RHEOLOGY · SPECTROSCOPY
Produ c t Spe ci f i cat i ons
Rheonaut Module for
HAAKE MARS Rheometer
Rheology combined with spectroscopy
The patented* Rheonaut® module for
the Thermo Scientific™ HAAKE™ MARS™
rheometer simultaneously measures
rheological properties and structural
changes on the molecular level using
FT-IR spectroscopy. This allows
extensive investigations of structural
changes under deformation/shear as
well as thermally induced or UVcuring. The new level of understanding
of rheological phenomena on the
molecular level enables researchers to
speed up formulation development and
process optimization.
As a “macroscopic” analytical method,
Rheology provides information on
the bulk behaviour of a sample
under specific conditions. However,
viscoelastic properties of a material
depend on its molecular structure.
*Resultec Analytic Equipment: DE 10140711, EP 02762251,
US 6988393, JP 4028484
Modular rheometer platform Thermo Scientific HAAKE MARS III with Rheonaut module and Thermo Scientific Nicolet™ iS™10
FT-IR spectrometer
Coupling an FT-IR spectrometer with a
rheometer allows the detection of changes
in rheological properties on the molecular
level, conformational changes and molecular
orientation as a function of shear or due to
chemical reactions.
Benefits of combined methods:
• Identical sample composition and history
• Simultaneous testing saves time
• Identical test conditions for both methods
• Reliable correlation of results
Benefits of the unique combination of
rheology with FT-IR spectroscopy:
• Patented technique in a compact and fully
integrated module
• ATR (attenuated total reflection) principle:
sample thickness can be adjusted to the
rheological needs and is independent from
the infrared spectroscopy requirements
• Diamond ATR element absolutely inert
against mechanical stress as well as
chemical composition of the sample
• Compatible with standard spectrometers
with a side port
• Thermo Scientific HAAKE RheoWin: one
software to control rheometer and FT-IR
spectrometer
Coupling an FT-IR spectrometer with a rheometer
2
3
Applications
The Rheonaut module integrated into the HAAKE MARS rheometer can be used to investigate a material’s rheological
behaviour that strongly depends on its molecular structure. Applications include investigations of chemical reactions,
inter- and intramolecular interactions such as stability testing as well as studying chain orientation in polymer melts
and solutions.
Extensive rheological investigations
on chemical reactions
Thermal and UV-curing
Inter- and intramolecular
interactions
Requirementsanddemandsinthecoatingsandadhesivesindustryconstantlyincreasewithrespectto
eco-friendliness,productqualityandproductionefficiency.Abetterunderstandingofkineticsofcuringunder
specificconditions,e.g.temperatureorUV-intensitiesaswellasfinalmechanicalpropertiesofthecross-linkedand
curedcoatingproduct(G’/G’’)areneededtochoosetherightformulation.Thisisessentialforoptimizingthe
process/applicationbehaviourwhileminimizingenergyfootprintinproduction.
Stability of emulsions
CombiningrheologyandFT-IRspectroscopy,rheologicalpropertiesofamaterialcanbecorrelatedwithongoing
(chemical)reactions,e.g.thedegreeofcross-linkingasafunctionoftime,temperatureradiation,shearordeformation.
TheThermoScientificfastoscillationsoftwaretoolmonitorsveryfastcuringreactionsintherheologicaldataand
FT-IRspectraonamillisecondtimescale.
WiththeRheonautmodule,theshearinducedchangesinemulsionmorphologycanbemonitored
in-situ.Theresultscanprovetheabilityofanemulsiontorepairthedamagecausedbymechanical
impactovertime.Theinformationonmolecularorganizationanddynamicsunderdeformationyields
exactknowledgeofinteractingfundamentalstructuringmechanisms.Thisresultsinoptimizedtuning
oftechnicalproperties,processengineering,andmaterialparameterswithrespecttoafunctionally
optimizedstructuringofemulsionsystems,andthereforereducedtime-to-market.
