nmr microscopy & high power diffusion · 2016. 12. 9. · couette cell, cone&plate cell,...

Innovation with Integrity

Dr. Dieter Gross

User Meeting, 2016

Paris

NMR Microscopy & High Power Diffusion

Innovation with Integrity

2

Pourous Media11%

Flow7%

Downhole well logging7%

Rheology5%

Chemical Engineering & Catalysts

5%

Electrophoresis, Batteries, Fuel Cells, Supercapacotors

5%

Dispersions, Emulsions, Suspensions, Micells

4%

Polymers and Gels3%Plants & Wood

3%Food3%

Tablets 1%

Biofilms & Membranes3%

Filters & Biofouling1%

Mice2%

Tissue & Cartilage6%

Insects1%

Contrast agents & Nanoparticles

1%

Drying1%

Glass1%

NQR1%

MPI1%

HR_MAS1%

Combustion1%

Probes & Transmitters2%

Magnets2%

DNP & Hyperpolarisation & Parahydrogen

3%

2D Correlation Spectroscopy4%

Acquisition & Processing Methods

16%

ICMRM Cambridge 2013

3

Coils

Micro Coils, Solenoid Coils, Saddle Coils, Birdcage and SAW Coils

4 4

Rf-Coils for Microimaging N

Field MHz

200 300 400 500 600 700 750 800 900 950 10

Magnet Types

Standard Bore 52 mm, Wide Bore 89 mm, Super Wide Bore 154 mm 3

Single tuned coils 1X or X

1H, 7Li, 13C, 17O, 19F, 23Na, 31P, 129Xe, … 121

Double tuned coils1 H/X

1H/2H, 1H/13C, 1H/19F, … 120

Special combinations X/X

19F/13C, … n/n

Planar Coils

50 mm

100 mm

500 mm

1 mm

2 mm

5 mm

10 mm

15 mm

20 mm

25 mm 10

Volume coils

1 mm 2 mm 5 mm 10 mm

15 mm

20 mm

25 mm 30 mm 35 mm 40 mm 66 mm 11

RF Coils for Microimaging

5 5

Coil Type Fields Diameters Single Tuned

Double Tuned N

Microcoil 10 4 121 4.840

Surface Coil 10 5 121 6.050


Volume Coil 10 10 121 12.100

Volume Coil 10 10 120 12.000

SWB Coil 4 4 121 1.936

SWB Coil 4 4 120 1.920

Total 44.846

Possible Coils for Microimaging

6 6

Coil Type Fields Diameters Single Tuned

Double Tuned N

Microcoil 10 4 121 4.840



Volume Coil 10 10 121 12.100

Volume Coil 10 10 120 12.000

SWB Coil 4 4 121 1.936

SWB Coil 4 4 120 1.920

Total 44.846

Developed Versions > 600

Only ~ 1.3 %

Realized Coils for Microimaging

7 7

Microimaging

RheoNMR

Laboratory on a Chip

Dieter Gross MRS / User Meetings 2016

RheoNMR

Combination of Rheology

MR Microscopy

N MR Spectroscopy

Dieter Gross

Bruker-Biospin GmbH Germany

Rheology deals with deformation and flow of matter

RheoNMR

Rheology is everywhere in our daily life

10

Parameters s Stress = Force/Area v Velocity . g time dependent strain or strain rate Viscosity = stress / strain

G viscoelastic modulus G = stress / strain rate G(w) = G’(w) + i G’’(w) G’ storage modulus (elastic) G’’ loss modulus (viscous)

RheoNMR

Examples of flow curves

Ares-2 Rheometer from TA Instruments

RheoNMR

Couette cell, cone&plate cell, plate&plate cell , tube

RheoNMR is the combination of

Rheology

MR Microscopy

NMR spectroscopy

Time Domain NMR (Relaxometry)

Rheology provides information about mechanical properties by viscosity, energy

storage and energy loss modulus determination.

