U.S. patent application number 16/406969 was filed with the patent office on 2019-08-29 for aluminum nitride synthesis from nut shells.
This patent application is currently assigned to The Government of the United States of America, as represented by the Secretary of the Navy. The applicant listed for this patent is The Government of the United States of America, as represented by the Secretary of the Navy, The Government of the United States of America, as represented by the Secretary of the Navy. Invention is credited to Edward P. Gorzkowski, III, Syed B. Qadri, Bhakta B. Rath.
Application Number | 20190261664 16/406969 |
Document ID | / |
Family ID | 62106467 |
Filed Date | 2019-08-29 |
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United States Patent
Application |
20190261664 |
Kind Code |
A1 |
Qadri; Syed B. ; et
al. |
August 29, 2019 |
Aluminum Nitride Synthesis from Nut Shells
Abstract
A method of producing Aluminum Nitride comprising milling nuts
into a powder, milling a powder of nanocrystalline Al.sub.2O.sub.3,
mixing, pressing into a pellet, providing nitrogen, heating, and
forming AlN. An Aluminum Nitride product from preparing powders of
nuts and Al.sub.2O.sub.3, mixing, and forming a powder,
pressurizing into a disk, pyrolizing in nitrogen, and forming AlN
in a pure form and in the wurtzite phase. An Aluminum Nitride (AlN)
from preparing powders of agricultural nuts, preparing powders of
nanocrystalline Al.sub.2O.sub.3, mixing the powders and thereby
forming a homogenous sample powder of agricultural nuts and
Al.sub.2O.sub.3, pressurizing the homogenous sample powder into a
disk, heat treating or pyrolizing the disk in a nitrogen
atmosphere, reacting the disk and the nitrogen atmosphere and
forming AlN, and wherein the AlN is nano-structured AlN and in a
pure form and in the wurtzite phase of AlN.
Inventors: |
Qadri; Syed B.; (Fairfax
Station, VA) ; Rath; Bhakta B.; (Oakton, VA) ;
Gorzkowski, III; Edward P.; (Odenton, MD) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
The Government of the United States of America, as represented by
the Secretary of the Navy |
Arlington |
VA |
US |
|
|
Assignee: |
The Government of the United States
of America, as represented by the Secretary of the Navy
Arlington
VA
|
Family ID: |
62106467 |
Appl. No.: |
16/406969 |
Filed: |
May 8, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
15786180 |
Oct 17, 2017 |
10292411 |
|
|
16406969 |
|
|
|
|
62422793 |
Nov 16, 2016 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C01P 2002/72 20130101;
C01P 2004/04 20130101; C01P 2002/82 20130101; C01B 21/0726
20130101; A23L 25/00 20160801; B82Y 30/00 20130101; B02C 17/20
20130101 |
International
Class: |
A23L 25/00 20060101
A23L025/00; B82Y 30/00 20060101 B82Y030/00; C01B 21/072 20060101
C01B021/072; B02C 17/20 20060101 B02C017/20 |
Claims
1. A method of producing nano-structures of Aluminum Nitride from
nut shells comprising: milling agricultural nuts into a fine nut
powder; milling nanocrystalline Al.sub.2O.sub.3 into a powder;
mixing the fine nut powder with the powder of nanocrystalline
Al.sub.2O.sub.3; pressing the fine nut powder and the powder of
nanocrystalline Al.sub.2O.sub.3 into a pellet; providing a nitrogen
atmposphere; heating the pellet to a temperature of about
1400.degree. C.; maintaining the temperature of the pellet at about
1400.degree. C.; cooling the pellet in air to a temperature of
about 670.degree. C.; eliminating the residual carbon; and forming
nano-structures of AlN.
2. The method of producing nano-structures of Aluminum Nitride from
nut shells of claim 1 wherein the step of maintaining the
temperature of the pellet at about 1400.degree. C. comprises an
interval of 5-6 hours.
3. A nano-structured Aluminum Nitride product from nut shells in a
pure form and in the wurtzite phase from the steps comprising:
milling agricultural nuts into a fine nut powder; milling
nanocrystalline Al.sub.2O.sub.3 into a powder; mixing the fine nut
powder with the powder of nanocrystalline Al.sub.2O.sub.3; pressing
the fine nut powder and the powder of nanocrystalline
Al.sub.2O.sub.3 into a pellet; providing a nitrogen atmposphere;
heating the pellet to a temperature of about 1400.degree. C.;
maintaining the temperature of the pellet at about 1400.degree. C.;
cooling the pellet in air to a temperature of about 670.degree. C.;
eliminating the residual carbon; and forming nano-structures of
AlN.