Products and markets:
• Adhesives
• Composites
Molecular orientation under shear
Products and markets:
•PharmaceuticalsandCosmetics
•Coatings
•Food
Properties of polymers
Mechanicalpropertiesofpolymersarestronglyinfluencedbythemolecularorientationthathappensduringvarious
processes,e.g.ExtrusionorPumping.CombiningtheRheonautmodulewithapolarizerenablesinvestigationsonthe
mechanicalpropertiesandthemolecularorientationundershearatthesametimetogetacompletedescriptionof
theirdependency.
Network formation of gelatine
Gelatineisanirreversiblyhydrolyzedformofcollagen.Theworldwideproductionamountofgelatineisabout
300,000tonsperyear.Gelatineisimportantinmanyapplications,especiallyforpharmaceuticalproducts.It
typicallyconstitutestheshellsofpharmaceuticalcapsules.Viathebackbonechemistryand/orspecificadditives,
customtailorednetworkformationenablestheadjustmentofthecontrolledreleasepatterntowardscertain
activepharmaceuticalingredients(API).TheRheonautmoduleenablestomonitortemperaturedependentsteric
hindrance,additiveactivityandnetworkformationin-situ.
SchematicDrawing:
SetupforpolarizedIRradiationattheATRsensor/sampleinterface:
ND:NormaldirectionattheATRsensor/sampleinterface
MD:Machinedirection(inflowdirectionofthesample)
E:Electricfieldvectorsofthepolarizedradiation
(parallelandperpendiculartoMD)
:Angleofincidence(45°)
Therheometerrotationcausesanorientationofthesamplemolecules.Dependingonthepolarizersetupchangesin
theabsorptionbandscanbemonitoreddependingonthemolecularorientation.Byusinglinearlypolarizedinfrared
radiation,theorientationofthefunctionalgroupsinapolymercanbemeasuredeitheralongthebackboneoronly
thesidechains.Thedifferenceinthebandintensitiesbetweenparallelandperpendicularpolarizedinfraredradiation
indicatesthedegreeofmolecularorientationforapolymer.
Products and markets:
Products and markets:
•Pharmaceuticals
•Polymers
•Food
Application Support
N
peptide/protein
pro
Products and markets:
•Pharmaceuticals
Purification
Selected Product Information:
t report
Produc
n 1.2)
P-037 (versio
Isolation
•Food
• V246MeasuringoffastUVcuringmaterialsusingoscillatorymeasurements
• V247Detailedanalysisofcuringreactionsofpolyurethaneresins
• V254CuringofanAcrylateGlue–RheologywithSimultaneousFTIR-Spectroscopy
• V257MonitoringEmulsionsMorphologyUnderShear
Solubilization
and Jint
Thermo
Nijman,
Germany
Products,
terization
al Charac
fic, Materi
Fisher Scienti
UV-induced curing reactions investigated
by simultaneous rheometry and FT-IR
measurements
Jan Philip Plog, Thermo Fisher Scientific, Material Characterization, Karlsruhe, Germany
Monito
ring Em
Shear
ulsions
via Sim
Morph
ulta
In-situ
olo
FT-IR Spe neous Rheom gy Under
ctrosco
etry and
py
Kiyoji Sugim
oto 1, Fritz
Karlsru
Soerge 2
he (DE) 2
l and
and Result
Manfre
d Feuste 3
ec analyti
l Therm
c equipm
o Fisher
ent Illerkirc
hberg (DE) Scientific, Yokoha
3
ma (JP) 1
,
Introduction
Key-words
• P037NewUVmoduleforUVcuringmeasurements
Refolding/
Clearage
er-Lehrheuer
Küchenmeist
Cornelia
s
asurement
curing me
In many industrial segments the use of UV curing materials
ated
with integr
for the processing or application of paints, inks, adhemodel
piece glass
sives, coatings, etc. is of upmost importance. This technord
surface.
the use
clamping of different standa late
segments
logy combines environmental and economical advantages
on
industrial ials for the profor plate/p
A selecti
In many
with improved product features.
