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Integrated Process

Technology for
Nanomaterial
Production

Bernd Sachweh
BASF AG, Ludwigshafen

Nanotechnoloy, Occupational and Environmental Health


Taipei, Taiwan, August 29 - Spetember 1, 2007
Process Engineering
Outline

„ Nanomaterials: definition, multidisciplinarity, market potentials


„ Production of nanomaterials
„ Integrated processes: Key to safe production routes
„ Nanoaersols: dynamics, measurement, risks
„ Summary

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Process Engineering
Definition nanotechnology

‹ We define nanoscience as the study of phenomena and


manipulation of materials at atomic, molecular and macro-
molecular scales, where
properties differ significantly from those at a larger scale

‹ and nanotechnologies as the design, characterisation, pro-


duction and application of structures, devices and systems
by controlling shape and size at the nanometer scale

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Process Engineering
Change of properties at the
nanometer scale
Next to quantum effects surface properties are playing a major
role due to the increased surface-volume ratio at the
nanometer scale

„ Chemical reactivity is higher


„ Electronic properties depend on the exact size
„ Optical properties are changing (absorption, scattering)
„ Mechanical properties (hardness)
„ Transport properties (heat, current)
„ Bioavailability
„ ...

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Process Engineering
Nanotechnology:
Convergence of the disciplines

Source: Hörber / Bachmann / Rohrer


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Process Engineering
Market potentials

Market potentials [billion €]


Forecast
500 Components
e.g. for automobiles, Î Annual growth
displays, solar > 10%
50 cells, textiles, ...
Materials and Formulations Î Market volume
e.g. modified thermoplastics, 2015
5 formulations of actives, surfaces, about €750 billion
nano-porous structures, …
Materials
0.5 e.g. organic
and inorganic BASF is active Sources:

particles, ... on all levels Growth forecast: European Commission,


DG Bank, BCC
Consumer Market Data from Sal. Oppenheim,
In Realis and Evolution Capital.
0.05
Value-adding chain
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Process Engineering
Innovation potential and new markets

Materials Nutrition & Energy Electronics Biotech


Pharma (ICT)

Mechanics Formulation Solar cell Printable Self-


Conductivity Targeting Fuel cell electronics organization
Processing Bioavailability Battery E-paper Clean-up
Barrier Release OLED CMP etc.
UV protection Diagnosis Capacitors etc.
Insulation Contrast etc.
Heat manage- agents
ment etc. Sensors etc.

Nanotechnology: cross-sectional and enabling technology


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Process Engineering
Nanotechnology:
Cross-sectional and interdisciplinary
Know-How Materials …used in End Products

Automotive
Coatings Components
Chemistry
Emulsions Paper
Physics
Nano- Dispersions Cosmetics
Analytics
materials
Plastics Textiles
Material
Science Films Displays
Biology Powders ....

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Process Engineering
Nanotechnology:
Cross-sectional and interdisciplinary

ZnO-NPs for sunscreens Flow improvement Self cleaning surfaces

5 µm

Hybrid dispersions Scratch resistant coatings Insulation


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Process Engineering
The two sides of nano

Technology Push Market Pull


„ Particles z Light-weight Materials
z Nanoparticles z Functional Packaging
z Nanotubes z Scratch-resistant Coatings
z Nanolayers z Functional Textiles
„ Materials z Insulation Materials
z Nanomodified Plastics z Energy Storage
z Nanomodified Coatings z Efficient Lighting
z Nanoporous Foams z New Cosmetics
„ Nanostructured Devices for z Water Treatment (Membranes
and Filters)
z Information & Communication
Technology z Information & Communication
Technology
z Medicine (Diagnostics &
Therapeutics) z Medicine
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Process Engineering
Nanoparticles are often the starting point
for a new material property

„Nano“ on its own is neither a product nor a value, but


if a nanoscale aspect essentially contributes to a
system solution, it will create added value.

Gold cluster
55 gold atoms
Sainte Chapelle, Paris
12. – 13. C.

