rexresearch.com
James PIKUL, et al.
Metallic Wood
https://www.sciencedaily.com/releases/2019/01/190128125314.htm
January 28, 2019
'Metallic wood' has the strength
of titanium and the density of water
Summary: Researchers have built a sheet of nickel with nanoscale
pores that make it as strong as titanium but four to five times
lighter.
High-performance golf clubs and airplane wings are made out of
titanium, which is as strong as steel but about twice as light.
These properties depend on the way a metal's atoms are stacked,
but random defects that arise in the manufacturing process mean
that these materials are only a fraction as strong as they could
theoretically be. An architect, working on the scale of individual
atoms, could design and build new materials that have even better
strength-to-weight ratios.
In a new study published in Nature Scientific Reports, researchers
at the University of Pennsylvania's School of Engineering and
Applied Science, the University of Illinois at Urbana-Champaign,
and the University of Cambridge have done just that. They have
built a sheet of nickel with nanoscale pores that make it as
strong as titanium but four to five times lighter.
The empty space of the pores, and the self-assembly process in
which they're made, make the porous metal akin to a natural
material, such as wood.
And just as the porosity of wood grain serves the biological
function of transporting energy, the empty space in the
researchers' "metallic wood" could be infused with other
materials. Infusing the scaffolding with anode and cathode
materials would enable this metallic wood to serve double duty: a
plane wing or prosthetic leg that's also a battery.
The study was led by James Pikul, Assistant Professor in the
Department of Mechanical Engineering and Applied Mechanics at Penn
Engineering. Bill King and Paul Braun at the University of
Illinois at Urbana-Champaign, along with Vikram Deshpande at the
University of Cambridge, contributed to the study.
Even the best natural metals have defects in their atomic
arrangement that limit their strength. A block of titanium where
every atom was perfectly aligned with its neighbors would be ten
times stronger than what can currently be produced. Materials
researchers have been trying to exploit this phenomenon by taking
an architectural approach, designing structures with the geometric
control necessary to unlock the mechanical properties that arise
at the nanoscale, where defects have reduced impact.
Pikul and his colleagues owe their success to taking a cue from
the natural world.
"The reason we call it metallic wood is not just its density,
which is about that of wood, but its cellular nature," Pikul says.
"Cellular materials are porous; if you look at wood grain, that's
what you're seeing? -- ?parts that are thick and dense and made to
hold the structure, and parts that are porous and made to support
biological functions, like transport to and from cells."
"Our structure is similar," he says. "We have areas that are thick
and dense with strong metal struts, and areas that are porous with
air gaps. We're just operating at the length scales where the
strength of struts approaches the theoretical maximum."
The struts in the researchers' metallic wood are around 10
nanometers wide, or about 100 nickel atoms across. Other
approaches involve using 3D-printing-like techniques to make
nanoscale scaffoldings with hundred-nanometer precision, but the
slow and painstaking process is hard to scale to useful sizes.
"We've known that going smaller gets you stronger for some time,"
Pikul says, "but people haven't been able to make these structures
with strong materials that are big enough that you'd be able to do
something useful. Most examples made from strong materials have
been about the size of a small flea, but with our approach, we can
make metallic wood samples that are 400 times larger."
Pikul's method starts with tiny plastic spheres, a few hundred
nanometers in diameter, suspended in water. When the water is
slowly evaporated, the spheres settle and stack like cannonballs,
providing an orderly, crystalline framework. Using electroplating,
the same technique that adds a thin layer of chrome to a hubcap,
the researchers then infiltrate the plastic spheres with nickel.
Once the nickel is in place, the plastic spheres are dissolved
with a solvent, leaving an open network of metallic struts.
"We've made foils of this metallic wood that are on the order of a
square centimeter, or about the size of a playing die side," Pikul
says. "To give you a sense of scale, there are about 1 billion
nickel struts in a piece that size."
Because roughly 70 percent of the resulting material is empty
space, this nickel-based metallic wood's density is extremely low
in relation to its strength. With a density on par with water's, a
brick of the material would float.