MR Microscopy provides information at the mechanical length scale by

spatially and temporally resolved velocity maps and shear rate maps.

NMR spectroscopy provides information at the molecular length scale by spatially and

temporally resolved NMR spectra, relaxation times and diffusion constants.

RheoNMR

Components of the

RheoNMR Accessory

Developed by Tim Brox

and Petrik Galvosas,

Victoria University of

Wellington, NZ

RheoNMR Accessory for MicWB40 Microimaging Probes

14 14

Application Examples

Food

Micells

Polymers

Granular Flow

2H spectroscopy under shear

RheoNMR

0 1000 2000 3000 4000

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Experimantal Data

FIT

Monom

er

convers

ion X

/ -

Reaction time t / -

15

Cylindrical Couette Cell

sauce slips at the inner surface,

variable shear across the annulus,

low slip at the outer surface,

transition in shear rate,

shear thinning towards the outer

surface

RheoNMR

Courtesy of Paul T. Callaghan

16

Test the macroscopic

properties:

“FLOW and PLOP”

The velocity is first decreasing,

then increasing with radius,

similar to plug flow.

Indication for yield stress

properties.

RheoNMR


17

NMR Flow Visualisation

of heterogeneous shear

and extension:

The fundamental

assumption of shear rate

constancy is not valid for

certain classes of fluid!

„Shear Banding“

RheoNMR


18

„Shear Banding“

Fluid separates into

coexisting phases of

widely differing viscosity.

Flow instability.

Molecular ordering

effects.

RheoNMR


KIT – The Research University in the Helmholtz Association

Institute of Thermal Process Engineering

www.kit.edu

Influence of Fluid Dynamics on Polymerization

Kinetics Measured by Rheo-NMR

Construction of an appropriate Rheo-NMR equipment

E. Laryea, G. Guthausen, T. Oerther, M. Kind

Reaction Monitoring under Shear

The influence of fluid-dynamics on the kinetics of polymerisation observed by RheoNMR

RheoNMR

Chemical reaction & NMR

spectrum under shear

Reaction Monitoring under

Shear

Courtesy of Nils Schuhardt and Esther Laryea, KIT Karlsruhe Germany

Institute of Thermal Process Engineering 21

Solvent: Xylene

Free Radical Polymerization (FRP)

09.12.2016

R = Radical, I =Initiator, M = Monomer, P = Polymer, k Coefficients , f = Radical efficiency

Initiation

Propagation

Termination

Decomposition f

f∙

)1

2(exp

][2exp][][

01

0

tk

k

IkMM d

d

d

t

pkf

k

kk 21with

Theoretical decay of monomer; batch polymerization

Institute of Thermal Process Engineering 22 09.12.2016

a b

8.0 6.4 4.8 3.2 1.6 0.0

chemical shift d / ppm

a b

a

b Methyl methacrylate

MMA Poly (methyl

methacrylate)

PMMA

Determination of monomer conversion by 1H NMR spectroscopy

1H NMR spectra of 50 wt% MMA,

49.5 wt% Xylene and 0.5 wt%

AIBN initial composition,

400MHz 5mm Tubes

Polymerization – Model System


Construction – Rheo-NMR Cell

Inner and outer cylinder made

out of PEEK

Gap width 1 mm

Radius ratio η =𝑅𝑖

𝑅𝑜= 0.895

Concentric arrangement

realized by bearings

Temperature control via a hot

nitrogen stream

Inner cylinder coupled with

speed controlled drive

09.12.2016

coupling

bearing

heating

adapter

inner

cylinder

outer

cylinder seal

bearing


7.5 7.0 6.5 6.0 5.5

Experimental data

Chemical shift \ ppm

Spectra under shear

Broad peaks induced by

the measuring cell

Workaround fit by

pseudo-Voigt functions

Nonlinear least-squares

solver

09.12.2016

a

b

Methyl methacrylate

MMA

c c

p- Xylene

a b

c

Fit is in good agreement with the experimental data

7.5 7.0 6.5 6.0 5.5

Experimatal data

Fit (overall)


