# Research Activity: Synthesis and Processing Science

Division: Materials Sciences and Engineering

Primary Contact(s): Jane Zhu
([Jane.Zhu@science.doe.gov](mailto:Tim.Fitzsimmons@science.doe.gov);
301-903-3811)

Team Leader: Robert Gottschall

Division Director: Patricia Dehmer, Acting

# Portfolio Description:

Synthesis and Processing Science addresses the fundamental understanding
necessary to extend from design and synthesis to the preparation of
materials with desired structure, properties, or behavior. This includes
the assembly of atoms or molecules to form materials, the manipulation
and control of the structure at all levels from the atomic to the
macroscopic scale, and the development of processes to produce materials
for specific applications. The goal of basic research in this area
ranges from the creation of new materials and the improvement of the
properties of known materials, to the understanding of such phenomena as
adhesion, diffusion, crystal growth, sintering, and phase transition,
and ultimately to the development of novel diagnostic, modeling and
processing approaches. This activity also includes development of *in
situ* measurement techniques and capabilities to quantitatively
determine variations in the energetics and kinetics of growth and
formation processes on atomic or nanometer length scales.

# 

# Unique Aspects:

• The Materials Preparation Center (MPC) at the Ames Laboratory is
operated for the purposes of understanding and further developing
innovative and superior processes and for providing small quantities of
unique, research-grade materials that are not otherwise available to
academic, governmental, and industrial research communities.

• Through the [C]{.underline}enter of Excellence for the
[S]{.underline}ynthesis and [P]{.underline}rocessing of Advanced
Materials (CSP), coordinated, collaborative research partnerships
related to synthesis and processing of advanced materials are promoted
between DOE national laboratories, universities, and the private sector.

-   Non-equilibrium processing methods are studied using advanced
    modeling techniques and experimental methods, including innovative
    real-time, *in-situ* techniques enabled by synchrotron radiation.

-   Advanced growth techniques and *in situ* diagnostics have been
    developed for the synthesis of improved thin-film structures of
    advanced materials.

**Relationship to Others:**

This program is intimately related to the other research activities in
the Division of Materials Sciences and Engineering as the synthesis and
processing of materials is critically important and must be tailored to
achieve optimal structure, properties and behavior.

Through materials supplied by the Ames MPC, linkage is provided to the
Office of Biological and Environmental Research, the academic community,
the industrial community and international research institutions. In FY
2002 the MPC provided materials to 14 users at DOE laboratories, 3 at
other federal laboratories, 46 universities, 72 industrial laboratories
and 37 international universities and institutions. Total orders totaled
\$515 k in FY 2002. During FY 2002 the MPC continued its effort to
prepare 24 kilograms of LaNi~5-x~Sn~x~ for the Jet Propulsion
laboratory. This hydrogen sorption material is to be used in fabricating
a Joule-Thompson cryocooler for background radiation measurements aboard
the joint ESA-NASA PLANCK Mission vehicle scheduled for launch in 2007.
A total of over 500 lbs of Sn-Ti alloy was prepared during FY 2002 for
the fabrication of superconducting wire to be used for the South Korean
K-Star Tokamack and the National High Magnetic Field Laboratory at
Florida State University.

Additional linkages within the Department of Energy are provided through
the Energy Materials Coordinating Committee. This research activity is
also linked with Defense Programs via Nanoscience Network. Interagency
coordination is provided by participation in the MatTec Communications
Group on Metals, the MatTec Communications Group on Structural Ceramics,
and the National Nanotechnology Initiative.

