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