Replicating this production process at commercially relevant sizes
is the team's next challenge. Unlike titanium, none of the
materials involved are particularly rare or expensive on their
own, but the infrastructure necessary for working with them on the
nanoscale is currently limited. Once that infrastructure is
developed, economies of scale should make producing meaningful
quantities of metallic wood faster and less expensive.
Once the researchers can produce samples of their metallic wood in
larger sizes, they can begin subjecting it to more macroscale
tests. A better understanding of its tensile properties, for
example, is critical.
"We don't know, for example, whether our metallic wood would dent
like metal or shatter like glass." Pikul says. "Just like the
random defects in titanium limit its overall strength, we need to
get a better understand of how the defects in the struts of
metallic wood influence its overall properties."
In the meantime, Pikul and his colleagues are exploring the ways
other materials can be integrated into the pores in their metallic
wood's scaffolding.
"The long-term interesting thing about this work is that we enable
a material that has the same strength properties of other super
high-strength materials but now it's 70 percent empty space,"
Pikul says. "And you could one day fill that space with other
things, like living organisms or materials that store energy."
Sezer Özerinç and Runyu Zhang of the University of Illinois at
Urbana-Champaign, and Burigede Liu of the University of Cambridge,
also contributed to the study.
The research was supported by the Department of Energy Office of
Science Graduate Fellowship Program, made possible in part by the
American Recovery and Reinvestment Act of 2009, administered by
ORISE-ORAU under contract no. DE-AC05-06OR23100.
https://www.nature.com/articles/s41598-018-36901-3
Scientific Reports volume 9, Article number: 719 (2019)
High strength metallic wood from
nanostructured nickel inverse opal materials
James H. Pikul, Sezer Özerinç, Burigede Liu, Runyu Zhang,
Paul V. Braun, Vikram S. Deshpande & William P. King
Abstract
This paper describes a nickel-based cellular material, which has
the strength of titanium and the density of water. The material’s
strength arises from size-dependent strengthening of load-bearing
nickel struts whose diameter is as small as 17 nm and whose 8 GPa
yield strength exceeds that of bulk nickel by up to 4X. The
mechanical properties of this material can be controlled by
varying the nanometer-scale geometry, with strength varying over
the range 90–880 MPa, modulus varying over the range 14–116 GPa,
and density varying over the range 880–14500 kg/m3. We refer to
this material as a “metallic wood,” because it has the high
mechanical strength and chemical stability of metal, as well as a
density close to that of natural materials such as wood.
Introduction
Cellular materials with spatially organized and repeating pore
geometries can have dramatic strength improvements as structural
elements shrink to the nanometer scale1,2,3,4. This paper
describes a nanostructured cellular material based on
electroplated nickel (8,900 kg/m3 bulk density), which has the
strength of titanium and the density of water (1,000 kg/m3). The
high strength arises from size-dependent strengthening of
load-bearing nickel struts whose diameter is as small as 17 nm and
whose strength is as high as 8 GPa. We refer to this material as a
“metallic wood,” because it has the high mechanical strength and
chemical stability of metal, as well as a density close to that of
natural materials such as wood.
Cellular materials with nanometer-scale structural elements
exhibit remarkable material properties5, for example high
strength3,6,7,8,9,10, high energy absorption4, ultra-low
density1,11,12,13,14, and high specific strength1,15,16. To
understand the origin of these enhanced properties, we can look at
the performance of single nanopillars which approximate a single
strut in a nanostructured cellular material. Compression tests on
nanopillars made from single crystal metals showed that reducing
pillar diameter increased pillar strength by up to an order of
magnitude more than the bulk material’s strength17,18,19. This
size-dependent strength enhancement has been widely studied in
single crystals17,18,20,21,22. In nanopillars made from
nanocrystalline metals, however, both an increase in strength (for
Ni and Au)23,24 and decrease in strength (for Ni and Pt)25,26 have
been observed as geometric dimensions were reduced to the size of
a single grain diameter. When nanocrystalline gold was used in the
struts of a nanostructured cellular material, the cellular solid
showed dramatic strength enhancement as the strut diameter
decreased3,6, but the conflicting results in nanopillars make it
difficult to predict if nanostructured cellular materials made
from nanocrystalline metals will exhibit a strength enhancement or
reduction.
