Nanoparticles in Organic Solvents with Polymers · 2017-12-21 · Institute of Mechanical Process...

Institute of Mechanical Process Engineering and Mineral Processing

Nanoparticles in OrganicSolvents with Polymers

Stability and Consequences Upon MaterialSynthesis Through Spray Drying

Martin Rudolph, Urs A. Peuker

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German Research Foundationproject: PE1160/7-1

[email protected]

*

June 29th 2011NanoFormulation 2011

Outline

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1) Motivation

2) Solution Method

3) Preliminary Investigations

4) Theory of Nanoparticle Interactions

5) Experiments - Stabilitya) Destabilization with non-adsorbing PMMA, PC, PSb) Stabilization with adsorbing PVB

6) Summary and Conclusion


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1 Motivation

[email protected] 29th 2011NanoFormulation 2011

• Synthesis of highly filledpolymer nanoparticle composites ( Nano > 10 %)

Magnetic Beads forsorptive Bioseparation

Hickstein, B., Peuker, U.A.J Appl Poly Sci, 112, 2366

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1 Motivation



Composite Micropowderfor Micro Injection

Molding

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1 Motivation



• Overcoming problem ofdispersing(deagglomeration + mixing)

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1 Motivation



• Overcoming problem ofdispersing(deagglomeration + mixing)

• We present an alternative modular process with thesolution and spray dryingmethod

Outline

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1) Motivation

2) Solution Method







• Polymers• Poly(methyl methacrylate)• Poly(vinyl butyral)• Poly(bisphenol A carbonate)

• Nanoparticles• Fe3O4 magnetite,

superparamagnetic

• Solvent(s)• Dichloromethane• Ethyl Acetate

• Surfactants• carboxylic acids (C14 - C18)

PVBPMMA

PC

15 n

m

2 Solution Method

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2 Solution Method


Outline

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1) Motivation

2) Solution Method






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3 Preliminary Investigations

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Investigations with TEM and pc-AFM


• TEM good distribution for spray driedmicrocomposite particle

TEM, spray dried particle

PMMA49 RS21 MAG30

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• TEM good distribution for spray driedmicrocomposite particle

• phase contrast AFMshows good distribution in an injection moulded sample

• BUT: both investigations onlyhave a very narrow field of view

phase contrast AFM,injection moulded sample

PMMA64 RS06 MAG30

Rudolph,M. Chem Ing Tech, 82, 2189 (2010)

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• phase contrast AFMlarge areas of higher phasevalues

phase contrast AFM,injection moulded sample

PMMA64 RS06 MAG30

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Investigations broad field pc-AFM and BSE-SEM


• phase contrast AFMlarge areas of higher phasevalues

• similar „clusters“ for BSE-SEM

back scattering electronSEM, sample as before

PMMA64 RS06 MAG30

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Agglomerates? / Primary Particles?


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PMMA61 – RS09 – MAG30PMMA61 – RS09 – MAG30 PMMA40 – RS10 – MAG50PMMA40 – RS10 – MAG50June 29th 2011NanoFormulation 2011

Investigations broad field pc-AFM and BSE-SEM

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PMMA61 – RS09 – MAG30PMMA61 – RS09 – MAG30 PMMA40 – RS10 – MAG50PMMA40 – RS10 – MAG50

Where are they from?Where are they from?


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Outline

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1) Motivation

2) Solution Method






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• strong VAN DER WAALS attractionleads to agglomeration

• stabilization against agglo-meration with surfactants byliquid-liquid phase-transfer

chemisorption andphysic-chemical deaggregation


surfactant of choice: ricinoleic acid

Machunsky, S. Coll & Surf A, 348, 186 (2009)

Gyergyek, S. J Coll Interf Sci, 354, 498 (2011)

4 Theory of Nanoparticle Interactions

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2

2

22H

AttractionvdW 24ln

22

42

6 hhh

hhhCE

12

,0

12

,21

1ln222FattyAcid

2

Repulsion entroprh

rhrhh

rrhTkA

rE

rHh

BornRepulsion entropAttractionvdW ninteractio EEEE

H 2r

Rosensweig,R.E. A.I.Ch.E.Symp.Ser., 5, 104 (1965)June 29th 2011NanoFormulation 2011


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• stability effects by polymeraddition

non-

adso

rbin

gad

sorb

ing

stabilizing destabilizing



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Depletion interaction – Phase diagrams

Ilett,S.M. PhysRevE, 51, 1344 (1995)June 29th 2011NanoFormulation 2011


Outline

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1) Motivation

2) Solution Method






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5 Experiments – stability

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• assessment of the massconcentration of primaryparticles wprimary

• centrifugation and determi-nation of the concentration withTGA, Photospectrometer

centrifugationxprimary, supernatant < 40 nm

diluted supernatant after centrifugation,

increasing cPoly

Rudolph,M. J Coll Interf Sci, 357, 292 (2011)June 29th 2011NanoFormulation 2011

Outline

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1) Motivation

2) Solution Method






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5a Destabilization with non-adsorbing polymers

