Photo-DSC 204 F1 Phoenix®
Photocalorimetry – Method, Technique and Applications
Photo-DSC 204 F1 Phoenix®
Photo-Calorimetry Is an Extension of Classical Calorimetry
for the Investigation of Light-Induced Processes.
Advantages of Photo-Calorimetry
Light- (mostly UV-) curing systems react very quickly (within a few seconds
at low isothermal temperatures) and are solvent-free. This makes them
very attractive for industrial applications.
Three different types exist: radical, cationic and dual-cure systems.
Dual-cure systems exhibit a combiation of thermal and light-curing
reactions and can be found, for example, in adhesives or paints.
The ability to measure the curing kinetics and degree of cure is essential for
the development of UV-curable resins and identification of optimal curing
times and conditions. Photo-differential scanning calorimetry (Photo-DSC)
is a powerful analytical tool for accomplishing these measurements.
Your Benefits
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Extension of the DSC technique
with light radiation capability
Analysis of photo-initiated
reactions in materials
Measurement of the light or
UV-light curing of polymer
resins, paints, inks, coatings
and adhesives
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Study of the influence of UV
stabilizers in pharmaceuticals,
cosmetics and foods (aging
effects)
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Optimization of temperature,
atmosphere, light intensity,
wave length and exposure time
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Determination of the reactivity
and curing time of the polymer
matrix in compounds
Made by NETZSCH
2
Various Commercial Lamps Can
Be Used for Optimum Curing
The Photo-DSC 204 F1 Phoenix® can
be equipped with mercury (Hg) lamps,
diode laser systems or high-power LED
lamps in order to achieve optimum
curing results.
Defined Light Source Distance
for Reproducible Measurements
Adjustable light guides provide for a
constant distance between the light
source and the sample and reference,
respectively. Only reproducible measurement conditions ensure precise
results. The light guides are mounted
on the automatic cover lift for easy
handling.
Flexibility and Efficiency Across
a Broad Temperature Range
Photo-DSC measurements can be carried
out between -100°C and 200°C. However, by simply using the additional manual
furnace lid, standard DSC tests can be
done – alternately or successively –
in the temperature range between
-180°C and 700°C with the appropriate
cooling device. Even measurements with
irradiation can be carried out with the
automatic sample changer (ASC). The
ASC can handle up to 192 samples in different crucible types.
Precise Control of the Atmosphere
Around the Sample
The gas-tight DSC cell in combination
with the integrated mass flow
controllers allows for precise control of
the composition of the atmosphere.
3
Photo-DSC 204 F1 Phoenix®
TRENDSETTING TECHNOLOGY
Photo-DSC Operation
Differential scanning calorimetry (DSC) is a thermoanalytical method in
which the difference between heat flow into a sample and into a reference,
when subjected to a controlled temperature program, is quantitatively
determined (definition based on DIN 51 007, ISO 11357-1 or ASTM E472).
In photo-DSC measurements, both the sample and reference are located
in one furnace and are irradiated simultaneously. The fiber optics are
firmly installed in the lid to ensure reproducible distances between the
fiber optics and the sample and reference.
The DSC measurement software communicates with the UV lamp,
triggering its pulses and – for certain models (see next page) – automatically controlling the pulse length and intensity. During the course of a
measurement, the signals detected are the sample temperature and heat
flow difference. By integrating the heat flow peak, the heat of curing can
be determined, providing meaningful data for development or process
optimization.
Light guides
Light source
DSC lid
DSC sensor with sample and reference pan
4
UV Light Sources – You Have the Choice
Software Features
Recommended are mercury lamps such as DELOLUX 04 or OmniCure®
S 2000 which allow for the selection of wide and narrow ranges; these
should have filters in the UV-A range between 280 nm and 315 nm and in
the UV-B range between 315 nm and 500 nm.
However, other commercially available lamps can also be adapted. For
optimized curing, a defined wavelength (e.g., 447 nm) can be used with
diode laser systems or high-power LED (e.g., 365 nm, 400 nm or 460 nm) –
depending on the resin to be cured.
