Automotive and Engine Technology (2021) 6:275–287

[Link]

ORIGINAL PAPER

Investigations to characterize the interactions of light radiation,

engine operating media and fluorescence tracers for the use
of qualitative light‑induced fluorescence in engine systems
Thorsten Schweizer1 · Heiko Kubach1 · Thomas Koch1

Received: 21 May 2021 / Accepted: 13 October 2021 / Published online: 23 October 2021
© The Author(s) 2021

Abstract
The light-induced fluorescence (LIF) represents an important tool for the continuous improvement and further development
of combustion engine systems regarding efficiency increase. In this work, the interactions between light-emitting diode
(LED) and laser diode light radiation, engine oil/fuel and three fluorescence tracers are investigated on an application-related
investigation system for the design of qualitative LIF experiments. Thereby two efficient light sources for engine combustion
chamber lighting are presented. For different engine oil/fuel tracer combinations, the fluorescence is examined in its intensity
and its spectrum depending on the temperature, concentration and temperature history. With oil temperature variations of
up to 150 °C, changes in the fluorescence spectrum and fluorescence intensities that decrease by up to 80% are evident. For
specific tracer oil/fuel mixtures, concentration-dependent maximum intensities and different temperature history behaviors
can be revealed. The results shown support the design of spectral engine examination setups and give tracer dosage recom-
mendations. Additionally, an engine LIF setup for in-cylinder tracking of engine operating media is presented.

Keywords Light-induced fluorescence · Engine combustion Chamber lighting · Concentration/temperature

characterization · Doped engine operating media · Engine LIF setup

Abbreviations 1 Introduction
LIF Light-induced fluorescence
LED Light-emitting diode On the way to climate-neutral mobility, the increasingly
SPF Short-pass filter complex development and improvement of engine systems
PM567A Pyrromethene 567A are of indispensable relevance. An increase in overall system
LSPI Low-speed pre-ignition efficiency depending on the specific engine system is sub-
PID Proportional-integral-derivative jected to a variety of conflicting goals (efficiency, emissions
RPM Revolutions per minute behavior, customer requirements, etc.) and therefore requires
BMEP Brake mean effective pressure efficient research and development tools. Light-induced fluo-
SP-F Short pass filter rescence is a tried and tested tool for questions of a qualita-
LP-F Longpass filter tive [1] and quantitative [2] nature. This study presents a
pragmatic test system for investigating the interactions of
laser and LED radiation with fluorescence tracers and liquids
as well as two inexpensive high-power light sources which
can be used for in-cylinder high-speed observations [3, 4].
The influencing parameters concentration, temperature and
* Thorsten Schweizer aging are examined with engine oils for modern downsiz-
[Link]@[Link] ing units with three different oil/tracer combinations in their
Heiko Kubach fluorescence behavior. In addition, an oil/tracer combination
[Link]@[Link] is assessed after the use in a combustion engine at a pre-
1 ignition load point. Furthermore, the concentration behav-
Institut für Kolbenmaschinen (IFKM), Karlsruher Institut
Für Technologie (KIT), Kaiserstraße 12, 76131 Karlsruhe, ior of a fuel/tracer combination is characterized. With these
Germany findings, especially qualitative engine LIF experiments can

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276 Automotive and Engine Technology (2021) 6:275–287

be efficiently planned and designed. One application is the static fluorescence quenching. With dynamic fluorescence
tracking of engine operating media movements and accu- quenching, also called collision fluorescence quenching, the
mulations within the combustion chamber via minimally excited state of the fluorophore is deactivated by contact
invasive endoscopic accessibilities, which can be used for with another molecule (quencher) in the solution. There are
pre-ignition mechanism synthesis [3, 4]. In the following, a large number of molecules that can act as collision quench-
the physical principles of fluorescence and fluorescence ers. A very prominent representative is oxygen. Quenching
quenching that are relevant to understand the results shown effects can also appear between the fluorescent molecules
are briefly outlined. For a more detailed description of the themselves, which is also known as concentration fluores-
complex molecular processes, reference should be made to cence quenching. In addition to the diffusion and collision-
the relevant specialist literature [5]. dominated effects, the complex formation of fluorescence
quenchers and fluorophores in the ground state can lead
1.1 Principle of light‑induces fluorescence to a loss of intensity. These processes are known as static
quenching. In addition, quenching effects can also occur due
For certain molecules, fluorescence can result from a three- to non-molecular processes such as the absorption of excita-
step process (see Fig. 1). In the first step the light energy of tion light by specific species. Long exposure to excitation
a photon (external excitation light source) is absorbed; an light can also lead to photobleaching (chemical quenching).
excited electron state S2 occurs (excitation). In the follow- The ability of a molecule to fluoresce can be permanently
ing excited state, which is limited in time, there are con- destroyed [5].
formational changes in the molecule and a large number of
possible interactions with its environment. Due to energy
dissipation, the fluorescence energy level S1 is below the 2 Investigation system and methodology
excitation energy level. This energy level can be emptied
by further processes (static and dynamic quenching, förster Figure 2 shows an overview of the applied LIF examination
resonance energy transfer or intersystem crossing), which system. An Acton SP2556 optical spectrometer from Prince-
reduces the quantum yield of the fluorescence radiation. In ton Instruments (focal length of 500 mm) with a 200 μm
the third step, the molecule returns to its ground state S0, entrance slit in combination with the image-intensified CCD
releasing photons (emission). The energy difference result- camera Princeton Instruments PI-MAX is used to record the
ing from the dissipation in the second step is known as the emission spectra. The maximum resolution corresponds to
Stokes shift [6]. 1024 × 256 pixels. The grating used for all experiments was
150 g/mm, which results in a detection range of approxi-
1.2 Fluorescence quenching mately 192 nm. The resolution is approx. 0.2 nm. A fiber
optic bundle with optical transmission of 190–1100 nm
A reduction in the fluorescence intensity can be triggered is used as a light guide for receiving and introducing the
by a wide variety of processes and is generally called (fluo- fluorescent light, which is held at right angles to the exci-
rescence) quenching. The excitation is deactivated without tation light source in the beaker at a small distance above
the emission of a photon. Basically, there is dynamic and the liquid. The recording is made via the Spectrograph PC
using WinSpec software. The trigger signal is recorded by
an additional measuring unit for the fluorescence spectrum/
temperature correlation.
The excitation light is introduced on the side of the beaker
just below the surface of the liquid at a short distance. For
this purpose, the LED and laser systems are each fixed in a
defined manner with a support structure. The light sources
are energized shortly before the start of the measuring point
via a laboratory power supply unit with defined param-
eters for a quantitative comparison of fluorescence inten-
sity within a series of measurement. The excitation light
intensity, defined by the set current, was slightly adapted
for the specific tracer/fluid combination considering the
intensity measuring range (Stoke-shifted fluorescent light)
of the spectrometer. A quantitative comparison between the
Fig. 1  Perrin Jablonski diagram of fluorescence and phosphorescence measurement series is only partially meaningful due to spe-
(Photophysics of fluorescent proteins 2020 [12]) cific sources of measurement errors or uncertainties listed