4. A nano-structured Aluminum Nitride product in a pure form and in
the wurtzite phase from the steps comprising: preparing powders of
agricultural nuts using ball milling with a SPEX 8000M including
stainless steel milling media; preparing powders of nanocrystalline
Al.sub.2O.sub.3 using ball milling including stainless steel
milling media; mixing the powders of agricultural nuts and the
powders of nanocrystalline Al.sub.2O.sub.3 using ball milling
including stainless steel milling media and thereby forming a
homogenous sample powder of agricultural nuts and Al.sub.2O.sub.3;
pressurizing the homogenous sample powder of agricultural nuts and
Al.sub.2O.sub.3 into a disk; heat treating or pyrolizing the disk
in a nitrogen atmosphere; and reacting the disk and the nitrogen
atmosphere and forming AlN; wherein the AlN is nano-structured AlN
and in a pure form and in the wurtzite phase of AlN.
5. The nano-structured Aluminum Nitride product in a pure form and
in the wurtzite phase of claim 4 wherein the steps further comprise
the step of: eliminating residual carbon by placing the disk in air
after the step of reacting the disk and the nitrogen atmosphere and
forming AlN; and wherein the disk is a 1 cm diameter disk with a
2.5-3 mm thickness.
6. The nano-structured Aluminum Nitride product in a pure form and
in the wurtzite phase of claim 4 wherein the step of heat treating
or pyrolizing the disk comprises temperatures exceeding
1400.degree. C. for an interval of 5-6 hours in a nitrogen
atmosphere; and wherein the step of eliminating the residual carbon
by placing the disk in air involves a temperature of 670.degree.
C.
7. The nano-structured Aluminum Nitride product in a pure form and
in the wurtzite phase of claim 4 wherein the step of heat treating
or pyrolizing the disk comprises a conventional furnace; and
wherein the step of pressurizing utilizes a hydraulic press.
8. The nano-structured Aluminum Nitride product in a pure form and
in the wurtzite phase of claim 4 wherein the steps further comprise
the step of: using an 18 kW rotating anode generator and a high
resolution powder diffractometer to characterize the structure of
the AlN using monochromatic CuK.alpha. radiation and further using
a 514 nm laser line to obtain Raman spectra on an inVia Raman
Microscope and scanning at about 15 mW laser power and an
integration period of 30 seconds.
Description
REFERENCE TO RELATED APPLICATION
[0001] This application is a non-provisional of, and claims
priority to and the benefits of, U.S. Patent Application No.
62/422,793 filed on Nov. 16, 2016 and U.S. patent application Ser.
No. 15/786,180 filed on Oct. 17, 2017, the entirety of each is
hereby incorporated by reference.
BACKGROUND
[0002] This invention concerns a new method for the formation of
abundant quantities of Aluminum Nitride (AlN) from a thermal
treatment of a mixture of aluminum oxide (Al.sub.2O.sub.3) and
shells of almond, cashew, coconuts, pistachio, and walnuts in a
nitrogen atmosphere at temperatures in excess of 1450.degree.
C.
[0003] This new method of synthesizing Aluminum Nitride from
various Nut Shells uses conventional heating or microwave heating
to produce nano-structures.
[0004] Billions of pounds of agricultural waste of nut shells such
as those of almonds, pistachios, walnuts, cashew, coconuts,
macadamia etc. are generated every year all over the world.
[0005] Aluminum Nitride (AlN) is a very useful material for
industrial and electronic applications due to its unique physical
properties.
[0006] AlN is an insulator in electronic device applications
because of high electrical resistivity, low thermal expansion,
resistance to erosion and corrosion, excellent thermal shock
resistance and chemical stability in air up to 1380.degree. C. with
surface oxidation occurring at 780.degree. C.
[0007] Surface acoustic wave sensors (SAWs) can be deposited on
silicon wafers because of AlN's piezoelectric properties and AlN
can be used as an RF filter for mobile phones.
[0008] AlN is synthesized in the bulk form by the carbothermal
reduction of aluminum oxide in the presence of gaseous nitrogen or
ammonia or by direct nitridation of aluminum. In order to get a
fully dense form, Y.sub.2O.sub.3 or CaO are required as additives
during the hot pressing.
[0009] Aluminum nitride is a wide gap semiconductor with band gap
between 6.01-6.05 eV at room temperature. It crystallizes in
wurtzite phase and has many potential applications in
microelectronics due to its relatively high thermal conductivity
(70-210 Wm.sup.-1K.sup.-1 to 285 Wm.sup.-1K.sup.-1). In addition,
other unique properties that make it an attractive for applications
include high electrical resistivity, low thermal expansion,
resistance to erosion and corrosion, excellent thermal shock
resistance and chemical stability in air up to 1380.degree. C. with
surface oxidation occurring at 780.degree. C.
