Photo-DSC 204 F1 Phoenix®

Photocalorimetry – Method, Technique and Applications

Analyzing & Testing

 Photo-DSC 204 F1 Phoenix®
Photo-Calorimetry Is an Extension of Classical Calorimetry
for the Investigation of Light-Induced Processes.

Advantages of Photo-Calorimetry Your Benefits

Light- (mostly UV-) curing systems react very quickly (within a few seconds
at low isothermal temperatures) and are solvent-free. This makes them
∙∙Extension of the DSC technique
with light radiation capability

∙∙
very attractive for industrial applications.
Three different types exist: radical, cationic and dual-cure systems. Analysis of photo-initiated
Dual-cure systems exhibit a combiation of thermal and light-curing reactions in materials

∙∙
reactions and can be found, for example, in adhesives or paints.
Measurement of the light or
The ability to measure the curing kinetics and degree of cure is essential for UV-light curing of polymer
the development of UV-curable resins and identification of optimal curing resins, paints, inks, coatings
times and conditions. Photo-differential scanning calorimetry (Photo-DSC) and adhesives

∙∙
is a powerful analytical tool for accomplishing these measurements.
Study of the influence of UV
stabilizers in pharmaceuticals,
cosmetics and foods (aging
effects)

∙∙Optimization of temperature,
atmosphere, light intensity,
wave length and exposure time

∙∙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 meas-
urement 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. Howev-
er, 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 dif-
ferent 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) – automat-
ically 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
∙∙Light source can be triggered
and controlled by DSC
should have filters in the UV-A range between 280 nm and 315 nm and in measurement software (time

∙∙
the UV-B range between 315 nm and 500 nm. control and intensity control)
However, other commercially available lamps can also be adapted. For Radiation impulse is selectable
optimized curing, a defined wavelength (e.g., 447 nm) can be used with by segment, by means of
diode laser systems or high-power LED (e.g., 365 nm, 400 nm or 460 nm) – activation/deactivation through
depending on the resin to be cured. a check box in the temperature

∙∙
The OmniCure® lamp is fully software controlled; selection of temper- program
ature, light intensity, wave length and exposure time can be carried out Selectable delay time for

∙∙
by the DSC Proteus® software. irradiation
The gas-tight construction of the DSC instrument allows for easy Evaluation of effective heat
measurement of the cross-linking of paints; this process is often sensitive of reaction by means of curve
to oxygen, which can act as an inhibitor. subtraction and time offset

∙∙
capability
Determination of relative or
absolute integral (degree of
conversion)

Technical Specifications
Photo-DSC 204 F1 Phoenix®

Temperature range ∙∙∙∙

-100°C to 200°C with irradiation module
Standard DSC measurements: -180°C to 700°C
Crucibles Open aluminum
Automatic Sample Changer (ASC) up to 204 sample pans (option)

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

5
 APPLICATIONS
DSC /(mW/mg)
↓ exo
0

400.4 J/g
-50

-100
Paints/Coatings
-150 DSC difference curve Adhesives/Inks
-200
Dental Composites
Pharma/Cosmetics
Food/Chemicals
2.0 2.5 3.0 3.5 4.0
Time /min

DSC /(mW/mg)
↓ exo
0

-50
second irradiation
first irradiation

-100
Photo-DSC Measurement
and Evaluation -150

The sample and reference are -200

irradiated with UV light at a
constant temperature until the
sample is cured. Afterward, the 0.0 0.5 1.0 1.5 2.0
Time /min
cured sample and the reference
are irradiated for a second time
for the same duration and at
DSC /(mW/mg)
the same temperature. Finally, ↓ exo
the difference between the 0
DSC /(mW/mg)
first and second irradiation
is calculated to determine 0
400.4 J/g
the pure heat of reaction -50
-10 HDDA
(curve subtraction). -20

-30
-100
oxygen 100% -170.1 J/g
-40
nitrogen:oxygen -267.7 J/g
-50 = 50%:50%
-150 DSC difference curve
nitrogen 100% -377.7 J/g
-60