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Automotive and Engine Technology (2021) 6:275–287 277

Fig. 2  Scheme of the fluores-

cence investigation system with
signal paths

below. Specific intensities of the excitation light were not sources were typically operated with about 2.5 A direct cur-
measured. Using a magnetic stirrer with integrated tempera- rent. The LED was cut in her spectral range with a 500 nm
ture control, the liquid/tracer mixture can be tempered and short-pass filter (SPF) and her light is guided to the beaker
stirred in a defined manner. The movement of the liquid via a quartz glass rod through an engine access sleeve. The
leads to a more homogeneous temperature distribution and specific emissions spectra from the lighting systems can be
avoids the cross-influence of photobleaching effects on the seen in Fig. 3.
measurement results. Three fluorescence tracers have been examined: BASF
­Oracet® Yellow 084 (452.5 g/mol) ­(Oracet® 084), Honey-
2.1 Engine operating media, light sources well ­Lumilux® Yellow CD 345 (555.8 g/mol) ­(Lumilux® CD
and tracer 345), Pyrromethene 567A (374.3 g/mol) (PM567A). These
could be directly dissolved in the media and showed a clear
The oil/tracer tests were carried out with the engine oils fluorescence response when excited with the featured light
Fuchs Titan Supersyn F ECO-B 5 W-20 (Fuchs 5W20), sources. Pyrromethene 597-8C9 also showed good solubil-
Titan Supersyn F Eco-DT 5 W-30 (Fuchs 5W30) and Cas- ity but not a good quantum yield with the light sources.
trol Magnatec Stop-Start 5 W-20 E (Castrol). These are oils DCM and Rhodamine 6G could not be directly dissolved
especially designed for modern Ford gasoline and diesel in the described engine oils. However, it should be pointed
engines. The fuel/tracer tests were carried out with CORY- out that there are various mediators for the dissolution of
TON advanced fuels “High LSPI” fuel. It has a RON value these tracers, which were not considered in this study. This
of 96.5 and is in accordance with the DIN EN 228 standard was derived from the idea of influencing the properties of
(DIN EN 228 [7]). the engine operating media as little as possible. Interesting
Light sources for engine examinations and especially solvents, considering the later use in engine oil, for DCM
for the implementation of LIF measurements should have a could be n-Hexane, n-Propanol and Vaseline oil [8]. The
narrow spectral range and a high beam power. In addition, absorption of DCM dye in ethanol is descripted in [9]. The
a compact design is advantageous for an efficient engine fluorescence characteristics of Rhodamine 6G in ethanol and
system integration. For the presented results a compact 7 W butanol are investigated in [10]. Detailed different organic
laser diode (NUBM44) with 3 optical lenses for beam shap- solvents effects of Rhodamine 6G can be found in [11].
ing as well as a high-performance LED (Osram OSTAR​
®
Projection Power LE B P3W 01) were used. Both light

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278 Automotive and Engine Technology (2021) 6:275–287

Fig. 3  Spectra of the light 1.1 1.1

sources used (left: laser diode at 1 449.5 1 472.1

S i gnal i ntensity / arb. uni t

S i gnal i ntensity / arb. uni t

0.5 A; right: LE B P3W 01 with 0.9 0.9
500 nm SPF 0.8 0.8
0.7 0.7
0.6 0.6
0.5 0.5
0.4 0.4
0.3 0.3
0.2 0.2
0.1 0.1
0 0
444 446 448 450 452 454 456 425 440 455 470 485 500 515
Wavelength / nm Wavelength / nm