In addition to nanoscale enhancement, the macroscopic properties
of nanostructured cellular materials are important when
considering them for engineering applications. Most articles on
nanostructured cellular materials report specific strength below
100 MPa/(Mg m3), which is comparable to polymers and common
metals1,3,4,6,7,8,9,10,11,12,13,14,15,16,27,28,29. Materials with
specific strength above 100 MPa/(Mg/m3) are attractive because
their strength approaches that of engineering metals and
ceramics1,15,16. However, the density of these materials can be
low, in the range of 6–410 kg/m3, which prohibits their use in
some applications. Consider, for example, a metal panel modeled as
a simply supported beam with length 1 m, cross-sectional thickness
1 mm, specific strength 100 MPa/(Mg/m3), and density 100 kg/m3.
For an application in which the panel supports a 100 N load at the
center, the sheet would require a minimum width of 15 m. In
contrast, a panel with specific strength 100 MPa/(Mg/m3) and
density 1,000 kg/m3 would require a minimum width of 1.5 m, which
is in general a more reasonable solution. Many structural
materials have density near 1,000 kg/m3, including engineering
polymers and naturally occurring materials such as wood. Only a
few articles report nanostructured cellular materials with density
near 1,000 kg/m3, and these articles focus on ceramics and carbon
based materials rather than metals4,16,29,30. In general, there is
a lack of published research on strong nanostructured cellular
materials that have enough mass to support loads found in
industrial applications.
Here we report a cellular material based on nanostructured nickel
inverse opal materials. The mechanical properties of this material
are governed by the size-dependent strengthening of
nanometer-scale structural elements, allowing large specific
strengths up to 230 MPa/(Mg/m3) in porous nickel. This specific
strength is larger than most high strength metals including high
strength stainless steel and Ti-6Al-4V31,32. The mechanical
properties of this material can be varied between natural
materials and high strength metal alloys by controlling the
geometric parameters within the cellular architecture; we
demonstrate materials with yield strengths over the range
90–880 MPa, specific moduli 7–25 GPa/(Mg/m3), and densities
880–14500 kg/m3. Using finite element simulations and well
established micropillar compression and nanoindentation testing,
we find that the material strength increases as the
nanometer-scale strut diameter decreases. The strut yield
strengths increase from 3.8 to 8.1 GPa as the strut diameter
decreases from 115 to 17 nm, which is a 4X increase over the 2 GPa
bulk deposited nickel yield strength.
Results
Figure 1a shows the fabrication of the inverse opal material.