-70
-200
-80

-90
320
2.0 340 2.5 360 380 3.0 400 4203.5 440 460
4.0
Time /min
Time /s

6
 0

-10 HDDA
-20

Paints under Different DSC-30

/(mW/mg)
DSC /(mW/mg)oxygen 100% -170.1 J/g

Atmospheres -40
0
0
nitrogen:oxygen -267.7 J/g
-50 = 50%:50%
-10 HDDA
-10 HDDA 100%
nitrogen -377.7 J/g
-60
The irradiation for 1s of a sample -20
-20
of hexanediol diacrylate (HDDA) -70
-30
-30 oxygen 100% -170.1 J/g
was investigated using three -80
-40
oxygen 100% -170.1 J/g
-40 nitrogen:oxygen -267.7 J/g
different atmospheres. The heat -90
-50 =nitrogen:oxygen
50%:50% -267.7 J/g
of crosslinking was at its highest -50 320 = 50%:50%
340 360 380 400 420 440 460
nitrogen 100% -377.7 Time
J/g /s
-60 nitrogen 100% -377.7 J/g
under an inert atmosphere of -60
-70
100% nitrogen (green curve) -70
with 378 J/g. A mixture of 50% -80
-80
nitrogen and 50% oxygen yielded -90
-90 320
268 J/g (blue curve); a pure 320
340
340
360
360
380 400
380Time /s 400
420
420
440
440
460
460
oxygen atmosphere, only 170 J/g Time /s

(red curve). There is obviously

DSC /(mW/mg) Temp. /°C
a competitive reaction due to ↓ exo 75
the influence of oxygen. 20
70°C
0 70

-390.1 J/g 65
-20
-291.2 J/g
Adhesives at Different
DSC /(mW/mg) Temp. /°C
DSC
-40 /(mW/mg)
↓ exo Temp.
60/°C
20 ↓ exo -193.5 J/g 75

Temperatures 20 75
70°C
-60 70°C 55
0 70
0 70
50°C
-80 -390.1 J/g 50
This fluorescent one-component -20 -390.1 J/g 65
65
-20 -291.2 J/g
modified epoxy resin is activated -100 -291.2 J/g 45
-40 60
with visible light of 400 nm -40 -193.5 J/g
-193.5 J/g
60
-120 40
to 500 nm. A cationic curing -60 55
-60 55
mechanism allows the adhesive to -140 50°C 35
-80 50°C 50
cure after having assembled the -80 30°C 50
-160
different components. A higher -100 2.0 2.5 3.0 3.5 4.0 45
-100 45
temperature accelerates this Time /min
-120 40
reaction. The adhesive is used for -120 40
bonding metal, glass, or plastics -140 35
-140 35
and especially for stress-equalizing 30°C
-160 30°C
bonding or sealing products. -160 2.0 2.5 3.0 3.5 4.0
2.0 2.5 Time3.0
/min 3.5 4.0
Time /min

Different Dental Composites DSC /(mW/mg) Temp. /°C

↓ exo
70
0
In dental applications, light-curing 68
dental composites are used as -2
restoratives (fillings) or veneering -105.5 J/g Adamant 66
-128.4 J/g Charisma
materials. The materials are DSC
-4/(mW/mg) Temp.64
/°C
DSC /(mW/mg)
↓ exo -137.4 J/g Admira Temp. /°C
generally composed of methac- 0 ↓ exo -141.5 J/g Evo Ceram
70
70
62
rylate systems such as bis-glycol- -60
68
dimethacrylate (bis-GMA) or -2
68
60
-2
-8 -105.5 J/g Adamant
urethane dimethacrylate UDMA). -105.5 J/g Adamant
66
66
58
-128.4 J/g Charisma
Additional monomers are used -4 -128.4 J/g
-137.4 J/g
Charisma
Admira 64
-4
-10 64
56
as diluent or to guarantee the -137.4 J/g
-141.5 J/g
Admira
Evo Ceram
-141.5 J/g Evo Ceram 62
cross-linking abilities of the -6
-6
-12
62
54
resin. Inorganic fillers up to 80 60
60
-8 52
weight percent improve the -8
-14 58
mechanical properties and reduce 2.5 3.0 3.5 4.0
58
-10 56
shrinkage during cross-linking. -10 Time /min 56
54
-12 54
-12
52
-14
52 7
-14
2.5 3.0 3.5 4.0
 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
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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.

NGB · Photo-DSC 204 F1 Phoenix® · EN · 0319 · NWS · Technical specifications are subject to change.

NETZSCH-Gerätebau GmbH
Wittelsbacherstraße 42
95100 Selb
Germany
Phone.: +49 9287 881-0
Fax: +49 9287 881 505
at@netzsch.com