-0.10

-0.05

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

Div

erg

ence / -

𝛾 = 𝜔𝑅𝑖

𝑠 = 124 1/s Apparent shear rate:

7.5 7.0 6.5 6.0 5.5

Experimental data

Fit 1 (Xylene,c)

Fit 2 (MMA,a)

Fit 3 (MMA,b)



Results – Monomer Conversion

09.12.2016

0 1000 2000 3000 4000

0.0

0.1

0.2

0.3

0.4

0.5

Are

a r

atio

A / -

Reaction time t / -

0 1000 2000 3000 4000

0.0

0.1

0.2

0.3

0.4

0.5

Are

a r

atio

A / -

Reaction time t / -

)1

2(exp

][2exp][][

01

0

tk

k

IkMM d

d

𝐴 𝑡 =𝐴𝑀𝑀𝐴 𝑡

𝐴𝑋𝑦𝑙𝑒𝑛𝑒 𝑡= 0.53 ∙ 𝑒−4.17∙10

−4∙𝑡

𝑋 𝑡 =𝐴 𝑡 = 0 − 𝐴(𝑡)

𝐴 𝑡 = 0

Determination of reaction rate constant 𝒌𝟏 by 1H NMR spectroscopy

0 1000 2000 3000 4000

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Experimantal Data

FIT

Mon

om

er

con

vers

ion X

/ -

Reaction time t / -

Area Ratio

Monomer conversion

Monomer concentration

𝑘1 = 2.7 ∙ 10−3𝑙0.5 ∙ 𝑚𝑜𝑙0.5

𝑠

with 𝑘𝑑 = 1.53 ∙ 10−4𝑠−1

𝛾 = 𝜔𝑅𝑖

𝑠 = 124 1/s Apparent shear rate:

s

The influence of fluid-dynamics on the kinetics of polymerisation observed by RheoNMR

Flowprofile in TCR

RheoNMR

Courtesy of Nils Schuhardt and Esther Laryea, KIT Karlsruhe Germany

Flow Observations of Granular Material

Granular material is defined as a collection of discrete macroscopic particles.

Natural examples include sand, soil and snow.

Numerous industrial processes involve granular material with examples from

agriculture (e.g. rice, sugar and seeds) to pharmaceutical production.

Depending on the properties of the individual particles, overall volume

concentration and applied external stimuli, granular materials can

behave as either a solid, liquid or gas.

NMR is a non-invasive technique for studying materials under shear.

The RheoNMR hardware is well suited for these studies.

The shear devices rheo cells can be tailored to the diameters of particles and

the desired number of grains spanning the fluid domain in SB / WB and SWB

magnets.

RheoNMR

Courtesy of Tim Brox, Petrik Galvosas, Jenifer Brown, Joe Seymour, Sarah Codd, Hilary Fabich, Daniel Holland

RheoNMR

Sample Mean Diameter

/mm ri /mm ro-ri /mm

Lobelia Seeds 0.3 16.0 7.65

Petunia Seeds 0.5 16.0 7.65

Vitamin E

Capsules 1 15.1 8.55

Mustard Seeds 2 11.1 12.55

Samples studies in a dedicated RheoNMR system for a super wide bore magnet.


Pulse program for granular flow experiments: Double slice selection 1D imaging

sequence with velocity encoding.

The broadband (hard) p pulse in the PGSE portion allowed short observation times D

over which fewer particle interactions would occur. The encoding time was fixed at

1 ms. For each system multiple experiments were conducted as a function of the

observation time D varied between 1.8 ms to 7 ms.

RheoNMR


Top: Axial MRI data for the four granular material systems;

(left to right) lobelia seeds, petunia seeds, vitamin E capsules and mustard seeds.

All images were 60mm by 60mm (256 points by 256 points).