2.2 Sample preparation temperatures, an oil/tracer combination in the beaker is con-

tinuously heated up to 150 °C on a magnetic stirrer. The
Fresh oil and fuel were each weighed to 200 ml and enriched heating behavior is determined by the settings of the internal
with the specific tracer quantities in Duran beakers. The control circuit of the magnetic stirrer (PID controller) and
tracer quantities were prepared using a precision balance recorded via an external unit. The same setting parameters
(Sartorius ENTRIS224-1S). For mixing, the fuel/tracer mix- (plate temperature: 300 °C, target temperature 170 °C) are
tures were each stirred for 5 min using a magnetic stirrer at used for all temperature tests presented. From 30 °C, three
1500 rpm. Afterwards the oil/tracer mixtures were also dis- spectrographic measurements are carried out every 10 °C.
solved in an ultrasonic bath at 60 °C for 20 min. A stir bar (750 rpm) in the asymmetrically attached beaker
ensures a more homogeneous temperature distribution in the
2.3 Investigation methodology oil volume. Spectrometer and light source parameters are set
as described above.
For LIF applications, in addition to the general spectral To characterize the aging behavior, two specific oil/tracer
response due to the combination of light, medium and tracer, mixtures were subjected to two temperature series meas-
knowledge of temperature, concentration and aging behavior urements with an interval of one week each (stored in the
is necessary for the design of the experiment. beaker at room temperature). In the second attempt, the sam-
To investigate the fluorescence characteristics (intensity, ples are thus subject to a temperature and time history. In
spectrum) of different tracer concentrations in oil and fuel, addition, an oil/tracer combination was used as lubricating
a defined amount of tracer is dissolved in the liquid medium oil in a combustion engine and spectrally examined after the
(200 ml) and then spectrally examined at 30 °C in the beaker use in a twenty-minute pre-ignition operation (1600 rpm,
when excited by laser or LED light. Starting with the small- 200 Nm, BMEP 25.2 bar). This resulted in great mechanical
est amount of tracer, the concentration is consecutively stress and contamination with fuel and combustion residues
increased in discrete steps in the same beaker. The beaker is of the oil/tracer combination.
removed for preparation after each measurement and then Reference should be made to the following specific
reinserted into the measuring device. Defined stops ensure sources of measurement errors or uncertainties in the exami-
a constant measuring position for the beaker, light intro- nation system:
duction and fluorescence signal recording. The respective The mixing process of medium and tracer can lead to
concentration series are recorded at constant temperature, concentration fluctuations. A slight rotational position
spectrometer and light source parameters to ensure a quan- change of the beaker can lead to an influence of different
titative relative comparison within a measurement series. wall thicknesses on the light intensity and refraction. The
The spectrometer (amplification factor, exposure time) and media expansion during a temperature series results in a
light source parameters (voltage, current) are coordinated change in the distance between the position of the liquid
with each other before each series of examinations so that surface and the light guide.
the lowest expected fluorescence intensity clearly stands out
from the measurement noise and the strongest fluorescence
intensity does not exceed the maximum measurement limits. 3 Results and discussion
A quantitative comparison of different measurement series
is therefore not permitted. For each measurement, all spectral measurement results
To examine the fluorescence characteristics (intensity, consist of the mean value of three individual measurements
spectrum) of specific tracer concentrations at different oil taken in quick succession. The examined tracer/liquid

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Automotive and Engine Technology (2021) 6:275–287 279

combinations represent a very complex system due to the 3.2 BASF O

­ racet® yellow 084
large number of different molecules and the associated great
potential for interaction. The mechanisms mentioned in the 3.2.1 Concentration characterization
discussion are only intended to represent a rough classifica-
tion of the general topic and not claim to be complete. Figure 5 shows the emission spectra of ­Oracet® 084 at 30 °C
in Fuchs 5W20 at different tracer concentrations and the
3.1 Self‑fluorescence engine operating media associated standardized signal intensity and peak wavelength
as a function of the concentration when excited by means of
Figure 4 shows the self-fluorescence spectrum of the engine a laser diode. The temperature-shifted excitation spectrum
oils Fuchs 5W20 and Castrol (left) when excited with the of the laser diode can be seen in the area around 465 nm.
laser diode, normalized to the maximum intensity as well (In comparison to Fig. 3, the spectrum shift results in par-
as laser light passing through the “High LSPI” fuel without ticular from the operation of the diode with larger numbers
generating a fluorescence answer (right). Due to the very of amperes.) The spectrum is characterized by a double peak
weak fluorescence signal and the necessary amplification at 490 and 515 nm and is strongly dependent on the con-
factors on the spectrograph, the laser excitation source can centration. With increasing tracer concentration, the relative
be clearly seen (at ~ 465 nm) and exceeds the signal strength signal intensity difference between the peaks increases and
of the autofluorescence despite right-angled signal record- the 515 nm peak becomes increasingly dominant. A self-
ing. The spectrum of the laser diode is slightly red-shifted fluorescence excitation that increases with the concentration
due to the high operating temperature. The measuring range can be responsible for this. No relevant peak wavelength
of the spectrograph ends shortly after 625 nm. The maxima change can be observed. The concentration-dependent maxi-
of the emission spectra are around 520 nm for Fuchs 5W20 mum fluorescence intensity shows a maximum in the range
and 530 nm for Castrol. When the “High LSPI” fuel is irra- between 6 and 8 mg O ­ racet® 084. Thereafter, probably the
diated, no self-fluorescence can be detected for any light increase in dynamic quenching effects in the form of increas-
source. ing collision quenching leads to a decreasing fluorescence
intensity. At 16 mg the solubility limit seems to be reached,
which is characterized by the tracer molecules beginning to
settle on the bottom of the beaker.

Fig. 4  Self-fluorescence spectra 1.1

of Castrol (purple, dashed) and 1
S i gnal i ntensity / arb. uni t

Fuchs 5W20 (green) (left); 0.9 520.2

Laser beam passing through 0.8
“High LSPI” fuel (right) 0.7
0.6
0.5
0.4
0.3 530.6
0.2
0.1
0
450 475 500 525 550 575 600 625 650
Wavelength / nm

Fig. 5  Emission spectra of 34000 1.1 533

­Oracet® 084 in 200 ml Fuchs 2 mg 1.0 530
S i gnal i ntensity / arb. uni t
S i gnal i ntensity / counts

5W20 (30 °C) with different 4 mg

Peak wavelength / nm

27200 0.9 527

tracer concentrations (left); 6 mg 0.8 524
Normalized signal intensity and 20400 8 mg 0.7 521
peak wavelength as a function 10 mg 0.6 518
of the ­Oracet® 084 concentra- 13600 12 mg 0.5 515
0.4 512
tion in 200 ml Fuchs 5W20 14 mg
0.3 509
(right)) 6800
16 mg
0.2 Signal intensity 506
0.1 Peak wavelength 503
0 0.0 500
450 475 500 525 550 575 600 625 650 0 2 4 6 8 10 12 14 16 18
Wavelength / nm Oracet® 084 / mg

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280 Automotive and Engine Technology (2021) 6:275–287

