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