Bottom: Velocity profiles for the respective granular system. In each experiment the motor

was rotated such that the tangential wall speed was 17.1 mm/s;

All velocity data were acquired with an encoding time D = 5 ms.

The vertical dashed lines indicate the boundaries of the shear cell while the horizontal

dashed line indicates the velocity of the moving wall.

RheoNMR


Spatially resolved velocity measurements could be used to describe the

variance in particle velocities.

By observing the variance of velocity as a function of observation time D it would be

possible to estimate the mean collision time;

At observation times less than the mean collision time the variance of velocity is

constant.

These mean collision times relate to the rheology and viscosity of the granular

material and would be of great use for refining theoretical descriptions of granular flow.

NOTE: This type experiment and interpretation of granular flow behavior at different D

is somehow similar to restricted diffusion experiments using short and long diffusion

times D.

RheoNMR


2H as a “tracer” for local order in systems under shear

RheoNMR

Courtesy of Tim Brox and Petrik Galvosas, Victoria University of Wellington NZ

2H as a “tracer” for local order in flowing systems

The spin 1 deuteron quadrupole moment interacts (of D2O or other deuterated solvents)

with the electric field gradients caused by the surrounding molecules (micelles, wormlike

surfactants) causing 2H spectral splitting depending on the local order in systems.

This can be used to probe the type and degree of ordered systems under shear by 2H

spectroscopy.

]3[2

)1cos3(

)12(4

3 22

2 IIII

QeVH z

ijzzQ

RheoNMR

Quadrupolar interaction spectroscopy

shear induced order in the wormlike

micelle solution of 18% CTAB / D2O

in 17 mm / 19 mm Couette cell

Cetyltrimethylammonium bromide

2H spectra of D2O as function of

radial position across the gap of

the Coutte cell


RheoNMR


Outer wall: low stress, single line

Inner wall: high stress,line splitting

finite quadrupol interaction

Formation of a nematic phase at high stress,

transition through a mixed phase region,

isotropic phase at low stress

RheoNMR

Courtesy of Tim Brox and Petrik Galvosas, Victoria University of Wellington NZ

2H spectra collected as a function of

accumulated strain

1. Mix triethylene glycol mono-n-decyl ether C10E3 in

9:1 D2O:H2O.

2. Load sample in Couette cell and shear it at 42o C

and a shear rate of 10 s-1 for approximately one

hour to establish the planar lamella phase (as

identified by 2H spectrum).

3. Once the La structure is established stop the motor

and set the temperature to 25o C where the sample

equilibrates for one and a half hours.

4. Acquiring data at a constant shear rate of 10 s-1

5. NMR data was acquired. a total of 400 NMR

experiments were run with a complete experiment

taking approximately 14 s (total experiment time

approximately 95 min)

Observation of Shear Induced Structural Transitions in a Lyotropic

Nonionic Surfactant System via deuterium spectroscopy

36 36

Conclusions

Spatially resolved velocity maps provide straight forward

identification of wall slip and information about granular flow

Spatially resolved velocity maps visualize changes in the shear

behavior and identifies shear bands

Spectroscopy under shear provides reaction monitoring in situ

under shear conditions

Deuterium spectroscopy under shear provides information about

local ordered or disordered structures on the molecular level

The combination of the NMR parameters with the traditional

rheology parameters enables a better characterization and control of

matter under flow and deformation

RheoNMR

0 1000 2000 3000 4000

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Experimantal Data

FIT

Monom

er

convers

ion X

/ -

Reaction time t / -

Acknowledgements !!!