First, monodisperse polystyrene (PS) particles of diameter
260–930 nm were self-assembled onto a gold/chromium coated
substrate in a face centered cubic (FCC) orientation. The PS was
sintered at 96 °C to improve stability and increase the
interconnect diameter between PS spheres. Nickel, 99.9%, was
electrodeposited into the voids of the PS structure, followed by
PS etching in tetrahydrofuran. The result was an open cell inverse
opal material having interconnected spherical pores in a
face-centered cubic orientation. For some samples, conformal
electrodeposition of either additional nickel or rhenium-nickel
alloy (80 wt% rhenium) increased the solids volume fraction, strut
diameter, and mass. The additional deposited nickel had the same
composition as the nickel used to fabricate the inverse opal
structure. Mechanically tested samples with rhenium are labeled
Re. The average grain sizes of the nickel film and nickel inverse
opals were 12.4 nm and 15.1 nm, calculated from the XRD data shown
in the supplementary information using the Scherrer equation. The
grain size was similar for coated and un-coated nickel samples. A
15 nm grain size in pure nickel corresponded to a ≈6.4 GPa
hardness33,34, near the peak hardness values of pure nickel, which
agreed well with our electrodeposited nickel thin film
nanoindentation hardness measurements of 5.8 GPa. The
self-assembly based fabrication method can produce material
samples larger than 100 mm2, while allowing ~10 nm control of
structure and chemistry by altering the polystyrene diameter,
processing temperature, and electroplating parameters. In
comparison, most methods for fabricating nanostructured cellular
solids with controlled and repeated unit cell morphologies are
limited to sample sizes with areas smaller than about 5 mm2
1,11,12,15,27,28,35. Figure 1b–g show SEM images of the material
with 500 nm pores fractured on the (111) plane. Figure 1b,c show
the inverse opal material with no coating and 0.16 solids volume
fraction. Figure 1d,e show the material uniformly coated with
21 nm of nickel, which increased the solids volume fraction from
0.16 to 0.35. Figure 1f,g show the nickel inverse opal material
uniformly coated with 25 nm of rhenium-nickel alloy, which
increased the solids volume fraction to 0.46. Figure 1h shows a
material with 500 nm pores, 2 cm2 area, and 15 µm thickness
fabricated on a gold/chromium coated glass slide. Figure 1i shows
a material with 300 nm pores and 20 µm thickness fabricated on
gold/chromium-coated polyimide. The material is flexible and when
prepared on a polyimide sheet could be bent past a 0.5 cm radius
(Fig. 1i). Table 1 shows the fabricated materials and their
geometric attributes such as coating thickness and volume
fraction...
Conclusion
In conclusion, we present metallic wood fabricated from nickel
inverse opals, which has the strength of titanium and the chemical
properties of a metal, while having the density of water and the
cellular nature of natural materials like wood. The high strength
of the metallic wood results from the size-dependent strengthening
of the inverse opal struts, which have up to 4X the yield strength
of bulk electrodeposited nickel and enable high specific strengths
of 230 MPa/(Mg/m3). The cellular structure can be controlled to
tune the modulus and strength each by a factor of 10X.
The metallic wood can be easily fabricated over 100 mm2 areas, can
be processed at room temperature, and can be combined with
additional functional materials, as demonstrated with the rhenium
coatings49. The high strength continuous metallic architecture
with isotropic elasticity, high hardness, and high strain energy
storage could be important for a variety of applications such as
energy storage50,51,52, heat transport53, and sensors54,55. Future
work could explore improvements in specific strength above
230 MPa/(Mg/m3) by incorporating lightweight metals such as
titanium or aluminum and developing roll-to-toll processing of
high strength porous metals from self-assembly..
[ Click to Enlarge ]
KR101625485B1
3D-GRAPHENE INVERSE OPAL
[ PDF ]
Abstract
The present invention includes a plurality of α-Fe in
the base material2O3Graphene inverse opal (α-Fe2O3/ GIO) is an
α-Fe stacked in three dimensions2O3Graphene inverse opal
(α-Fe2O3Relates to / GIO) structure, according to the present
invention α-Fe2O3Yes forming a fin inverse opal structure (1)
after laminating a polystyrene (PS) particles in the base
material, followed by electrodeposition of nickel (Ni)
3-dimensional polystyrene (PS) opal (opal) structure; (2) forming
a three-dimensional nickel inverse opal (inverse opal) structure
(3D-NIO) by removing the 3D-opal structure PS; (3) forming the
three-dimensional nickel inverse inverse opal structure an opal
structure and carbide using a polyol solution in the presence of a
Ni catalyst, to remove the three-dimensional nickel inverse opal
structure, a three-dimensional graphene (3D-GIO); And (4) the
three-dimensional inverse opal structure yes FeCl the pin3Then
immersed in an aqueous solution, heating the α-Fe2O3Graphene
inverse opal (α-Fe2O3/ GIO) can be produced according to the
manufacturing method for forming a structural body, α-Fe according
to the invention 2O3Graphen