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Manfred Hennecke BAM Berlin IRMM 2010-11-23
Reference Materials for Material Science and Technology
BAM Federal Institute for Materials Research and Testing, D-12200 Berlin, Germany
Manfred Hennecke
The Profile of BAM
The Federal Institute for Materials Research and Testing, Berlin
MissionPromotion of the development of German economy
FunctionMaterials-technological and chemical-technological national institute
GuidelineSafety in technology and chemistry
ActivitiesResearch and development 70 %Testing, analysis, approvals 10 %Consulting and information 20 %
TasksIn the interacting fields of materials – chemistry –environment – safety
Manfred Hennecke BAM Berlin IRMM 2010-11-23
Reference Materials at BAM
about 300 materials in catalogue 2010
RMs at BAM: Overview I
Traditional focus on metals, 1912 „normal steel“ for determination
of carbon in steel
Iron and Steel: Pure iron, (un)alloyed steel, alloys, cast iron, ferro
alloys, ores, ceramic materials, slags
Nonferrous metals: Al, Al alloys, Zn, lead alloys, copper, copper
alloys, tungsten
Inorganic materials: ceramics, siliconnitride, siliconcarbide,
boroncarbide, pure materials for reconstitution analysis, glasses
(Cr(VI))
Primary pure (inorganic) substances
Isotopic composition of boron (safety of nuclear plants and
containers for nuclear materials)
RMs at BAM: Overview II
Environmental, food and feed matrix materials
Gas mixtures (up to 20 components)
Porous materials for gas adsorption and mercury intrusion
Materials for optical properties (fluorescence, water in glass)
Layered materials (mainly for surface analysis)
Polymer materials (determination of molar mass)
Elastomers (abrasion, swelling)
Biological and microbiological species (alive!, of course)
BUT…RMs forMaterials Science and Technology ?
Today, we use a seemingly unlimited variety of advanced materials which safety and availability is taken for granted for macro-, micro-, and nanoscopic building blocks
Besides broadly applied and well characterized materials such as wood, polymers, and metals, more intangible materials willgain importance
Measurement and testing of materials has always been part of materials (chemical) metrology,although often approached in less rigid, morephenomenological manner in engineering
For materials chemistry, a complete understanding of the arrangement of atoms, ions, and molecules in the material as well as its overall structural andphysical properties is needed
Werner von Siemens
1816 - 1892
„To measure is to know“
Manfred Hennecke BAM Berlin IRMM 2010-11-23
Example:
Be elemental !
Solid Materials and the BAM Approach
Purity Copper 1 Copper 2
‘Nominal Metallic’ 0.999 999 (m6N) 0.999 9 (m4N)
‘Metallic' based (by
BAM)
0.999 997
± 0.000 002
0.999 978
± 0.000 010
Total (certified by
BAM)
0.999 44
± 0.000 17
0.999 969
± 0.000 010
Materials certified for total purity hardly exist
Usually they are incompletely characterised using semi-quantitative
measurement techniques
The Approach: Measure just everything…
Approach: Element = 100 % - sum of Impurities
Measurement of all impurity elements (including O, N ...)