37 37

Montana State Folks, Sarah Codd, Jenifer Brown, Hilary Fabich, Joe Seymour, Tim Brox

KIT, Esther Laryea

Gisela Guthausen

Cambridge & Wellington Folks, Daniel Holland, Hilary Fabich, Petrik Galvosas,Tim Brox

Wageningen, John van Duinhoven

Lab on Chip

for

NMR Microscopy and Localized Spectroscopy

D. Gross, Bruker-Biospin GmbH Germany

39

Standard equipment:

• Bruker Spectrometer

• Microimaging Accessory with 60 A gradient amplifiers

• Micro5 imaging probe and gradient (max strength:4.8 G/cm/A = 2.8 T/m @ 60 A)

• ParaVision software

• Micro-coil rf-inserts

Lab on a Chip

40

• Multi-turn spiral surface coils

• Geometry suitable for flat samples (tissue slices, cell layers)

• Easy access

• Compatible with optical microscopy

• ID = 1000 – 20 μm, OD = 1300 – 158 μm

P.M. Glover, R.W. Bowtell, G.D. Brown, P. Mansfield, Magn. Reson. Med. 31 (1994) 423-428 C. Massin, F. Vincent et al., J. Magn. Reson. 164 (2003) 242-25

NMR Microscopy with Isotropic Resolution below 10 μm Using Dedicated Hardware and Optimised Methods

Lab on a Chip

41

Micro Chamber Micro Chamber asembled with

the encapsulating connector

Encapsulating connector pieces

Samples in a Micro Chamber mounted on a

Micro Coil

Courtesy of Vicent Estede, University of Valencia, Spain

Lab on a Chip

42

Micro Chamber kit mounted

on top of the Micro Coil Insert

Samples in a Micro Chamber mounted on a

Micro Coil

Courtesy of Vicent Estede, University of Valencia, Spain

Lab on a Chip

43

Micro Chamber kit mounted

on top of the Micro Coil Insert

pure water was pumped through the support tubing

Micro Chamber mounted on a Micro Coil

Lab on a Chip

44

Sample in a Micro

Chamber

mounted on a

Micro Coil

overlay of the vector field and the FLASH image of water in the chamber

(in black & white without flow) with the light microscope image of the chamber

mounted on top of the microcoil

Lab on a Chip

45

MicroChamber

fresh MicroChamber

Polluted !!!

Lab on a Chip

Samples in a

Micro Chamber

mounted on a

Micro Coil

Blocked

flow

regions !!!

Construction of a new surface coil design

Simple Design, Surface coil shape adapted to a meander sample cell or a Y-mixer

Surface

Coil

Meadowcroft et al., 2007:

Housing Meander sample container

Courtesy of Dominik Meyer, Giesela Guthausen, Karlsruher Institut für Technologie (KIT), Germany

Lab on a Chip

Flow in a Y Mixer

4 0 -4

Ethanol

[ppm]

8 6 4 2 0

[ppm]

Wasser

Resonator

Saddle coil


Water

Ethanol

Lab on a Chip

T1 weighted image and Velocity Map H2O-Ethanol

Left: high signal intensity of water (shorter T1), low signal intensity of ethanol (saturation effect caused by longer T1)

Right: higher velocity of ethanol,

Water is flowing partly into the ethanol input channel !

No strong mixing !

Ethanol

Wasser

T1-weighted 1H image Velocity map


Lab on a Chip

49 49

Lab on a Chip

50 50

Broadband Diffusion Probe DiffBB

1H&19F

Broadband 31P to 15N

2H Lock

ATMA Automatic Tuning / Matching

Variable Temperature

New broadband gradient probe with ATMA for diffusion applications optimized for very strong gradient pulses up to 17 T/m fast switching times of less than 300 ms

variable temperature application -40°C to +150°C available as BBO and BBI versions available for Great60 and Great10 amplifiers

51 51

Broadband Diffusion Probe DiffBB

Material science labs in research and industry

Batteries and electrolytes in situ (e.g. 1H, 7 Li, 19F, 23Na, 31P)

Polymers (e.g. 1H, 2H, 13C, 19F)

Porous systems (e.g. 1H)

Food / Pharma (e.g. 1H, 13C, 23Na)