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Process Engineering
Technology overview for synthesis of
high-performance nanoparticles
Gas-based processes:
„ Flame synthesis
„ Hot wall reactor
„ Plasma technologies
„ Desublimation
„ Chemical vapor deposition
„ Physical vapor deposition
Liquid-based processes:
„ Atomic layer deposition
„ Nano-grinding
„ Precipitation (Nozzle, Co-Precipitation,
Miniemulsions, HIGRATEC)
„ Sol-Gel-Synthesis
„ Hydrothermal decomposition
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Process Engineering
Integrated Process starting with gas
phase synthesis

Flame Gas Electrostatic


synthesis quenching stabilization

Transfer into
Organic coating
liquids

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Process Engineering
The Integrated Process
Core/Shell Particles
Flame synthesized
H2O with
material
additives
N2 N2 Waste
gas

(Wet-)E-Filter

Organic Hot wall


Desublimation
material reactor
Powder

Stabilized suspension
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Process Engineering
Principle of a flame synthesis

quenching gas
additives

air or
shield gas
(fuel)
precursor
(solid/liquid/gaseous)
evaporation of quenching
reactor
precursors (s/l) zone

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Process Engineering
Adjustable size & morphology
on a nano-scale
„ Most important process parameters:
¾ Temperature profile (adjustable by quenching rate)
¾ Residence time
¾ Concentration of precursors

Faster temperature decrease


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Process Engineering
Quenching technologies

Mixing of 2 gas flows Supersonic expansion


Cooling rate: 15.000 K/s Cooling rate: 1.000.000 K/s

1 bar Hot gas + 1 bar


700°C sublimed material 700°C

Cooperation
Quench gas with University of
Kaiserslautern

Quench gas

Cool gas +
particles
1 bar 200 mbar
190°C 190°C

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Process Engineering
Stabilization against spontaneous
agglomeration
„ Instantaneous charging after particle formation
„ Charging kinetics must be higher than agglomeration kinetics
100
N2

Efficiency, Losses
80

60

Optimum
40

Desublimation 20

0
Problems: 6 8 10 12 14 16
• Corona quenching Corona voltage (kV)
• Losses
Cooperation with University of Karlsruhe
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Process Engineering
Separation of nanoparticles by a wet
electrostatic precipitator
Liquid with
additives
Waste
H O +gas
Off-gas
2
additives

(Wet-)ESP

Flame synthesis

suspension

Stabilized Suspension

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Process Engineering
Test equipment for desublimation

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Process Engineering
Coated metal oxides from flame synthesis

50 nm 20 nm

SiO2 on ZnO SiO2 on TiO2


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Process Engineering
Nanotechnology –
advantage and risk
Potential hazard and risk from using nanomaterials have to
be evaluated and minimized case-by-case

Advantage Risk

Nanotechnology + Environment, Health and Saftey =


Sustainable Innovation
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Process Engineering
Nanoaerosols exhibit strong dynamic
changes

Agglomeration kinetics depends on

ƒ Particle size
ƒ number concentration

Number frequency
ƒ residence time

Source Recipient

Partikel size

time after release

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Process Engineering
Standard technology for nano aerosols

Scanning Mobility Particle Sizer (SMPS)


Measurement of size distribution in the nanometer and submicron
regime
TSI (USA) Grimm (D)

Measurement of number concentration

CPC
Condensation Particle Counter

DMA
Electrostatic classifier

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Process Engineering
Modification of Nanoparticles during
time after generation (1)
ƒ Model system: electrical neutral NaCl nanoparticles
1,0E+08 250
number concentration [#/cm³]

ƒ number concentration

Partcile size [nm]


1,0E+07 200 decreases

Modell ƒ Typical half life time in


N0 ambient environment with
1,0E+06 N( t ) = 150
1 + N0 ⋅ K ⋅ t increased exposure:
~ 10 – 20 Minuten

1,0E+05 100 ƒ Paricle size increases


1 10 100
Zeit [min]

ƒ SMPS-Measurement (duration 5 min.) is affected when used e. g. at


working place environments during spontaneous release of nanoparticles!
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Process Engineering
Modification of Nanoparticles during
time after generation (2)

1,5E+07
Partikelgrößenverteilung [#/cm³]

ƒ Preferred growth form larger


3 Minutes
particles

1,0E+07 ƒ Shift monomodal – bimodal


distribution by agglomeration

ƒ Reduced hazadous poteial


5,0E+06 30 Minutes
during exposure?
60 Minutes

0,0E+00
10 100 1000
Particle size [nm]

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Process Engineering
Characterization requirements

Primary particles Agglomerate-


REM/TEM distribution
offline SMPS
Number frequency

online

Multi dimensional aerosol


120000 :1 200 nm
characterization
10 100 1000
but Offline!
Particle size [nm]
ƒ no process control possible
ƒ no ad-hoc measures at working
place possible
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Process Engineering
What does multidimensional aerosol
characterization mean?
Toxicological Working place Production
studies readings control