The OmniCure® lamp is fully software controlled; selection of temperature, light intensity, wave length and exposure time can be carried out
by the DSC Proteus® software.
The gas-tight construction of the DSC instrument allows for easy
measurement of the cross-linking of paints; this process is often sensitive
to oxygen, which can act as an inhibitor.
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Light source can be triggered
and controlled by DSC
measurement software (time
control and intensity control)
Radiation impulse is selectable
by segment, by means of
activation/deactivation through
a check box in the temperature
program
Selectable delay time for
irradiation
Evaluation of effective heat
of reaction by means of curve
subtraction and time offset
capability
Determination of relative or
absolute integral (degree of
conversion)
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Key Technical Data
Photo-DSC 204 F1 Phoenix®
Temperature range
Crucibles
∙∙∙∙
-100°C to 200°C with irradiation module
Standard DSC measurements: -180°C to 700°C
Open aluminum
Recommended Hg-lamp types
DELOLUX 04
OmniCure® S 2000
Max. power
9.9 W/cm2
>10 W/cm2
Wavelength range
315 nm to 500 nm*
320 nm to 500 nm*
Irradiation time
0.1 s to 1000 s
0.2 s to 1000 s
Orifice diameter
8 mm, 4 mm, 2 mm
8 mm, 4 mm, 2 mm
Life time (lamp)
1500 h
2000 h
* Variable and extendable with various filters
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APPLICATIONS
DSC /(mW/mg)
↓ exo
0
400.4 J/g
-50
-100
-150
Paints/Coatings
Adhesives/Inks
Dental Composites
Pharma/Cosmetics
Food/Chemicals
DSC difference curve
-200
2.5
2.0
3.0
Time /min
3.5
4.0
DSC /(mW/mg)
↓ exo
0
-50
second irradiation
first irradiation
Photo-DSC Measurement
and Evaluation
The sample and reference are
irradiated with UV light at a
constant temperature until the
sample is cured. Afterward, the
cured sample and the reference
are irradiated for a second time
for the same duration and at
the same temperature. Finally,
the difference between the
first and second irradiation
is calculated to determine
the pure heat of reaction
(curve subtraction).
-100
-150
-200
0.0
0.5
1.0
Time /min
1.5
2.0
DSC /(mW/mg)
↓ exo
0
DSC /(mW/mg)
0
400.4 J/g
HDDA
-50
-10
-20
-30
-100
-40
-50
-150
-60
oxygen 100%
-170.1 J/g
nitrogen:oxygen
= 50%:50%
DSC difference curve
nitrogen 100%
-267.7 J/g
-377.7 J/g
-70
-200
-80
-90
6
320
2.0
340
2.5 360
380 3.0 400
Time
/min
Time
/s
4203.5
440
460
4.0
0
-10
Paints under Different
Atmospheres
The irradiation for 1s of a sample
of hexanediol diacrylate (HDDA)
was investigated using three
different atmospheres. The heat
of crosslinking was at its highest
under an inert atmosphere of
100% nitrogen (green curve)
with 378 J/g. A mixture of 50%
nitrogen and 50% oxygen yielded
268 J/g (blue curve); a pure
oxygen atmosphere, only 170 J/g
(red curve). There is obviously
a competitive reaction due to
the influence of oxygen.
HDDA
-20
DSC-30
/(mW/mg)
DSC /(mW/mg)oxygen 100%
-40
0
nitrogen:oxygen
0
= 50%:50%
-50
-10
HDDA
-10
HDDA 100%
nitrogen
-60
-20
-20
-70
-30
oxygen 100%
-30
oxygen 100%
-80
-40
nitrogen:oxygen
-40
-90
=nitrogen:oxygen
50%:50%
-50
340
360
-50 320 = 50%:50%
nitrogen 100%
-60
nitrogen 100%
-60
-70
-70
-80
-80
-90
-90 320
340
360
320
340
360
DSC /(mW/mg)
↓ exo
20
-170.1 J/g
-267.7 J/g
-377.7 J/g
-170.1 J/g
-170.1 J/g
-267.7 J/g
-267.7 J/g
380
400
-377.7 Time
J/g /s
-377.7 J/g
420
440
460
380
400
380Time /s 400
Time /s
420
420
440
440
460
460
Temp. /°C
75
70°C
70
0
Adhesives at Different
Temperatures
This fluorescent one-component
modified epoxy resin is activated
with visible light of 400 nm
to 500 nm. A cationic curing
mechanism allows the adhesive to
cure after having assembled the
different components. A higher
temperature accelerates this
reaction. The adhesive is used for
bonding metal, glass, or plastics
and especially for stress-equalizing
bonding or sealing products.