# 

# Significant Accomplishments:

This program has changed the way people understand and think about the
preparation of materials. Experimental, theoretical and computational
tools are developed and applied to advance the scientific understanding
of complicated thermodynamic and kinetic phenomena underlying processes
ranging from self-assembly to the far from equilibrium reactions that
take place in welding. In the welding area, a coupled thermodynamic and
kinetic model was developed to describe stability of the principal
phases in stainless steels. This knowledge has led to the modification
of the standard diagram used to choose welding electrode compositions
for stainless steels. Additional modeling work utilizing massively
parallel computers has permitted the linkage of macro- and microscopic
scale phenomena during the melting and solidification of a weld. This
permits simulation and visualization of weld microstructure as a
function of processing conditions, e.g. during the melting, addition of
new compounds, and resolidification that occurs during welding.
Experimentally, tracking of real-time phase transformations that occur
during weld solidification are made possible using synchrotron radiation
and provide invaluable data to support scientific modeling and
simulation and leads to better electrode design. The later work received
the 2001 Spararagen Award from the American Welding Society. A current
application in electrode design is the new understanding of the
consequences of \"self shielding\"\--that is preventing adverse
reactions with air through additions of aluminum or other powders to the
electrodes on compound (phase) stability leading to understanding of
potential changes in electrode composition on properties of welded
components. Recognitions include the two recipients of the Warren F.
Savage Award from the American Welding Society

In the self-assembly area, developing scientific understanding of
surfactant interactions with ceramic compounds and other materials,
including biological tissues, has permitted the growth of ordered porous
ceramic structures duplicating template structures from the nanoscale to
the macro scale.

Specific achievements include:

-   Investigations of self-assembled heteroepitaxial semiconductor
    quantum dots using real-time stress sensing and light scattering
    showed how elastic repulsion determines evolution of dot arrays.
    Repulsion promotes spatial ordering, accelerates ripening kinetics,
    and enhances quantum dot phase transition.

-   A rapid, efficient self-assembly process for making nanophase
    composites that mimic the complex construction of seashells was
    developed and it resulted in a strong and tough (crack resistant on
    impact loading) material.

-   Ceramic substrates were synthesized with tailored and regularly
    ordered nanoscale pore sizes of controlled shapes and sizes. It was
    then found that these substrates would remove deadly heavy metals
    such as mercury, lead and silver from water.

-   A breakthrough in the fundamental understanding of the processing of
    ceramic aerogel films led to a new, non-toxic, low temperature and
    low-pressure process to produce such films in an environmentally
    benign manner. This discovery overcame the sixty-year barrier to the
    large-scale commercial utilization of these films, won the
    prestigious Iler Award of the American Chemical Society and was
    cited as an important discovery by the Wall Street Journal.

-   Established a Materials Preparation Center to provide outside
    researchers from academia, industry and government laboratories with
    research quality and quantities of unique, carefully controlled
    research-grade materials and crystals that would not otherwise be
    available. The following technologies were enabled by this Center:

    -   Lead free solder

    -   Magnetocaloric gadolinium-silicon-germanium alloys

    -   Recyclable lightweight automotive composite materials

    -   Terfenol-D which is a mangetostrictive alloy containing terbium,
        dysprosium, and iron that was developed at the Center and led to
        the spin-off of a new private sector company which now markets
        this material

-   

-   Quasicrystal coatings produced by plasma-arc spray that have
    superior wear resistance and thermal insulation behavior coupled
    with reduced surface friction for potential thermal barrier wear
    resistant coating applications in aircraft-engine components.

-   A uniform three-dimensional coating process known as \"Plasma Ion
    Immersion Processing\" was improved so as to fabricate hard coating,
    such as diamond-like carbon, that exhibit low sliding friction and
    superior wear resistance. This process achieves a uniform
    implantation rate over a very large surface, a very high rate of
    implantation, and has the ability to produce a uniform thickness and
    quality coating over complex three-dimensional geometries, and is
    cost-effective.

-   

-   A nanophase molecular template method was developed to synthesize
    films that exploit the dielectric properties of air to achieve
    ultra-low dielectric constants for the next generation of
    microelectronic devices and computers.

