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Microwave Technology

Principles
Microwaves are high-frequency electromagnetic waves in the same frequency band as radar waves. Only 4
microwave frequencies are permitted for industrial and scientific use. Of these, 2.45 GHz is the most
frequently used.

Electromagnetic waves are interconnected electric and magnetic fields which change over time and
propagate at the speed of light through space. The electromagnetic field produced is described by the field
strength vectors E and B.

E
=c
B

E...electric field
B...magnetic field
c...speed of propagation
λ...wavelength

λ

c

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Microwave Technology

Properties of electromagnetic waves

All electromagnetic waves are sky waves which propagate at the speed of light and transport energy (without
loss in a vacuum; with loss in dielectric material).
They show the same effects as light:
• Interference
• Diffraction
• Refraction
• Reflection
• Polarizability
Which of these effects occurs depends on the wavelength and the molecular structure.

Microwaves
• are reflected by non-polar metals
• pass through ceramic, glass and porcelain
• are absorbed by food, human tissue and polar materials
Microwave radiation is not an ionizing radiation and is therefore not hazardous for human tissue.

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Microwave Technology

Producing microwaves
Low microwave frequencies can be produced using electron tubes or transistors. High and very high
frequencies (>100 MHz) are produced by klystrons, magnetrons or traveling wave tubes
In decomposition instruments, microwaves are produced using magnetrons.

Operating principle: Magnetron
A magnetron is a metallic vacuum tube, consisting of a cathode and an anode, which is surrounded by a
permanent magnet frame.
A high voltage is applied to a heated rod (cathode) to emit electrons. These electrons are drawn into a
circular path by the applied magnetic field. These electrons hit the outer wall of the tube (anode), which is cut
at regular intervals radially to the chamber (resonator). Within these incisions the polarity of the electrical
field reverses with the desired frequency and produces microwaves. These are emitted via an antenna, e.g.
in the microwave oven.

Resonators Anode

Cathode

Heating

Uncoupling Loop

Picture from: Christian Wolf

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Microwave Technology

Material behavior in the microwave
The capacity of a substance to absorb microwave energy is expressed by its dielectric loss factor tan δ,
which is represented by the dielectric loss (ε´´) and the permittivity (dielectric constant) (ε´).
tan δ = ε´´ / ε´

The lower the loss factor, the lower the absorption capacity of the substance. Materials with a low absorption
capacity can be used as neutral components, e.g. as vessel material.
Some substances, e.g. water, have a relatively high loss factor at room temperature but this decreases once
a certain temperature has been reached.
The dielectric loss factor is dependent on:
• the substance
• the frequency
• the temperature

Materials tan δ [3 GHz, T=25 °C]
Quartz 0.6
Borosilicate 10.6
PTFE, PFA 1.5
PE 3.1
PVC 55
Ceramic 5.5
Water (25 °C) 1570
Water (95 °C) 470

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Microwave Technology

Microwave absorption
To heat a substance, the material must couple to the microwaves. In other words, the substance must
absorb electromagnetic energy.
Generally speaking, two mechanisms are available:

Dipole rotation
This is the case with materials which have a pronounced dipole (water, acids, solvents). In the rapidly
changing electric field, the molecules try to orient themselves in the direction of the field lines. This sets them
in rotation-vibration. The energy absorption from the microwave field is more intensive the closer the
resonance frequency of the molecule is to the frequency of the microwave.

δ− δ− δ−

δ+ δ+ δ+

Dipole moments
[Debye]
HF 1.82
HNO3 2.17
HCl 1.03
H20 1.844
C3H8O 1.66
NH3 1.46
CCl4 0
CH3Cl 1.87

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Microwave Technology
Ionic conductance
Heating in the electromagnetic field also occurs when there are free ions (electrolytes, glassy materials and
ceramic materials).

Both mechanisms, dipole rotation and ionic conductance, are influenced by various factors:
• Wavelength

• Physical properties of the solution
o Permittivity (dielectric constant)
o Polarity
o Temperature
o Viscosity
o Thermal capacity

• Ion characteristics (ionic conductor)
o Size
o Concentration
o Charge
o Mobility

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Microwave Technology

Advantages of microwave technology
When heating material using thermal convection, the heating occurs from the outside in.
Microwave energy heats the material from the inside out. The dielectric dissipation is independent of the heat
flow on the surface of the material.
Benefits:
• Time minimization

• Energy minimization
• No inertia. When the microwave radiation is switched off, the source of heat is immediately removed
from the object

Example: Heating a vessel in an oil bath (A) and using microwaves (B)
Heating from outside in – heating from inside out

(A) (B)

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Microwave Technology

Microwave decomposition
Decomposition is the conversion of a solid sample into a liquid, homogeneous state.
This makes the sample easier to aliquot and has all the prerequisites for an interference-free qualitative and
quantitative determination of the elements or compounds of interest. After mechanical sample preparation,
decomposition is the most time-consuming step in wet-chemical procedures. It is therefore very useful to
optimize this step and reduce the required time while retaining or increasing the quality of the analysis.

Requirements of the decomposition procedure:
• Exclusion of systematic errors by preventing
o Contamination
o Loss of analytes
o Adsorption of analytes on the vessel surface
• The decomposition must be complete for the task in hand
• Removal of distorting matrices and prevention of matrix extension e.g. from the decomposition acids
used
• Simple operation with minimum required time, work and instrument operation

All these requirements are fulfilled by a closed, microwave-heated system.