Different Dental Composites
In dental applications, light-curing
dental composites are used as
restoratives (fillings) or veneering
materials. The materials are
generally composed of methacrylate systems such as bis-glycoldimethacrylate (bis-GMA) or
urethane dimethacrylate UDMA).
Additional monomers are used
as diluent or to guarantee the
cross-linking abilities of the
resin. Inorganic fillers up to 80
weight percent improve the
mechanical properties and reduce
shrinkage during cross-linking.
-20
DSC /(mW/mg)
DSC
-40 /(mW/mg)
↓ exo
20 ↓ exo
20
-60
0
0
-80
-20
-20
-100
-40
-40
-120
-60
-60
-140
-80
-80
-160
-100 2.0
-100
-390.1 J/g
65
-291.2 J/g
Temp. /°C
Temp.
60/°C
75
75
55
70
70
50
65
65
45
60
60
40
55
55
35
50
50
-193.5 J/g
70°C
70°C
50°C
-390.1 J/g
-390.1 J/g
-291.2 J/g
-291.2 J/g
-193.5 J/g
-193.5 J/g
50°C
50°C
30°C
2.5
3.0
Time /min
3.5
4.0
-120
-120
40
40
-140
-140
-160
-160 2.0
2.0
45
45
2.5
2.5
30°C
30°C
35
35
3.0
3.0
Time
/min
Time /min
3.5
3.5
DSC /(mW/mg)
↓ exo
0
4.0
4.0
Temp. /°C
70
68
-2
DSC
-4/(mW/mg)
DSC /(mW/mg)
↓ exo
0 ↓ exo
-60
-2
-2
-8
-4
-4
-10
-6
-6
-12
-105.5 J/g
Adamant
-128.4 J/g
Charisma
-137.4 J/g
Admira
-141.5 J/g
Evo Ceram
66
Temp.64
/°C
Temp. /°C
70
70
62
68
68
60
-105.5 J/g
-105.5 J/g
-128.4 J/g
-128.4 J/g
-137.4 J/g
-137.4 J/g
-141.5 J/g
-141.5 J/g
Adamant
Adamant
Charisma
Charisma
Admira
Admira
Evo Ceram
Evo Ceram
66
66
58
64
64
56
62
62
54
-8
-8
-14
-10
-10
2.5
3.0
Time /min
3.5
4.0
56
56
54
54
-12
-12
-14
-14
60
60
52
58
58
52
52
2.5
3.0
3.5
4.0
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The NETZSCH Group is a mid-sized, family-owned German company
engaging in the manufacture of machinery and instrumentation with
worldwide production, sales, and service branches.
The three Business Units – Analyzing & Testing, Grinding & Dispersing and
Pumps & Systems – provide tailored solutions for highest-level needs. Over
3,300 employees at 210 sales and production centers in 35 countries across
the globe guarantee that expert service is never far from our customers.
NETZSCH-Gerätebau GmbH
Wittelsbacherstraße 42
95100 Selb
Germany
Phone.: +49 9287 881-0
Fax: +49 9287 881 505
[email protected]
NGB · Photo-DSC 204 F1 Phoenix® · EN · 0916 · NWS · Technical specifications are subject to change.
When it comes to Thermal Analysis, Calorimetry (adiabatic & reaction) and
the determination of Thermophysical Properties, NETZSCH has it covered.
Our 50 years of applications experience, broad state-of-the-art product line
and comprehensive service offerings ensure that our solutions will not only
meet your every requirement but also exceed your every expectation.