modules
X-P)
inks,
mater
curing
paints,
temperaturegeometries (TM-Xlike a
of UV
A curing process can be followed by dynamic rheological
ation of
great
ring
logies
or applic
etc. is of
techno
cessing
plus
es measu
measurements, since the build-up of a network in the
coatings,
different
combin
al-heating
adhesives, This technology advan- using
t, electric
sample is directly related to the change of the viscoelastic
tor, are
ical
Peltier-elemen g or a circula
ific
importance. al and econom
properties (G’, G“, etc.) of that sample.
range of
ct feao Scient
liquid coolincover a wide
• Therm MARS
environmentimproved produ
.
By combining oscillatory rheological measurement with a
to
ration for
with
applications e can
HAAK E
available
ture
III configu
ific
and
tages
s
second analytical technique an even more comprehensive
MARS
o Scient
incl. tempera
UV modul
production temperature
6000
• Therm
ements
Fig. 1: HAAKE
tures:
the new
hput in
insight into the characteristics of curing processes can
erature
measur
RheoStress
curing
r throug
HAAKE
UV curing
Alternatively with the (temp le for
to faster
• Highe
be achieved. Such a supplemental tool can be e.g. FT-IR
l
ned
thanks
ring
e of less
modu
contro
ses
combi
l
aut
be
becaus
• UV-cu
proces
d therma
bility
spectroscopy. For a curing process or phase transition
nglled) Rheon rements of rheor profita
• UV assiste
manufacturi nt contro
measu
• Highe
spectra
in general a rheometer can analyze the time dependent
space in
aneous
eatme
curing
and FTIR
required
es
for post-tr
tion
for simult l properties
change of the viscoelastic properties of a material. The
need
chang
oscilla
need
no
ral
logica
• Fast
and no
plants,
structu
viscoelastic properties of a material however depend on
st fumes
investigate
(FastO SC)
e [1].
of exhau
ble
n- to
its structure and especially its structural changes during a
the sampl
tection
al availa
for enviro
within
cts
option
Ex-pro
for
d
the
curing process. Infrared spectroscopy is an excellent
of
and
mende
t-free produ
The use
is recom
processes
• Solven
nt contool for determining structural changes on a molecular
e hood
friendly
d ambie
safety
mental
of
- sampl rements beyon
level.
working
s, includ
made out ved
is
measu
feature
impro
t
n
tempe
This hood
We will present technical details of new UV-curing se-tup
ized produc ion and abrasio
used for
ditions.
• Optim
can be
corros
for the Thermo Scientific MARS rheometer and show
cal resisPEEK and to 260 °C.
r
ing a better better chemi
rheoin
adapte
up
the experimental results of the investigation of an UVs
and
tion,
bility
ry
tor
rature
E RheoW
protec
HAAK
ring geomet g the collima
ated meabetter forma curing macuring processes for an acrylate based coating for optical
Using the re fully autom es can
adjustin
Fig. 2: Measu
tance and
on UV
ng and
fibers. The presented data includes rheological as well as
softwa
rements
Thermo
routin
for mountiguide
For measu module for the MARS meter and evaluation automatic
spectroscopic data.
and light
new
eters
suring
ing an
terials a
E rheom
ation):
d includ
source.
HAAK
been dethe applic
be create
UV light
ls
Scientific tress 6000 has
ding on
ing of the
Measurement and set-up
ts of an
curing materiaed
(depen
trigger
RheoS
consis
fast
e
with
and
1:
mirror
lly for very
the so-call
With the patented Rheonaut module a standard FT-IR
This modul
Version
glass plates
Especia
mode integrated
veloped.