**Mission Relevance:**

This research supports the Department of Energy's overarching goals for
improved energy efficiency and protection of the environment. Specific
relevant applications include hard and wear resistant surfaces to reduce
friction and wear; high-rate, superplastic forming of light-weight,
metallic alloys for fuel efficient vehicles and other structures needed
in fuel-efficient land and air transportation applications;
high-temperature structural ceramics and ceramic matrix composites for
high-speed cutting tools, bearings, engines and turbines (to enable fuel
efficiency and low-pollutant emissions); ordered intermetallic alloys
for harsh applications (requiring heat, load, wear and corrosion
resistance), including engines and turbines (also to enable fuel
efficiency and low pollutant emissions); non‑destructive analysis for
early warning of impending failure and on-line flaw detection and
quality assurance during production; response of magnetic materials to
applied static and cyclical stress; and plasma, laser, and charged
particle beam surface modification to increase corrosion and wear
resistance; and welding and joining, including dissimilar and
non-metallic materials.

# 

# Scientific Challenges: 

Understanding the physics and chemistry for the synthesis and
processing, as well as the thermodynamics and kinetics of reaction of
nanoscale materials and structures and the elements of the processing
environment are critical to the preparation of larger components. There
are significant experimental, theoretical and computational challenges
in understanding what is occurring so that the benefits of nanoscale
phenomena can be realized in larger scale components. Major scientific
challenges also remain in the fabrication and the fundamental
understanding in the non-trivial assemblies of inorganic, organic and
biomimetic materials. This research activity will develop carefully
designed experiments to directly compare measured behavior to results of
systems modeling.

For thin films systems, future efforts are required to solve materials
problems such as the adhesion and the thermal and environmental
stability. Although there is steady progress in the synthesis and
processing of materials, there still exists a serious deficit in the
ability to produce (new) materials with desired properties and
microstructures by rational design and synthesis. Experimental methods
and theoretical models need to be developed to achieve mesoscopic
structures perhaps via self-organized growth using various kinds of
templates. Scientific challenges also lie in new composite materials
with various matrices, and in ecologically-benign materials.

**Funding Summary:**

**Dollars in Thousands**

**[FY 2002]{.underline}** **[FY 2003 Request]{.underline}** **[FY 2004
Request]{.underline}**

14,497 18,595 18,570

> **[Performer]{.underline} [Funding Percentage]{.underline}**
>
> DOE Laboratories 78.5%
>
> Universities 21.5%

These are percentages of the operating research expenditures in this
area; they do not contain laboratory capital equipment, infrastructure,
or other non-operating components.

**Projected Evolution:**

• Increased emphasis on understanding the opportunities and challenges
presented by nanoscale materials and by the processing of larger
components containing nanoscale materials.

• Science based understanding of advanced synthesis and processing
methods such as self-assembly, molecular-directed nanostructure
formation, and novel deposition methods will be investigated. This
understanding will be applied of to attain new structures and
compositions, to fabricate materials with new functionalities, and to
reduce the energy and environmental impact of processing.

• Processing research will be extended to include new ceramic,
intermetallic, semiconducting, organic and biomimetic materials and
material structures, including nanocrystalline materials, films,
coatings, and crystals. Analytical techniques and modeling will be
developed and applied to determine and predict the relationship of
synthesis and processing parameters to structure, purity, deformability,
residual stresses, toughness, adhesion, and electronic, optical and
magnetic properties.

• Welding process models will be refined and extended to solidification
of aluminum alloys. The relationship of process conditions to
microstructure development in various alloy welds will be studied by
real-time, *in-situ* x-ray diffraction enabled by synchrotron radiation.
Follow-on work will investigate supercooling effects in welding, and
determine the residual stress distribution in welds and spatial
distribution of different phases in different locations of the weld
heat-affected-zone.

• Processing capabilities of the Materials Preparation Center will be
expanded to provide intelligent process control and modeling and to
provide new innovative synthesis and processing techniques. Plans
include the use of a plasma-heated skull-melting furnace with
capabilities to cast or atomize materials. Follow on efforts in
microstructure-sensitive processing and providing real-time monitoring
of processing and correlation with process models.

• An understanding of interfacial interactions at the molecular level
will be developed, and their influence on molecular conformation and
ordering will be shown for evolving nanostructures. An understanding of
how short and long-range molecular forces mitigate the formation of
ordered amorphous structures will be extended to develop an
understanding of how biological systems control the formation of ordered
assemblages of crystalline nanoparticles.

November 13, 2023