Measurement of total impurity content (bulk and surface)
Result: w(E) known to better than 0.01 %
Aim: System of primary material for use within the NMIs, transfer
to application via cooperation
Example: BAM-A-Primary-Cu-1
w(Cu, BAM-Y001)= 0.999 968 ± 0.000 010 with k = 2
H He
< 2.1 < 0.001
Li Be B C N O F Ne
< 0.31 < 1.1 < 3.2 0.04 0.2 1 < 2 < 0.001
Na Mg Al Si P S Cl Ar
0.002 < 0.05 < 0.07 < 0.002 < 2 5.4 < 0.6 < 0.001
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
< 0.002 0.1 < 0.06 < 0.32 < 0.04 0.07 0.01 < 5 < 0.11 1.64 matrix 0.057 < 0.11 < 0.12 0.5 0.22 < 0.014 < 0.001
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
< 0.05 < 0.014 < 0.03 < 0.015 < 0.02 < 0.06 < 0.001 < 0.03 < 1.6 < 0.014 11.3 < 0.015 < 0.05 0.14 1 < 0.22 < 0.09 < 0.001
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
< 0.0057< 0.017 < 0.002 < 0.003 < 0.003 < 0.12 < 0.009 < 0.004 < 0.007 < 0.007 < 0.008 < 0.03 < 0.005 0.47 0.23 < 0.001 < 0.001 < 0.001
Fr Ra Ac
< 0.001 < 0.001 < 0.001
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
< 0.0057< 0.002 < 0.21 < 0.001 < 0.007 < 0.003 < 0.001 < 0.001 < 0.001 < 0.001 < 0.001 < 0.001 < 0.001 < 0.002
Th Pa U
< 0.02 < 0.001 < 0.001
Determined below limits of determinations
Determined above limits of determinations
Determination not relevant; estimated
Manfred Hennecke BAM Berlin IRMM 2010-11-23
Polymerson offer and on demand
Standard Reference Elastomers SRE
Abration resistance tests of rubber:
Norm: DIN 53516, DIN ISO 4649
Road surface grip tests:
Skid Resistance Tester (SRT) :
Determination of micro-roughness
In combination with efflux meter (Moore)
Determination of macro-roughness
In Future: Development of
reference materials for
vulcanization property
tests
E-Waste
Your Laptop = 1 g Gold + 20 mg Indium + …
Targets for recycling of consumer electronics:
metals (valuable + toxic), thermoplastics
Overcome analytical problems in recycling
Recycling needs solid sample analysis
For recycling, fast solid sample analysis is
needed due to the demand on throughput
Especially XRF, LIBS and LA-ICP-MS are very
popular, due to ease of operation and
turn-around time
But: All methods are limited to microanalysis
Virtually no RMs are available for microanalysis
only „informal“ materials exist, e.g. glasses NIST
SRM 610/612 trace element composition or MPI-DING glasses
RMs for Consumer PolymersRoHS directive regulates Cd, Pb, Hg, Cr(VI), and polybrominated flame retardants in polymers
XRF is the method of choice…but matrix dependent, i.e. total mass absorption of each RM should be matching unknown samples, while surface, thickness, and form (e.g. granulates or solids) should be similar
RMs for XRF and LA-ICP-MS/OES should contain a sufficient number of mass fraction levelsavailable as granulate and as solid discs to cover the differentvarieties of sample formsvarious thicknesses with respect to the commonly utilized thicknesses in electronic industry e.g. for housings.microscopic homogeneity for µ-XRF and LA-ICP-MS
APPROACH
ABS as base polymer: Cd, Cr, Hg, Pb and Br were mixed into the polymer melt by extrusionCd, Cr, and Hg were taken as oxidesPb as stearate and Br as decabromodiphenylic ether
RM for E-Waste & RoHS
Mans, C., C. Simons, et al., New polymeric candidate reference materialsfor XRF and LA-ICP-MS - development and preliminary characterizationX-Ray Spectrometry 38, 52-57 (2009)
Sy-µXRF and LA-ICP-MS Study
Line scan Sy-µXRF
Material is sufficientlyhomogeneous formicroanalysis
Production on demand!!
MOF: a promising RM project
Attention, you need chemistry !
MOF – Metal-Organic Frameworks
Novel class of porous crystalline materials
Hybrid materials = Inorganics knots + organic linker molecules
Modular assembly for variable applications
MOF as RMs ?
MOF – Synthesis
Classical Synthesis MechanochemicalSynthesis
Type of reaction
often complicated (autoclave, high temperatures, inert gas…)
simple, solid-state-reaction, w/o solvents
Reactiontime
long , often days very short, 10-30 minutes
Yield Moderate to low high, even quantitative yields
Purity Desolvation – costly treatmentand often network destruction, i.e.
single-crystals
fine powdered products with large surface, ready-to-use
Green Chemistry !