Oracet® 084 also shows comparable double peak charac- increase in the temperature-dependent diffusion potential
teristics in Castrol oil (Fig. 6). The emission maximum for presumably leads to severe collision quenching. The first
the investigated step size of 3 mg is at 6 mg ­Oracet® 084. emission peak decreases over proportionally with increasing
A change in peak wavelength is not observed. The relative temperature and the spectrum becomes single peaked. The
signal intensity difference between the peaks increases and, Stokes shift remains constant.
at high concentrations, leads to a strong decrease in the first Figure 8 shows the normalized signal intensities and
peak. The underlying physical effects could be analogous to peak wavelengths as a function of temperature, concentra-
the 5W20 sample. tion and number of tempering when excited by means of a
laser diode in Fuchs 5W20. The two concentrations 7 mg
3.2.2 Temperature and aging characterization and 16 mg show a marked difference in temperature behav-
ior. When the 7 mg mixture is heated for the first time, the
To characterize the temperature dependence of the emission fluorescence intensity increases to 70 °C and then drops to
spectrum on specific tracer concentrations, this is recorded about 60% of the maximum intensity at 150 °C. The spec-
in 10 °C steps from 30 to 150 °C oil temperature. Aging is trum at 30 °C and 150 °C shows a slightly enlarged Stokes
shown by running a temperature series twice per concentra- shift. There is a comparable peak behavior to Fig. 7. In
tion at a time interval of one week. general, additional oxidation effects of the oil seem to
Figure 7 shows the emission spectra of 7 mg ­Oracet® 084 influence the system behavior. The second heating, how-
in 200 ml Fuchs 5W20 at different mixture temperatures dur- ever, leads to a continuous decrease in intensity to about
ing the second heating cycle and the associated standardized 40% of the initial level and shows a constant Stokes shift.
signal intensity and peak wavelength as a function of the The first heating of the 16 mg mixture leads to a continu-
temperature when excited by means of a laser diode. 7 mg ous decrease to below 20% of the maximum intensity with
was in the concentration area of maximum signal intensity at a slight increase (approx. 2%) in the last temperature point.
30 °C in the concentration characterization test. As a result The Stokes shift remains at a constant level with a slight
of the increase in oil temperature, there are more and more increase at 150 °C. Compared to the 7 mg mixture, it is on
quenching effects and thus a pronounced decrease in fluores- a slightly higher level. The second heating of the 16 mg
cence intensity down to about 40% of the initial level. The mixture leads to a continuous decrease in the fluorescence

Fig. 6  Emission spectra of 1400 1.1 533

­Oracet® 084 in 200 ml Castrol 3 mg 1.0 530
S i gnal i ntensity / arb. uni t
S i gnal i ntensity / counts

(30 °C) with different tracer 6 mg 0.9 527

Peakwavelength / nm
1120
concentrations (left); Normal- 9 mg 0.8 524
ized signal intensity and peak 12 mg 0.7 521
840
wavelength as a function of the 15 mg 0.6 518
­Oracet® 084 concentration in 560
0.5 515
200 ml Castrol (right)) 0.4 512
0.3 509
280 0.2 Signal intensity 506
0.1 Max. wavelength 503
0 0.0 500
450 475 500 525 550 575 600 625 650 0 3 6 9 12 15 18
Wavelength / nm Oracet® 084 / mg

Fig. 7  Emission spectra of 32000

T_Oil 30°C
­Oracet® 084 (7 mg) in Fuchs T_Oil 40°C
1.1 533
5W20 (200 ml) at differ- 1.0 530
S i gnal i ntensity / arb. uni t

T_Oil 50°C
Peak wavelength / nm

0.9 527
ent temperatures during the 24000 T_Oil 60°C
S i gnal i ntensity / counts

T_Oil 70°C 0.8 524

second heating (left); Normal- T_Oil 80°C 0.7 521
ized signal intensity and peak T_Oil 90°C
0.6 518
wavelength as a function of 16000 T_Oil 100°C
0.5 515
temperature (right)
T_Oil 110°C
T_Oil 120°C 0.4 512
T_Oil 130°C 0.3 509
8000 T_Oil 140°C 0.2 506
Signal intensity
T_Oil 150°C
0.1 Peak wavelength 503
0.0 500
0 20 40 60 80 100 120 140 160
450 475 500 525 550 575 600 625 650 Oil temperature / °C
Wavelength / nm

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Automotive and Engine Technology (2021) 6:275–287 281

Fig. 8  Normalized signal inten- 1.1 530

Oracet® 084 7mg 1st heating
sity (left) and peak wavelength 1.0
Oracet® 084 7mg 2nd heating
525
(right) as a function of the 0.9 Oracet® 084 16mg 1st heating
­ racet®

Signal inte nsity / arb. unit

temperature of different O 0.8 Oracet® 084 16mg 2nd heating

Pe ak wave le ngth / nm
520
084 concentrations and the 0.7

number of temperature series in 0.6

515
200 ml Fuchs 5W20 0.5 Oracet® 084 7mg
1st heating
0.4
Oracet® 084 7mg 510
0.3 2nd heating
Oracet® 084
0.2 16mg 1st heating 505
0.1 Oracet® 084
16mg 2nd heating
0.0 500
20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
Oil temperature / °C Oil temperature / °C

1.1 533 80 °C. (A second heating with the Castrol oil was not car-
1.0 530 ried out.)
0.9 527
Higher concentrations show a greater variance in the gra-
Signal inte nsity / arb. unit

0.8 524
dient of the signal intensity curve. An initial steeper decrease
Peak wavelength / nm
and a flatter course at higher temperatures, which generally
0.7 521
0.6 518
speaks for increased interactions compared to low tracer
0.5 515
0.4 512
dosages. It can be assumed that a slightly increased concen-
0.3 509
tration in comparison to the 30 °C maximum intensity con-
0.2 506 centration could be advantageous for temperature and aging
0.1 503 effects with regard to a maximum fluorescence intensity.
0.0 500 Higher concentrations tend to shift the emission spectrum
20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
Oil temperature / °C
slightly to red, especially under the influence of temperature.
Signal intensity Oracet® 084 8mg 1st heating Signal intensity Oracet® 084 8mg 2nd heating
Signal intensity Oracet® 084 20mg 1st heating Peak wavelength Oracet® 084 8mg 1st heating 3.3 Honeywell ­Lumilux® yellow CD 345
Peak wavelength Oracet® 084 8mg 2nd heating Peak wavelength Oracet® 084 20 mg 1st heating