– has
quartz
glass
with an
measuring
spectrometer with side port and the Thermo Scientific
Circular
tory tests
ring:
upper shaft ngeable quartz a colli- a new SC for oscilla
offers
clamp
ing quartz
te
SC
spread
HAAKE MARS rheometer are coupled to form one
for
FastO
excha
separa
FastO
Tool for
and an
ped [2].
a holder
500 Hz
is
measuring unit (Fig.1).
well as
222-2038 glass clamps
which
been develo ition rate of
plate, as
pcs.) for
guide,
of
ms) indeFor investigating UV curing materials with the Rheonaut
rings (3
plus light
ring head of a data acquis point per 2
plates
ncy.
Clamp
mator
measu
glass
data
freque
beam
to the
module a new fixture for the HAAKE MARS rheometer
222-2039 circular quartz
(i.e. one the oscillation
UV light
of 8 mm
mounted
t of
source,
eter. The
platform has been developed. This module consists of
diameter
penden
le light
with a
the rheom
glass plates
availab
ator and
quartz
an
upper shaft with an integrated mirror and an exchangeercially
r
mm
8
collim
Circula
a comm
tion
ter of able quartz glass plate (Fig.2), as well as a holder for a
ing of
ed by the
is directnformaation
222-2040 with a diame
e consist
Order iinform
mirror,
with
first bundl
ated
UV modul
ed by the
for use collimator plus light guide, which is mounted to the
lly from
222-2036 a shaft with integr ring
(10 pcs.) 222-2039
then reflect sample vertica
plate.
holder
glass
the
HAAKE MARS measuring head (Fig.2). The UV light
ring
screw
geclamp
ed into
pcs.) for
mirror,
h the quartz the upper
rings (3
beam of a commercially available light source, first bundled
ing an exchan
above througglass plate is
Clamp
glass plates
geofor mount glass plate
by
222-2041 circular quartz
mmcollimator and then reflected by the mirror, is
measuring
a20the
quartz
The quartz
of
plate
/
able
part
ter directed
a plate
r and collim
plate is
platesinto the sample vertically from above through
with a diame glass
plate of
l
incl. adapte light guide
s the lower
contro
ar quartz the quartz
mm glass plate (Fig.2). The quartz glass plate is the
rature
an UV
metry, wherea
tor for
042 Circul diameter of 20
und UV
rd tempe a temperature
222-2
guide
a
standa
a
for
with
of
with
(UV light not included)
for use
this allows e within a wide
module,
(10 pcs.)
sampl
light source
222-2041
1
l of the
contro
clam ring
range.
ters of
temperature plates with diame the
rature
accessories:
for
glass
Necessary with lower tempe aut
available
Quartz
ities
mm are
eter
nt viscos
) or Rheon
Rheom
8 and 20
rediffere
Peltier
The
measu
(e.g.
es.
to the
aneous
module
adaption
of the sampl ble in
rties and
for simult
moduli
module
are availa
gical prope
and G
glass plates s: a circular model, ments of rheolo
quartz
a,
ring
plates
nt version
FT-IR spectrle quartz glass
two differe a separate clamp
a simple
needs
exchangeab
steel, as
which
stainless well as a one
made of
n as
st versio
low-co
1
• P033Spectroscopicalinsightintorheology
Expression
IB isolation
for UV
module
New UV
• V258UV-inducedcuringreactions
Overview
Purpo
se:
emulsions Investigation
with submi of the dynam
Metho
ics of molec
cron drople
ds: Simul
ular organ
taneo
ts
utilizing
the Rheon us rheometry under shear.
ization
of
Resul
aut modu
and in-situ
Fig. 1: left: HAAKE MARS III rheometer with Rheonaut module ts: Provid
le.
