gyrotron microwave processing
Figure 6. WCx coating on low carbon steel through 83 GHz Gyrotron microwaveprocessing
7/28/2019 Novel Approaches to Materials Synthesis and Processing with Microwaves
14/16
Some preliminary results have been published [7-10], while others are undervarious stages of processing. Figs.5, 6 and 7 show some preliminary materials
processing results: rapid synthesis of SiOx fibers, coating of WCx on low carbon steel
and ceramic-metal joining. Detailed research & development efforts are underway at
Figure 7. Examples of ceramic-metal brazing done with the 83 GHz Gyrotron facility
the NRL facility to apply the Gyrotron radiation to the various possibilities that have
been identified.
The new CRS-NRL 83 GHz Gyrotron processing facility at the NRL, together
with the 0.915 GHz and various 2.45 GHz microwave processing facilities of the
Penn State MRL microwave processing group who are collaborators, offer unique
opportunities for developing novel advanced materials processing technologies
employing microwaves of various frequencies 0.915, 2.45 and 83 GHz. There are
numerous applications for multi-frequency microwave processing, and the
effectiveness of different frequencies for various processes are currently being
evaluated.
Conclusions
Significant advances and developments have taken place during recent years in the
application of 0.915 and 2.45 GHz microwaves to materials synthesis and processing.
Parameters leading to extremely fast reaction kinetics and new reaction pathways
producing specific material phases at lower temperatures than that possible by
conventional methods, have been established through novel approaches for several
7/28/2019 Novel Approaches to Materials Synthesis and Processing with Microwaves
15/16
materials. Reduction in processing times compared to conventional routes, coupledwith better physical properties of the processed material, are leading to better and
cheaper products through microwave processing now becoming a reality
particularly specialty ceramics. Most significant recent developments include
sintering of powdered metals and fabrication of transparent ceramics in a single step
process.
The establishment of the 83 GHz Gyrotron materials processing facility offers
further possibilities. The unique Gyrotron beam characteristics enable new ways of
selectively heating parts of a component for specific processing advantages. It is
being developed as a valuable industrial tool for developing novel technological
solutions that were considered impossible or impractical, earlier.
Acknowledgements
The Gyrotron related work was performed through a SBIR contract from the Navy to
the Center For Remote Sensing, Inc. The gyrotron facility was developed by the
Center For Remote Sensing, Inc. and is currently available for various users; those
interested should contact www.cfrsi.com. KAC acknowledges that most of the
Gyrotron microwave materials processing work mentioned here were performedwhile associated with CRS Inc.
. Support for the research at Penn State MRL has been provided by the Office of
Naval Research and the Defense Advanced Research Projects Agency.
References
1. Roy, R., Agrawal, D., Cheng, J.P. and Mathis, M. 1997 Microwave processing: triumph ofapplications-driven science in WC-composites and ferroic titanates. Ceram. Trans. 80, 3-26.
2. Clark, D.and Sutton, W.H. 1996 Microwave processing of materials. Annu. Rev. Mater. Sci., 26, 299-331.
3. Schiffman, R.F. 1995 Commercializing microwave systems: paths to success or failure. Ceram. Trans.
59, 7-174. Vaidhyanathan, B. and Rao, K.J. 1997. Synthesis of Ti, Ga and V Nitrides: Microwave assisted
carbothermal reduction and nitridation, Chem. Mater., 9, 1196-1200
5. Gedevanishvili, S., Cherian, K.,Agrawal, D., and Roy, R. 1999. Synthesis of silicon nitride whiskersby microwave heating. Solid-State Chemistry of Inorganic Materials II, Mater. Res. Soc. Symp. Proc.
547, 413-417
6. Roy, R., Agrawal, D., Cheng, J., and Gedevanishvili, S., 1999. Full sintering of powdered-metal bodiesin a microwave field. Nature, 399, 668670.
7/28/2019 Novel Approaches to Materials Synthesis and Processing with Microwaves
16/16
7. Fliflet, A.W., Bruce, R.W., Fischer, R.P., Kinkead, A.K., Gold, S.H., Ganguly, S. and Cherian, K.1999. Initial operation of a gyrotron-powered millimeter-wave beam facility for microwave processingof materials. Submitted to 24th Int. Conf. On IR&MMW, Monterey, California USA.
8. Ganguly, S. and Cherian, K. 1999. Multi-frequency microwave processing facility for advancedmaterials. Materials Technology: A Strategic Industry Report on Emerging Materials, RelatedInnovations, Technologies, Applications, Markets, Technology Transfer and Advanced Performance
Materials, 14 (4) 239-240
9. Bruce, R., Fliflet, A., Fischer, R., Kinkead, A., Gold, S., Ganguly, S. and Cherian, K., 1999. MaterialHeating Experiments with a Gyrotron-Powered Millimeter-Wave Beam. Presented at: 41st Annual
Meeting of the Division of Plasma Physics, APS, Seattle, USA.
10. Roy, R., Cherian, K.A., Badzian, A., Schriempf, J.T., and Petach, T.P., 2000. Solid State Synthesis &Processing by Microwave & Laser Photons. Presented at: Laser Applications in DoD Conference, The
Pennsylvania State University, USA