3.3.1 Concentration characterization
Fig. 9  Normalized signal intensity and peak wavelength as a function
of the temperature of different O­ racet® 084 concentrations and the
number of tempering in 200 ml Castrol Figure 10 shows the emission spectra of Honeywell
­Lumilux® CD 345 in Fuchs 5W20 (30 °C) at different
tracer concentrations as well as the associated standardized
intensity up to 130 °C to about 32% of the initial intensity, signal intensity and peak wavelength as a function of the
after which a slight increase to about 40% at 150 °C can concentration when excited by means of a laser diode. In
be observed. The Stokes shift in the temperature range of the area around 462 nm, the temperature-shifted excitation
30–60 °C is at the level of the 7 mg mixture. From 70 °C spectrum of the laser diode can be seen again. The spectrum
it corresponds to the level when the 16 mg mixture was is characterized by a double peak (499 and 524 nm) and
heated for the first time. is strongly dependent on the concentration. A signal inten-
Figure 9 shows the normalized signal intensities and peak sity difference between the peaks that increases relative to
wavelengths as a function of temperature, concentration and the concentration can only be observed weakly. The second
number of tempering when excited by means of a laser diode peak becomes more dominant as the concentration increases.
in 200 ml of Castrol. In Castrol oil there is a very compara- The concentrations 4 and 6 mg show a slightly dominant
ble picture. When heated for the first time, the 8 mg mixture first peak, which is why there is a peak wavelength shift
shows its maximum intensity at 60 °C, after which it drops here. The concentration-dependent fluorescence intensity
to about 75% of the maximum intensity. The second heating shows a maximum in the range around 12 mg ­Lumilux®
leads to a continuous decrease in intensity to about 54% of CD 345. After that, quenching effects will probably occur
the initial intensity. Both series of tests show an approxi- more intensely, analogous to ­Oracet® 084.
mately constant Stokes shift. The significantly higher dosed Figure 11 shows the emission spectra of ­Lumilux® CD
sample (20 mg) shows a very strong drop to 80 °C to about 345 in Coryton “High LSPI” fuel (17 °C) at different
24% of the initial intensity when heated for the first time. At tracer concentrations as well as the associated standard-
150 °C it still has about 17% of the intensity. In the Stokes ized signal intensity and peak wavelength as a function of
shift, an increased level can be observed, especially from the concentration when excited by LED light. In contrast

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282 Automotive and Engine Technology (2021) 6:275–287

Fig. 10  Emission spectra of 32000 1.1 534

­Lumilux® CD 345 in Fuchs 2 mg 1.0 530

S i gnal i ntensity / arb. uni t

S i gnal i ntensity / counts
4 mg
5W20 (30 °C) with different

Peak wavelength / nm
25600 0.9 526
6 mg
tracer concentrations (left); 8 mg 0.8 522
Normalized signal intensity and 19200 10 mg 0.7 518
peak wavelength as a func- 12 mg 0.6 514
tion of the ­Lumilux® CD 345 12800
14 mg 0.5 510
16 mg 0.4 Signal 506
concentration in Fuchs 5W20
0.3 intensity 502
(right) 6400 0.2 Peak 498
0.1 wavelength 494
0 0.0 490
450 475 500 525 550 575 600 625 650 0 2 4 6 8 10 12 14 16 18
Wavelength / nm Lumilux® CD 345 / mg

to the oil, the spectrum is characterized by a single peak 3.3.2 Temperature and aging characterization
at 527 nm and is strongly dependent on the concentration.
The single peak characteristic must be due to the different The characterizations take place analogously to the ­Oracet®
molecular composition of the liquid. The concentration- 084 examinations. Figure 12 shows the emission spectra of
dependent fluorescence intensity shows a maximum in 11 mg ­Lumilux® CD 345 in 200 ml Fuchs 5W20 at differ-
the range between 26 and 33 mg L ­ umilux® CD 345. After ent mixture temperatures during the second heating cycle
that, the quenching effects increase again. In a direct com- and the associated standardized signal intensity and peak
parison to engine oil, there is a significantly better solu- wavelength as a function of the temperature when excited
bility and a greater concentration potential. by means of a laser diode. As a result of increasing quench-
ing effects, there is a pronounced decrease in fluorescence
intensity down to 37% of the initial level with increasing oil
temperature. In all temperature series, the first emission peak

Fig. 11  Emission spectra of 15000

2 mg
­Lumilux® CD 345 in Coryton 4 mg 1.1 542
6 mg 1.0 540
“High LSPI” (17 °C) with
S i gnal i ntensity / arb. uni t

12000 8 mg

Peak wavelength / nm
10 mg 0.9 538
different tracer concentrations
S i gnal i ntensity / counts

12 mg 0.8 536
(left); Normalized signal inten- 14 mg
0.7 534
16 mg
sity and peak wavelength as a 9000 18 mg 0.6 532
function of the ­Lumilux® CD 20 mg
22 mg 0.5 530
345 concentration in Coryton 6000
24 mg
0.4 528
26.5 mg
"High LSPI" (right)) 29.5 mg 0.3 526
33 mg
35 mg 0.2 Signal intensity 524
3000 37.5 mg 0.1 Peak wavelength 522
0.0 520
0 0 4 8 12 16 20 24 28 32 36 40
450 475 500 525 550 575 600 625 650 Lumilux® CD 345 / mg
Wavelength / nm

Fig. 12  Emission spectra of 35000

T_Oil 30°C
­Lumilux® CD 345 (11 mg) in T_Oil 40°C
1.1 542
Fuchs 5W20 (200 ml) at dif- 1.0 539
S i gnal i ntensity / arb. uni t

T_Oil 50°C
28000
Peak wavelength / nm

0.9 536
ferent temperatures during the T_Oil 60°C
S i gnal i ntensity / counts

T_Oil 70°C 0.8 533

second heating (left); Normal- T_Oil 80°C
0.7 530
ized signal intensity and peak 21000 T_Oil 90°C
0.6 527
T_Oil 100°C
wavelength as a function of T_Oil 110°C 0.5 524
temperature (right) 14000 T_Oil 120°C 0.4 521
T_Oil 130°C
T_Oil 140°C 0.3 518
T_Oil 150°C 0.2 Signal intensity 515
7000
0.1 Peak wavelength 512
0.0 509
0 20 40 60 80 100 120 140 160
450 475 500 525 550 575 600 625 650 Oil temperature / °C
Wavelength / nm