FT-IR spectr
es insigh
under
deform
and spectrometer;
t into molec
oscopy
ational
ular organ
right: HAAKE MARS III configuration for UV-curing measureflow.
ization
ments incl. temperature control
and
dynam
Introductio
n
ics
Emulsions
cal, health are of wide interes
care and
t
consist
cosmetic in the food, pharm
of at
aceutiand stabili least two liquid industries. They
zers. Emuls
typically
phases
making
ions exhibi , surfactant
it difficu
agents
t
lt
micros
copic level. to understand complex rheolo
gy,
flow pheno
A comm
on
mena on
shear deformtechnique utilize
a
d to
ation is
showing
light micros analyze emulsi
droplet
ons under
Fig. 2: HAAKE
distributions copy. Howe
micron
Fig. 2: left: Measuring geometry and adapter for mounting and
scale canno
MARS
NICOL
with drople ver, emulsions
adjusting the collimator and light guide;
rheom
ET iS10
because
FT-IR spectroeter with Rheon
ts
of given t be visualized
middle: Upper shaft with integrated mirror;
using light on the subresolution
factors
aut module
meter.
of light
Materials
right: Holder for collimator plus closed hood
microscopy
and
microscopy constraints.
of drople
For this
ts
arise when Other limitin
study, as
of the two with equal size
g
the concen
upper plate of a plate/plate measuring geometry, whereas
available
model
is high
phases
tration
or the refract
substances,
In such
hand cream
are too
cases, the
fractio
similar.
the lower plate is either a standard temperature control
three comm
ive indices
emulsions
ns of
rheometer
Therm
ercially
with high
o Scient
were suppli oil in water
module or the Rheonaut module for simultaneous meaequipp
contai
ific
volum
FT-IR
ed by a
spectrometeed with the Rheon HAAKE MARS
samples
surements of rheological properties and FT-IR spectroscopy.
manufacturening submicron e
varied
and in-situ
r provid
aut modu
drople
r of cosme
with respec
position
es simult
The use of the optional available sample hood is recommendle and
only. No
tics. The ts
and offers FT-IR spectro
t to their
scopy under aneous rheom a
further
a
hydro
ed for measurements above ambient conditions. This
sample
etry
emulsion versatile tool
preparation carbon comfor efficien shear deform
Methods
research
hood is made of Teflon and can be used for temperatures
ation
was require
rheom
t and
and
The patent
d.
up to 240 °C. This new setup enables the user to expose tool etry and FT-IR stability testing comprehensi
ve
ed Rheon
. Simult
spectroscopy
in under
FT-IR spectro
aut modu
aneous
a material to UV-radiation while collecting rheological
standing
in concen
proves
meter
le
the
couple
to be a
NICOLET
microscopic
trated emuls
with side
and spectroscopic data at the same time.
useful
In this
port (here: s a standard
iS10) to
state of
ions.
contri
MARS
Thermo
droplets
rheometer. the Thermo
the dynam bution, we want
Scientific
Scientific
The lower
ics of molec
to presen
HAAK
under
plate of
t some
ular organ
E
shear.
(Peltier
the rheom
results
ization
or electri
eter is temper
of an emuls on
cal)
element
ature contro
ion
that serves and features
lled
reflection)
as the ATR a monolithic
(attenuated diamond
Compared sensor, offerin
g a single
total
to standa
internal
troscopy
rd infrare
reflection.
or
d transm
the sample specular reflect
ion spectro ission specthickness
needs and
scopy techni
can thus
is
ques,
copy requir independent be adjusted to
the
from
rheological
ements.
the infrare
d spectr
Fig. 1: Schem
os1
the HAAKE atic diagram
of couplin
MARS
rheometer.
g an FT*IR
spectro
meter to
Lookingforsomethingelse?Contactus!
info.mc.de@thermofisher.com
Application
Notes V-257
Proteinsareafastgrowingmarketinthepharmaceuticalindustry.Nomatterwhichproteinis
synthesizedinsolution,itneedstobepurified.Onestepofthepurificationprocessisusuallyfiltering.
Duringthefilteringstep,oddsarehighthattheproteindenaturatesduetothehighshearratesinthe
filterpores.UnderstandingtheprocessiscrucialforthemanufacturerandtheRheonautyieldsthe
answerbymonitoringthesheardependentdenaturationofproteinsolutionsinaverysensitiveway.