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Microwave Technology

Prevention of contamination by the decomposition agent

Contamination by the decomposition agent can be prevented either by using purchased super-pure acids or
subboiling analytical reagent quality acids to purify them.

Prevention of contamination by the vessels

The vessels can be cleaned by cleaning digestion or evaporation equipment.

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Microwave Technology
Prevention of contamination by the vessel walls

Adsorption on the vessel walls is prevented by using highly pure materials which are chemically and
thermally resistant, e.g. PFA, PTFE and quartz glass.

PTFE Polytetrafluorethylene Properties

High melting point (342°C)
High thermal stability
Chemically inert
Fire-resistant
Low water absorption/adsorption
Insoluble

PFA Perfluoralkoxy
—[(CF2)4- CF(-O-CF2-CF2-
CF3) — (CF2)5]n—. High melting point (310°C)
High thermal stability
Chemically inert
Low water absorption/adsorption
Insoluble

Quartz

Pure
Chemically resistant
Thermal-shock resistant
Temperature resistant
Pervious to UV and IR
Electrically insulating properties

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Microwave Technology

Comparison: Open and closed decomposition

Open decomposition

Samples and reagents are heated on a hotplate, in a sand bath or in a microwave-heated system. The
sample and reagents are in open vessels made of glass, quartz, glassy carbon or PTFE. The gas vapors
which are produced are either extracted or caught by a reflux condenser and returned to the reaction
mixture.
The maximum reaction temperature is dictated by the boiling point of the acid mixture at ambient pressure.

Sample amount 0.5 to 10 g

Reagent consumption 10 to 100 mL

Decomposition duration 2 to 10 h

Use:
• Inhomogeneous samples
• Easy to dissolve samples
• High analyte concentration
• In combination with flame AAS

Benefits:
• Simple and reasonably priced equipment
• Easy to use
• High sample throughput, very good for inhomogeneous samples
• Any reaction gases can evaporate unhindered (no buildup of pressure)

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Microwave Technology
Disadvantages:

• Maximum temperature is limited to the boiling point of the reagent mixture; poor decomposition
quality
• Long decomposition time
• Use of H2SO4 to increase the temperature of the mixture
Disadvantages of sulfuric acid:
Difficult to produce pure sulfuric acid
Interferes with many subsequent analysis methods due to its high viscosity and
forms sulfates with low solubility when mixed with many metals (e.g. Cd, Pb, etc.),
which leads to values which are lower than the actual values
• High consumption of reagents, high numbers of blank readings
• Evaporated reagents must be refilled during the decomposition
• Possible contamination from reagents and the environment
• Produces corrosive air in the laboratory, despite using an fume hood
• Loss of volatile elements
Hg (elemental)
As, B, Cr, Ge, Pb, Sn, Te, Ti, Zn, Zr (as halogen compounds)
Os, Rh, Ru (under oxidative conditions)
Se, Te (under reductive conditions)
• Large vessels (i.e. 250ml) with large surfaces, adsorption effects and loss of analytes
• Time-consuming cleaning required after decomposition

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Microwave Technology

Closed decomposition

Sample and reagents are heated in closed pressure vessels made of fluoroplastics (PFA, PTFE, PTFE-TFM)
or quartz. The pressure vessels can be heated conventionally (autoclave, heating block) or using microwave
technology. The reaction is controlled via temperature and pressure sensors.
The maximum reaction temperature depends on the thermal stability and pressure stability of the vessel
material used.

Sample amount 0.1 to 1 g (organic sample matrix)
0.5 to 5 g (inorganic sample matrix)

Reagent consumption 2 to 10 mL

Decomposition duration 0.2 to 1 h

Use:
• All materials
• Matrices which are difficult to dissolve
• For all measuring methods (spectrometry, voltammetry)

Benefits:
• High temperatures (up to 320°C depending on the instrument and vessel type)
• High pressures (up to 80 bar depending on the instrument and vessel type)
• Complete decomposition results due to the high temperatures and pressures
• Simple acid mixtures; HNO3 is sufficient for organic samples
• H2SO4 or HClO4 are not required
• Low reagent volumes, reduction of blank readings and reagent costs
• Short reaction times
• No loss of volatile elements
• Does not lead to corrosive air in the laboratory
• Small vessels and inert materials, extremely low adsorption effects and no loss of analytes

Disadvantages:

• Higher purchase cost
• Limited sample weight (higher weights produce larger amounts of reaction gases which remain in the
vessels and lead to pressure which must be controlled)

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Microwave Technology

Microwave-assisted extraction

Solvent capacity for heating by microwaves:

Poor Fair Good

CCl4 Acetone Dichlorobenzene

Benzene Ethylacetate 1-Butanol

n-Hexane Acetonitrile Methanol

Toluene Chloroform Propan-2-ol

Dichloromethane Water Ethanol

Tetrahydrofuran DMF Ethyleneglycol

If solvents are used for microwave-assisted extractions, there must be sufficient polar solvents in the mixture.
The polar solvent volume must be at least 3 mL.

For more information on our microwave decomposition instruments, take a look at our
website:
http://www.anton-paar.com/sample-preparation/microwave_CXSN-5QTJQ5.en.0.jsp

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