13

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Automotive and Engine Technology (2021) 6:275–287 283

decreases with increasing temperature and the spectrum shows a more comparable temperature behavior of the dif-
becomes single peaked. The Stokes shift remains constant. ferent concentrations. Higher concentrations show again a
Figure 13 shows the normalized signal intensities and greater variance in the gradient of the signal intensity curve.
peak wavelengths as a function of temperature, concentra- Overall, ­Lumilux® CD 345 and ­Oracet® 084 show a very
tion and number of tempering when excited by means of a comparable system behavior. Again, a slightly increased
laser diode (Fuchs 5W20). The two concentrations 11 mg concentration in comparison to the 30 °C maximum inten-
and 16 mg show a marked difference in temperature behav- sity concentration could be advantageous for temperature
ior. When the 11 mg mixture is heated for the first time, there and aging effects with regard to a maximum fluorescence
is a sharp drop in intensity up to 60 °C and a subsequent intensity. Aging investigations of fuel/tracer mixture have
increase to 80 °C until it drops again to around 46%. The not been done due to the fuel evaporation characteristics.
second heating, however, leads to a continuous decrease in
intensity to about 37% of the initial level. Both temperature 3.4 Pyrromethene 567A
series show a constant Stokes shift. Here, too, oil oxidation
effects seem to influence the fluorescence. The first heating 3.4.1 Concentration characterization
of the 16 mg mixture leads to a continuous decrease in the
fluorescence intensity with the exception of the 90 °C value Figure 14 shows the emission spectra of PM567A in Fuchs
to a final level of approx. 31%. The Stokes shift remains at 5W20 (30 °C) at different tracer concentrations and the asso-
a constant level with slight fluctuations. The second heat- ciated standardized signal intensity and peak wavelength as
ing leads to a continuous decrease to 46% of the maximum a function of the concentration when excited by means of
intensity. The Stokes shift is constant with the exception of a laser diode. The spectrum has a peak at 546 nm and is
the 30 °C value. In general, the second temperature series strongly dependent on the concentration. A slight redshift

1.1 540
Lumilux® CD 345 11mg 1st heating
1.0 Lumilux® CD 345 11mg 2nd heating
0.9 535 Lumilux® CD 345 16mg 1st heating
Lumilux® CD 345 16mg 2nd heating
Signal inte nsity / arb. unit

0.8
Pe ak wave le ngth / nm

530
0.7
0.6
525
0.5
0.4 Lumilux® CD 345
11mg 1st heating 520
0.3 Lumilux® CD 345
11mg 2nd heating
0.2 Lumilux® CD 345 515
16mg 1st heating
0.1 Lumilux® CD 345
16mg 2nd heating
0.0 510
20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
Oil temperature / °C Oil temperature / °C

Fig. 13  Normalized signal intensity (left) and peak wavelength (right) as a function of the temperature of different ­Lumilux® CD 345 concentra-
tions and the number of temperature series in 200 ml Fuchs 5W20

Fig. 14  Emission spectra 25000 1.1 552

of PM567A in Fuchs 5W20 8 mg 1.0 551
S i gnal i ntensity / arb. uni t
S i gnal i ntensity / counts

(30 °C) with different tracer

Peak wavelength / nm

20000 10 mg 0.9 550

concentrations (left); Normal- 12 mg 0.8 549
ized signal intensity and peak 15000 14 mg 0.7 548
wavelength as a function of the 16 mg 0.6 547
PM567A concentration in Fuchs 0.5 546
10000
0.4 545
Titan Super 5W20 (right)
0.3 544
5000 0.2 543
Signal intensity
0.1 Peak wavelength 542
0 0.0 541
450 475 500 525 550 575 600 625 650 6 8 10 12 14 16 18
Wavelength / nm PM 567A / mg

13

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284 Automotive and Engine Technology (2021) 6:275–287

with increasing concentration can be seen. Up to 16 mg a Figure 17 shows the normalized signal intensities and
steady increase in intensity is visible and a slight redshift is peak wavelengths as a function of temperature, concentra-
indicated. The concentration limit is not reached. tion and number of tempering when excited by means of a
Figure 15 shows the emission spectra of PM567A in laser diode in Fuchs 5W20 and in Fuchs 5W30. Both tem-
Fuchs 5W30 (30 °C) at different tracer concentrations and perature series with 16 mg and excitation by means of a
the associated standardized signal intensity and peak wave- laser diode show a very similar behavior in terms of both
length as a function of the concentration when excited by the decrease in intensity and the redshift. The concentration
means of LED light. The excitation spectrum of the LED of 25 mg in Fuchs 5W30 also shows a comparable intensity
can be observed weakly in the range around 468 nm. The behavior, but with a flatter intensity loss curve up to 70 °C.
spectrum shows an increasing redshift with increasing con- An overall larger Stokes shift can be observed due to the
centration. Up to 25 mg PM567A, a flat increase in intensity higher concentration. Despite the greatest loss of intensity,
is visible, which indicates that the maximum concentration PM567A shows the most similar behavior across all test
potential will soon be reached. series, which suggests good temperature stability. (A second
heating with 25 mg PM567A was not carried out.)

3.4.2 Temperature and aging characterization 3.5 Spectral comparison

Figure 16 shows the emission spectra of 16 mg PM567A Figure 18 shows the spectral comparison of the tracers
in 200 ml Fuchs 5W20 at different mixture temperatures in examined in Fuchs 5W20 when excited with a laser diode
the second heating cycle and the associated standardized and LED. The laser spectra are recorded at an oil tempera-
signal intensity and peak wavelength as a function of the ture of 120 °C, whereas the LED spectra are recorded at
temperature when excited by means of a laser diode. With 30 °C. This can be seen in the temperature-sensitive Stokes
the exception of the 70 °C value, a constant drop in intensity shift of PM567A. Otherwise the characteristic features of
down to approx. 19% can be observed. In contrast to O ­ racet® the emission spectra are very similar. The tracer amounts
084 and L­ umilux® CD 345, PM567A shows a pronounced have been 7 mg for O­ racet® 084, 11 mg for L­ umilux® CD
®
redshift with increasing temperature. 345 and 16 mg for PM567A. ­Oracet 084 has the smallest