Npro fusion
technology
Application Notes V-258
Denaturation of proteins
Weprovidecomprehensiveproductandapplicationsolutionsandourapplication
specialistteamisonhandtoansweryourquestions.
Specifications of the Rheonaut Module
Data acquisition and storage:
CompatiblewithseveralstandardFT-IRspectrometers
• “FT-IRspectroscopymodule”fortheThermo
ScientificHAAKERheoWinsoftwarewith
integratedcontroloftheFT-IRspectrometer
(forselectedspectrometermodelse.g.Nicolet
iS10,iS50),automaticsynchronizationof
rheologicaldataandFT-IRspectra
• ThermoScientificNicolet™iS™10compactspectrometer
forbasicmeasurements
• ThermoScientificNicoletiS50flexibleresearch-grade
spectrometerforadvancedmeasurements(learnmoreat
www.thermoscientific.com/spectroscopy)
Temperature control units (exchangeable):
Measuring principle:
• Peltierunit:0°–120°C
• ATRusingasinglereflectioncrystal
(diamondwith1mm²surfacearea)
• Electricalunit:30°C–400°C*
Produ c t Spe ci f i cat i ons
Spectrometer:
*Forhightemperaturessamplehoodrequired
Measuring geometries and accessories:
Detectors (exchangeable):
• DTGS(DeuteratedTriglycineSulfate)aseconomicalversion
(standard)
• MCT(Mercury,Cadmium,Telluride)forveryfastspectra
acquisitions
• InertgasatmospheretoavoidabsorptioninfluencesbyH2OorCO2
Options:
• Platesandconeswithdiametersupto60mm
• Samplehoodtominimizetemperaturegradient
withinthemeasuringgap
• UV-curingmodulewithexchangeablequartzglass
plateswithdiametersupto20mm
Dimensions:
dependingonspectrometerusedWxDxH:2000x600x890mm
• Manuallycontrolledpolarizer
(NicoletiS10FT-IRincl.HAAKEMARScontrollerboxandcomputer)
Spectrometers
TheThermoScientificNicoletiS50andNicoletiS10FT-IRspectrometersarecompatiblewiththeRheonautmoduleand
addchemicalinformationtoyourrheologystudies.
ThermoScientificNicoletiS50FT-IR
spectrometerwithABXAutomatedBeamsplitter
exchanger,built-indiamondATR,andRaman
moduleinthesamplecompartment.
Nicolet iS50
Nicolet iS10
Research-gradeFT-IRspectrometerupgradeablefrombasic
spectroscopytoautomatedmulti-rangeanalysis.
Singlerange,validatedspectrometerwithmid-IRornear-IR
capabilitiesdesignedforrugged,fast-pacedoperation.
• Flexiblemulti-ranging–manualorautomatic
• SamplecompartmentforThermoScientificSmart™
andStandardaccessories
• Multipledetectorson-board
• Built-indiamondATR
• TGA-IRfordeformulationusingMercuryTGASoftwarefor
rapidanalysis
• TouchPointcontrolfortechniquesetupandoperation
• iS50Ramanmoduleoffersmotorizedstage,USBcamera,
andtotalsoftwaresolution
• Rapidscanningforfastkinetics,includingultrafasttimeresolvedcapability
• Multipleemissionports
• SpectralrangefromvisibletoFar-IR
• Mid-IRorNear-IRfixedrangewithmanualsourceswap
• SamplecompartmentforSmart™andStandardaccessories
• Singledetectorson-board
• ATRthroughaccessories
• TGA-IRfordeformulationusingMercuryTGAsoftware
forrapidanalysis
• Integratedscanbuttonsforoperations
thermoscientific.com/mc
©2012/11ThermoFisherScientificInc.·RheonautisatrademarkofResultecAnalyticEquipment.Copyrightsinandtothetubeofglueimage,thepillsimage
andtheemulsionimageareownedbyathirdpartyandlicensedforlimiteduseonlytoThermoFisherScientificbyiStockphoto.Thisdocumentisforinformational
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