Strong gradient pulses at fast switching times for samples with slow diffusion and short T2 or T2* relaxation times Generation of a collection of experiments for different nuclei and at variable temperatures in one session support by ATMA without the need for changing the probe

52

Ion Mobility in Ionic Liquids by Multi

Nuclear PGSE NMR (MN-PGSE)

• Ionic liquids (IL) also called RTIL room temperature ionic

liquids are molten Salts, liquid at room temperature

• Advantages of Ils:

• Thermally stable

• Hardly inflammable

• Low vapor pressure

• Many technical applications:

• Chemical engineering, …

• Fuel cells

• Super capacitors

• Li-ion batteries

53

Application Note

Ion Mobility in Ionic Liquids by Multi Nuclear PGSE NMR

State of the Art Lithium-Ion Batteries

• Electrolytes consisting of LiPF6 in volatile alkyl carbonates.

• High ionic conductivity around 10 mS/cm at room temperature

• Lithium transference number around 0.35

Test Sample:

0.5 molar LiTNF2 (Lithium bis-Trifluoromethanesulfonimide) (LiTFSI) in

1-Butyl-1-methylpyrrolidinium bis(trifluormethylsulfonyl)imid,

in 1 mm capillary tube

Ion Mobility in Ionic Liquids by Multi Nuclear PGSE NMR

Test Sample:

0.5 molar LiTNf2, often called LiTFSI, dissolved in bmpy NTf2.

Li+ +

• Different Ions in the solution can be detected by looking at different nuclei

• Ion clusters

• Ion clustering can be controlled by additives

• Zwitterions

• Series of PGSTE diffusion experiments at variable temperature

(0oC to 100oC) • 1H, 19F, and 7Li

were measured during one automatic run

• Convection not visible

D independent of D

Sample in Capillary

MN-PGSE:1H, 19F, and 7Li Diffusion Ionic Liquid as used in Lithium-Ion Batteries

D D

• Different ions have different diffusivities

Differences will depend on additives

• All follow the

same thermal activation behavior

• Deviation from Arrhenius law is probably due to the temperature dependence of the viscosity


D D

• Even at low temperature single exponential behavior

Fast exchange


• ATMA improves

temperature series,

tuning changes due

to temperature

changes can be

compensated

• ATMA enables

different nuclei

• 1H and 19F are on

the same rf

channel, which

must be tuned at

each change of the

nucleus

DiffBB:1H, 19F, and 7Li Diffusion Ionic Liquid as used in Lithium-Ion Batteries

60

60

High Power Diffusion Probe, DiffBB

High power package

= diffBB + GREAT60 + BCU20

= broadband diffusion probe + 60 A gradient amplifier + gradient cooling

> 17 T/m (1700 G/cm) @ 60 A

> 2% duty cycle @ 60 A

D < 10-14 m2/s*

*If relaxation rates permit

61

61

High Power Diffusion Probe, DiffBB

Low power package

= diffBB + GREAT3/10 + air cooling

= broadband diffusion probe + 10 A gradient amplifier + air cooling

> 2.8 T/m (280 G/cm) @ 10 A

> 2% duty cycle @ 10 A

D < 10-12 m2/s*

Special package price!

*If relaxation rates permit

62

62

High Power Diffusion Probes

Diff50

Diff50 Diff30 DiffBB

RF-coils exchangeable exchangeable fixed

Rf-channels 2 2 BB plus 2H lock

Frequencies 2 nuclei

2 nuclei

broadband

Max Gradient ~ 28.5 T/m ~ 17.5 T/m ~ 17 T/m

Variable Temperature

-40°C to 80°C

-40°C to 80°C

-40°C to 150°C

Tune/Match manually manually ATMA

Imaging Option

with Micro5 gradients system

with Micro5 gradient system

No

Diff30 DiffBB

63 63

www.bruker-biospin.com

nmr microscopy & high power diffusion · 2016. 12. 9. · couette cell, cone&plate cell,...

Documents