Fig. 15  Emission spectra 25000 1.1 566

of PM567A in Fuchs 5W30 14mg 1.0 564
S i gnal i ntensity / arb. uni t
S i gnal i ntensity / counts

(30 °C) with different tracer 18mg

Peak wavelength / nm
20000 0.9 562
21mg
concentrations (left); Normal- 0.8 560
25mg
ized signal intensity and peak 15000 0.7 558
wavelength as a function of the 0.6 556
PM567A concentration in Fuchs 0.5 554
10000 0.4 552
5W30 (right)
0.3 550
5000 0.2 548
Signal intensity
0.1 Peak wavelength 546
0 0.0 544
450 475 500 525 550 575 600 625 650 12 14 16 18 20 22 24 26
Wavelength / nm PM 567A / mg

Fig. 16  Emission spectra of 35000

T_Oil 30°C
PM567A (16 mg) in Fuchs T_Oil 40°C
1.1 573
5W20 (200 ml) at differ- 1.0 570
S i gnal i ntensity / arb. uni t

28000 T_Oil 50°C

Peak wavelength / nm

0.9 567
ent temperatures during the
S i gnal i ntensity / counts

T_Oil 60°C
0.8 564
second heating (left); Normal- T_Oil 70°C
0.7 561
ized signal intensity and peak 21000 T_Oil 80°C
0.6 558
T_Oil 90°C
wavelength as a function of T_Oil 100°C 0.5 555
temperature (right) 14000 T_Oil 110°C 0.4 552
T_Oil 120°C 0.3 549
T_Oil 130°C 0.2 546
Signal intensity
7000 T_Oil 140°C 0.1 Peak wavelength 543
T_Oil 150°C
0.0 540
0 20 40 60 80 100 120 140 160
450 475 500 525 550 575 600 625 650 Oil temperature / °C
Wavelength / nm

13

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Automotive and Engine Technology (2021) 6:275–287 285

1.1 575
1.0
570
0.9
Signal inte nsity / arb. unit

0.8

Pe ak wwave le ngth / nm
565
0.7
560
0.6
0.5 555
0.4
0.3 550
PM567A 16mg 1st heating 5W20 PM567A 16mg 1st heating 5W20
0.2
PM567A 16mg 2nd heating 5W20 545 PM567A 16mg 2nd heating 5W20
0.1
PM567A 25mg 1st heating 5W30 PM567A 25mg 1st heating 5W30
0.0 540
20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
Oil temperature / °C Oil temperature / °C

Fig. 17  Normalized signal intensity (left) and peak wavelength (right) as a function of the temperature of different PM567A concentrations and
number of tempering

1.1
512.9 524.0 563.9
on the tracer/oil mixture. Subsequently, a drained 200 ml oil
1 sample was spectrally examined when excited by means of
0.9
LED light. The results are shown in Fig. 19. For comparison,
Signal inte nsity / arb. unit

0.8
0.7
the spectrum of a fresh 16 mg/200 ml PM567A/Fuchs 5W30
0.6 sample at 30 °C when excited by means of LED is shown.
0.5 Despite the harsh conditions in the engine, the tracer
0.4
remains active and shows the expected behavior. In a direct
0.3
0.2
comparison, the maximum of the emission spectrum is
0.1 spectrally blue-shifted, which is probably due to the con-
0 centration reduction by fuel dilution. The comparable inten-
sity of the excitation light and emission spectrum in the
450 475 500 525 550 575 600 625 650
Wavelength / nm

Oracet® 084 @120°C Laser Oracet® 084 @30°C LED

engine-driven oil/tracer sample in the diagram is striking,
Lumilux® CD 345 @120°C Laser Lumilux® CD 345 @30°C LED which indicates a very low general fluorescence intensity.
PM567A @120°C Laser PM567A @30°C LED
This statement can be made on the basis of the experimen-
tal design: excitation light introduction is placed in a right
Fig. 18  Spectral overview of the examined tracers at 30 °C (LED)
angle to the fluorescence light recording. Hence the intensity
and 120 °C (Laser) in 200 ml Fuchs 5W20
difference between excitation light and fluorescence light
increases drastically. This is, among other things, due to
the changed optical oil properties, in particular due to com-
bustion residues and fuel dilution, as well as the specific
­ umilux® CD 345 with
Stokes shift with 58 nm, followed by L structure of the examination system. Figure 20 shows an
62 nm. PM567A has the largest Stokes shift with 102 nm. application-related investigation example on an engine with
The 120 °C oil temperature comparison was chosen because minimally invasive endoscopic accessibilities. The fluores-
of real word engine oil temperatures. In general, both light- cence signal is observed by on long-pass filtered camera via
ing sources give a similar fluorescence picture. an endoscope. The excitation light is introduced into the
combustion chamber via two short-pass filtered LED engine
3.6 Use in engine operation lighting systems (adaption of spectral range). Due to the
spectral range of the LED´s the use of a 525 nm long-pass
In engine tests with a modern downsizing unit, a fresh filter for a clear separation of excitation light and fluores-
engine oil batch of 3.75 L Fuchs 5W30 was mixed with cence light is necessary. Hereby a large stoke shift relates to
300 mg PM567A (≙ 16 mg/200 ml) and a 20 k cycle pre- better fluorescence light detection efficiency. Specific fuel
ignition test was carried out. This 25 min full load engine accumulations can be detected at the liner bore top area after
operation puts great mechanical, thermal and chemical stress

13

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286 Automotive and Engine Technology (2021) 6:275–287

Fig. 19  Spectral comparison 1.1

between an oil/tracer mixture 1
used in an internal combustion

S i gnal i ntensity / arb. uni t

0.9
engine and a fresh oil/tracer 0.8
mixture 0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
450 475 500 525 550 575 600 625 650
Wavelength / nm