Multidimensional aerosol characterization

Particle size distribution Agglomerate fraction Morphology


Partikelgrößenverteilung

SMPS

9 100 nm
10 100 1000
Partikelgröße [nm]

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Process Engineering
Clear principles for nanotechnology
BASFs Code of Conduct Nanotechnology
Based on our commitment to Responsible
Care®, we defined clear principles:
„ We identify sources of risk for employees in
our laboratories, production plants, packing
and storage facilities and eliminate these
using appropriate measures in conduction
with safety actions
„ We take the risks of new technologies in
products and processes seriously and work
continuously to identify potential
environmental and health risks.
„ We are committed to transparency and
contribute constructively to public debate
and drawing up legislation. www.corporate.basf.com/de/sustainability/
dialog/nanotechnologie/verhaltenskodex.htm
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Process Engineering

BMBF-project

Companies and scientific institutions join forces to research the effects of industrially-
produced nanoparticles on human health and the environment.

„ Start: 1st march 2006


„ duration: 3 years
„ Project volume: 8 Mill. €
„ BMBF: ca. 5.2 Mill. €
„ Industry part: ca. 2.8 Mill. €
Partners:
BASF AG ItN Nanovation GmbH
Bayer MaterialScience AG IUTA e.V.
Degussa AG SOLVAY Infra Bad Hönningen GmbH
Forschungszentrum Karlsruhe GmbH SusTech GmbH
IBE e.V. Universität Bielefeld
IGF Universität des Saarlandes
Universität Münster
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Process Engineering
Safety Issue: Nanotechnology
European Activities & Projects
„ EU-projects: Nanosafe 1, Nanosafe 2 (development of measurement techniques and
research on the toxicological properties) and Nanoderm
„ Working group “Opportunities, Ecological and Health Aspects of Nanotechnology”
established by DECHEMA
„ Working group “Responsible Use and Production of Nanomaterials” established by
VCI/DECHEMA
„ German BMBF-project “NanoCare” to develop a short term inhalation model to assess the
biological effect of nanoparticles

„ British Royal Society, Study: Nanoscience and nanotechnologies: opportunities and


uncertainties (July 2004)

„ DEFRA: Characterising the potential risks posed by engineered nanoparticles

„ ECETOC: White Paper on Nanomaterials (2005)

„ European Commission: Scientific Committee on Emerging and Newly-identified Risks


„ European Technology Platform Sustainable Chemistry, a multi-stakeholder initiative
(Chemical industry, academia, national governments, EU-Commission, NGOs) of the
European Commission
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Process Engineering
Our Commitment to Transparency and
Dialogue also Applies to Nanotechnology

We are committed to transparency


and an objective and constructive
public debate.

„ Website about current


trends
„ Dialogue Paper to
promote public debate
„ Presentations at
international
conferences

http://corporate.basf.com/de/sustainability/dialog/nanotechnologie
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Process Engineering
BASF included in the Innovest Nanotechnology Index
for Responsible Development of Nanotechnology

‹ Index compiled by
Innovest Strategic Value Advisors,
a New York-based investment research firm
‹ Index contains 15 companies chosen from
a set of 200 public and 100 private companies
‹ Companies were reviewed for qualities that
Innovest believes to be appropriate in offsetting
potential perception concerning nanotechnology
‹ In particular early efforts to offset risks through
product strategy, risk management and
product stewardship were assessed
‹ BASF has achieved especially good results
in product stewardship

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Process Engineering
WORKSHOP: Exchange of experience,
Networking in the community

17. April 2007, BASF Feierabendhaus

Scientific dialog between experts form


ƒ Industry (Bayer, Degussa, Merck, Wacker, BASF...)
ƒ Academia (Uni Karlsruhe und Dresden, BAM...)
ƒ Authorities (Bayrisches Staatsministerium für Umwelt,
Gesundheit und Verbraucherschutz)
ƒ Accident prevention association (BGIA, BG Chemie)

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Process Engineering
Summary

„ Free handling of nanopowders should be avoided


„ Transfer of gasborne into a matrix is preferable within the process
„ Embedding “Nano” into a matrix of high volume products is also
prerequisite for access into the value chain
„ Consistent characterization of aerosols is necessary for different
disciplines (toxicology, working place, process control)
„ Fast measuring systems are required due to high dynamic changes
of aerosols
„ Characterization has to be carried out in a multi-dimensional way to
derive clear correlations between aerosol properties and effects
„ New instruments have to be developed!

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