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MM

AP

C

destabilization: decreasing primaryparticle concentration with increasingpolymer concentrationJune 29th 2011NanoFormulation 2011

F in %80 70 60 50 40 30

cMag = 24.4 g/l

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MM

A

kinetics of coagulation: not rapid fast drying after mixing should reducelarge amount of agglomerates

Prim

ary

Par

ticle

s

Agg

lom

erat

es


kinetics measuredwith DLS

Sympatec Nanophox

cMag = 1.2g/lcPoly = 58.9 g/l

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[email protected]

MM

A

kinetics of coagulation: problem ofcomparability to stability investigationdue to very low colloid concentrationJune 29th 2011NanoFormulation 2011

kinetics measuredwith UVVISat 600nm

cMag = 1.2g/lcPoly = 58.9 g/l

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• Nano-Fe3O4 dispersionunder microscope withcMag = 1.5 g/l

• addition of PMMA leadsto larger light-opticallyvisible agglomerates,

= 15 min

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• Nano-Fe3O4 dispersionunder microscope withcMag = 1.5 g/l

• addition of PMMA leadsto larger light-opticallyvisible agglomerates

• inverted BSE-SEM ofspray dried particlesPMMA64-RS06-MAG30show agglomerates aswell

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• similar agglomeratesizes for dispersion andmoulded BSE-SEM crossection

Outline

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1) Motivation

2) Solution Method






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5b Stabilization with adsorbing polymer

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VB

stabilization: increasing primary particleconcentration with increasing polymer concentration

PVB

PMMA, PC

cPoly

PMMA

PC


F in %80 70 60 50 40 30

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VB

particle size: increase in particle sizewith adsorbing polymer layer forming, of Langmuir type (line)

PVB

PMMA, PC

cPoly


F in %80 70 60 50 40 30

40


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VB

adsorption isotherm: Langmuir type adsorption of PVB on sterically stabilized nanomagnetite

PVB

PMMA, PC

cPoly

04.0/497.0

,1

PVBmax,

Poly

PolyPVBmax,

kggck

ck


F in %80 70 60 50 40 30

Outline

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1) Motivation

2) Solution Method






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Solution and spray drying process issuitable for nanocomposite synthesis

HOWEVER: nanoparticle interactionshave to be considered

Added, solved polymers will influencenanoparticle interaction

Stabilization through adsorbingpolymers reveals suitability of thesolution method

6 Summary and Conclusion

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PV

BP

CP

MM

AJune 29th 2011NanoFormulation 2011

Institute of Mechanical Process Engineering and Mineral Processing

43

Thanks for yourinterest!

Sponsored by theGerman Research Foundation:

DFG (PE1160/7-1)

Martin Rudolph

[email protected]


Meet me at poster D-PO3-20» Nanofix – Nanoparticle-wax-formulationsas Additives for Extruder Compounding«

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Supplemental

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Filler Homogeneity – SEM Analysis (F = 30 %)

cov(A) = 0.98

cov(A) = 5.45

Com

poun

ding

Solu

tion/

Dry

ing

B-SEMcross section Binary Voronoi

coefficient ofvariance - cov


45

Supplemental

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PMMA61 – RS09 – MAG30PMMA61 – RS09 – MAG30

PMMA49 – RS21 – MAG30PMMA49 – RS21 – MAG30

Phase contrast AFM analysis

Rudolph,M. CIT, 82, 2189 (2010)June 29th 2011NanoFormulation 2011

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Supplemental

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Phase contrast AFM analysis


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Supplemental


D – surfactant (detergent) ratio

F – filler concentration

• Composition

nano

surfactant

mmD

polymersurfactantnano

nano

mmmmF

1

1

surfactant

polymer

1

nano

polymer

polymer

111

111

DDF

DF

Poly – polymer concentration

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Supplemental


• Interparticle Distance

1

surfactant

polymer

nano

polymernano

3

nano

111

1433

DF

xID

49

Supplemental


solid

solidsolidDCMPoly 1

1c

DFccc

50

Supplemental


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Supplemental


• Gravimetric Characterisation with TGA/FTIR

over

all

cent

rifug

ed

overallMag,w

centriMag,wxStokes = (20 ± 2) nm

characteristic mass-loss

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Supplemental


• Segregation Effects with Spray Drying

fraction x50,3 wMagm(600°C-800°C) /

wMagyield

cylinder 8 µm 47.1 % 15.8 % 29.2 %cyclone 5 µm 44.5 % 15.9 % 60.5 %

filter 3 µm 21.5 % 18.7 % 10.3 %

TGA PSDcylinder cyclone filter

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Supplemental

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• Spray Drying

• Büchi lab scale spray dryerco-current, inert-loop

• x50, composite 4 µm

• up to 100g/h composites

low highviscosity/concentration


Nanoparticles in Organic Solvents with Polymers · 2017-12-21 · Institute of Mechanical Process...

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Transcript of Nanoparticles in Organic Solvents with Polymers · 2017-12-21 · Institute of Mechanical Process...