MII(CH3COO)2 · n H2O + y L-H → MLy · n H2O + 2 CH3COOH↑
Additional: - second ligand - small amount of solvent (kneading)
Characterization of the Products
Comparison of different synthetic routes:
1. Mechanochemical, 2. Electrochemical (Basolith, BASF),
3. ethanolic solution
Nitrogen Adsorption
Klimakow et al., Chem.
Mater. accepted.
Already existing:
The unavoidable Nano
Manfred Hennecke BAM Berlin IRMM 2010-11-23
The unavoidable Nano:
Some other promising projects
(Again, you need chemistry!)
Synthesis of Nanoparticle Systems
Implementation of microreaction technology:
Reproducable and reliable synthesis with control of
i) average particle size, ii) size distribution and iii) surface
Synthesis of Nanoparticle Systems
100nm
sel. solvent
i.e. H2On
PB130-PEO66-H
Polymersomes based on block copolymers
in selective solvents, average sizes smaller
100 nm, narrow size distributionTEM from solution after drying
TEM(from solution)
100 nm
Iron Oxide Nanoparticles
in aqueous dispersion, pH controlled,
electrostatic stabilization
Simple Gold Nanoparticles ?
A simple reaction starting from
HAuCl4 using citrate as reducing
agent gives gold NP with available
sizes in the range of 16 – 147 nm
Problems: polydispersity,
reproducibility, and mechanism
State of the art:
not suitable as RM
Enustun, Turkevich, JACS 85, 3317 (1963)
Turkevich, Diss. Faraday Soc. 55 (1951)
HAuCl4 (aq.) Au NPNa3C6H5O7
100 °C
LaMer‘s Burst Nucleation Theory
LaMer, et al., JACS 72, 4847 (1950)
Finney, et al. J. Coll. Int. Sc. 317, 3514 (2008)
Time
Ato
mic
con
cen
tra
tio
n rapid self-
nucleation
growth by
diffusion
critical limiting supersaturation
Growth process of nanoparticles understood ?
Choose your Method…
SAXS: size / shape / number of particles; XANES: oxidation state
samples were continuously taken from the batch solution in order to monitor the progress of nanoparticle formation
E = 11.9 keV
Levitation: (really not a trick of Harry Potter)
Investigation of levitated droplets in an ultrasound trap
Droplet volume 5 µL, pL-Droplets can be fed by piezo
pumps
Aggregation and crystallization can be followed, no walls
In situ spectroscopy from dilute solution to the solid state
In-situ SAXS / XANES
90 60
30 0
AuIII
Au0
XANES SAXS
Sodiumcitrate as reducing & stabilizing agent
Partiale radius 6-9 nm
Polydispersity of about 10%
Duration of the synthesis is about 90 min at 75°
Experimental and Theoretical Radii of Au NP
Small…But… Synthesis of Aerosol Systems ?
Global radiative forcing (RF) estimates and ranges in 2005
+ typical geographical extent (spatial scale) of the forcing
+ assessed level of scientific understanding (LOSU)
Just in Time Production of Aerosols
The set-up allows production of defined
monodispers aerosols „just in time“
- but it is a dynamic system, not a RM
Some Conclusions
The best instrumentation is just sufficient to develop and to characterize RM. You need methods that provide a complete understanding of the involved mechanism on a molecular andatomic level
In many cases, a rational synthetic approach can pave the road to advanced RMs
Nanomaterials will require definitions of properties which will bedifficultly (at least !) traceable to the SI but are of significantrelevance for the customer
For the years to come, some RM will be only available throughproduction at the site of use
Innovation in analytical chemistry is a must for superior nextgeneration RMs -- otherwise you will become a „bottle-ist“
Thanks to:
Franziska Emmerling
Norbert Jakubowski
Michael Maskos
Ulrich Panne
and many coworkers