Driven engine oil + PM567A @ 30°C LED

Fresh engine oil + PM567A @ 30°C LED

Fig. 20  Exemplary use of doped engine operating media for in-cylinder accumulation investigations with an engine LIF setup

full load engine operation, which further correlate to local PM567A sometimes showed significant behavior differ-
deposit build-up; a sub-mechanism to pre-ignition initiation. ences. All tracers though can be used in engine oil.
In this special case oil accumulations on the intake valve Oracet® 084 has an emission intensity maximum in the
after pre-ignition related oil injection tests can additionally tested engine oils at 30 °C in the concentration range of
be detected. 6–8 mg/200 ml. ­Lumilux® CD 345 shows this at around
12 mg/200 ml for engine oil and around 24 mg/200 ml for
“High LSPI” fuel. Both tracers show a very low concentra-
4 Summary and conclusion tion influence on the Stokes shift. For PM567A, the con-
centration-dependent fluorescence maximum was not yet
In the investigations presented, the fluorescence behavior reached at 25 mg/200 ml in engine oil. However, the curve
of ­Oracet® 084, ­Lumilux® CD 345 and PM567A in engine trend shows that the maximum concentration potential will
oils when excited by a laser diode or LED was shown. In soon be reached. There is also a concentration-dependent
addition, ­Lumilux® CD 345 was also examined in fuel. redshift of the spectrum.
The effects of concentration, temperature and aging on the The temperature and aging characteristics are very
fluorescence spectrum were shown using a pragmatic fluo- constant with PM567A. At oil temperatures of 150 °C, a
rescence investigations system. Overall, O­ racet® 084 and decrease in the fluorescence intensity to below 20% of the
®
­Lumilux CD 345 showed very similar behavior, whereas initial intensity can be observed. There is also a clear Stokes

13

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Automotive and Engine Technology (2021) 6:275–287 287

shift increase with increasing temperature. ­Oracet® 084 and 2. Stevens, R.E., Ma, H., Stone, C.R., Walmsley, H.L., Cracknell, R.:
­Lumilux® CD 345 show a concentration-dependent tempera- On planar laser-induced fluorescence with multi-component fuel
and tracer design for quantitative determination of fuel concentra-
ture and aging behavior with an almost constant Stokes shift. tion in internal combustion engines. SAGE J. (2007). [Link]
Losses of intensity between 40 and 80% can be observed. org/​10.​1243/​09544​070JA​UTO162
With both tracers a slightly increased concentration in com- 3. Zöbinger, N., Schweizer, T., Lauer, T., Kubach, H., Koch, T.:
parison to the 30 °C maximum intensity concentration could Experimental and Numerical Analysis on Two-Phase Induced
Low-Speed Pre-Ignition. Energies 14, 5063 (2021). [Link]
be advantageous for temperature and aging effects with org/​10.​3390/​en141​65063
regard to a maximum fluorescence intensity. 4. Schweizer, T., Kubach, H., Zöbinger, N., Lauer, T., Eder, M.,
A large Stokes shift is advantageous for qualitative engine Grabner, P., Schießl, R., Liu, C.C.: Initial Pre-ignition. Final
observations with the lighting systems used, which is why report for the FVV-project no. 1328 (2021)
5. Lakowicz J.R. (2006) Principles of Fluorescence Spectros-
the PM567A is particularly suitable here. copy. Third Edition. Springer US, [Link] oi.​o rg/​1 0.​1 007/​
978-0-​387-​46312-4
Acknowledgements This work was supported by the Deutsche 6. Johnson, I.D.: Molecular probes handbook a guide to fluorescent
Forschungsgemeinschaft (DFG—German Research Foundation) Pro- probes and labeling technologies, 11th edn. Life Technologies,
ject number 237267381 Collaborative Research Center/Transregio 150 Carlsbad (2010)
“Turbulent, chemically reactive, multi-phase flows near walls”. The 7. DIN EN 228: Automotive fuels—unleaded petrol—requirements
authors want to thank the DFG for funding this project. and test methods, German version EN 228:2008
8. Bondarev, S.L., Knyukshto, V.N., Stepuro, V.I., Stupak, A.P.,
Funding Open Access funding enabled and organized by Projekt Turban, A.A.: Fluorescence and electronic structure of the laser
DEAL. dye DCM in solutions and in polymethylmethacrylate. J. Appl.
Spectrosc. 71(2), 194–201 (2004)
9. Nabavi, S.H., Khodabandeh, M.H., Golbabaee, M., Moshaii,
Declarations A.: Absorption of DCM dye in ethanol: experimental and time
dependent density functional study. Int. J. Optics Photon. 12(1),
Conflict of interest On behalf of all authors, the corresponding author 43–56 (2018)
states that there is no conflict of interest. 10. Mishra, Y.N., Yoganantham, A., Koegl, M., Zigan, L.: Investiga-
tion of five organic dyes in ethanol and butanol for two-color
Open Access This article is licensed under a Creative Commons Attri- laser-induced fluorescence ratio thermometry. Optics 1(1), 1–17
bution 4.0 International License, which permits use, sharing, adapta- (2020)
tion, distribution and reproduction in any medium or format, as long 11. Zehentbauer, F.M., Moretto, C., Stephen, R., Thevar, T., Gil-
as you give appropriate credit to the original author(s) and the source, christ, J.R., Pokrajac, D., Richard, K.L., Kiefer, J.: Fluorescence
provide a link to the Creative Commons licence, and indicate if changes spectroscopy of rhodamine 6G: concentration and solvent effects.
were made. The images or other third party material in this article are Spectrochim. Acta Part A Mol. Biomol. Spectrosc. 121, 147–151
included in the article's Creative Commons licence, unless indicated (2014). [Link]
otherwise in a credit line to the material. If material is not included in 12. Photophysics of fluorescent proteins, ibs Institut de Biologie
the article's Creative Commons licence and your intended use is not Structural, France, Online [Link]
permitted by statutory regulation or exceeds the permitted use, you will groups/​dynam​ics-​and-​kinet​ics-​of-​molec​ular-​proce​sses-​group-m-​
need to obtain permission directly from the copyright holder. To view a weik/p​ ixel/p​ hotop​ hysic​ s-o​ f-fl
​ uore​ scent​ /?l​ ang=f​ r. Accessed 19 Oct
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References
1. Ting, L.L.: Development of a laser fluorescence technique for
measuring piston ring oil film thickness. J. Lubrication Tech.
102(2), 165–171 (1980). [Link]

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