[0010] Epitaxially grown thin film crystalline aluminum nitride is
used for surface acoustic wave sensors (SAWs) deposited on silicon
wafers because of AlN's piezoelectric properties. Another important
application for AlN is its application as an RF filter which is
widely used in mobile phones, which is also called a thin film bulk
acoustic resonator (FBAR). AlN is synthesized in the bulk form by
the carbothermal reduction of aluminum oxide in the presence of
gaseous nitrogen or ammonia or by direct nitridation of aluminum.
In order to get fully dense form, Y.sub.2O.sub.3 or CaO are
required as additives during the hot pressing.
[0011] Among the agriculture waste products, there are two types,
one containing silica and carbonaceous matter and the other one
contains mostly carbonaceous matter and no silica. The first kind
includes rice husk, wheat husk, and peanut shells. We have
demonstrated that they can be utilized to produce industrially
important materials such as SiO.sub.2, SiC, Si.sub.3N.sub.4, and
zinc silicate by pyrolizing them in air, argon or in nitrogen
atmospheres.
[0012] The second kind of agriculture residues are nut shells which
contain only carbonaceous matter such as almond, walnuts,
pistachio, coconuts, macadamia, cashew, etc. Billions of pounds of
nut shells are produced annually all over the world and will be
available if they can be harnessed in the synthesis of industrially
important materials. Recently, it was reported that mixed phases of
SiC and Si.sub.3N.sub.4 can be produced by carbothermal reduction
and nitridation of a mixture of silica and macadamia powder.
[0013] We have demonstrated in our recent work that by adding ZnO
to powder of wheat or rice husk, pure zinc silicate can be produced
with photo-luminescent properties.
[0014] Here, we have developed the formation of AlN from the nut
shells powder by adding nanocrytalline powders of Al.sub.2O.sub.3
to the nut shells powder of almond, walnut, coconut, macadamia,
pistachio and cashew and pyrolising them in nitrogen atmosphere at
1400 to 1500.degree. C.
[0015] Energy dispersive X-ray fluorescence technique was used to
determine the elemental composition of the nuts with very slight
variation among them. The formation of pure wurtzite phase of AlN
was confirmed by x-ray diffraction and Rietveld analysis and Raman
spectroscopy. Transmission electron microscopy was used to confirm
the nanocrystallinity of AlN and to characterize the size
distribution.
SUMMARY OF DISCLOSURE
Description
[0016] A new method of making Aluminum Nitride from Nut Shells
involving the formation of abundant quantities of AlN from a
thermal treatment of a mixture of aluminum oxide (Al.sub.2O.sub.3)
and shells of almond, cashew, coconuts, pistachio, and walnuts in a
nitrogen atmosphere at temperatures in excess of 1450.degree.
C.
DESCRIPTION OF THE DRAWINGS
[0017] The following description and drawings set forth certain
illustrative implementations of the disclosure in detail, which are
indicative of several exemplary ways in which the various
principles of the disclosure may be carried out. The illustrated
examples, however, are not exhaustive of the many possible
embodiments of the disclosure. Other objects, advantages and novel
features of the disclosure will be set forth in the following
detailed description when considered in conjunction with the
drawings.
[0018] FIG. 1 illustrates X-ray diffraction patterns taken with
CuK.alpha. radiation of AlN synthesized from Almond powder and
aluminum oxide powder in nitrogen at a temperature of 1450.degree.
C. showing the wurtzite phase.
[0019] FIG. 2A illustrates a TEM micrograph of AlN samples
fabricated from almond showing the nanocrystalline nature.
[0020] FIG. 2B illustrates a TEM micrograph of AlN samples
fabricated from almond showing the nanocrystalline nature.
[0021] FIG. 2C illustrates a TEM micrograph of AlN samples
fabricated from walnut showing the nanocrystalline nature.
[0022] FIG. 2D illustrates a TEM micrograph of AlN samples
fabricated from walnut showing the nanocrystalline nature.
[0023] FIG. 3 illustrates Raman Spectra of the AlN sample derived
from almond confirming the wurtzite phase.
[0024] FIG. 4A illustrates X-ray diffraction scan of
Al.sub.2O.sub.3 mixed with almond showing peaks corresponding to
corundum phase. The vertical lines correspond to the expected peaks
of alumina.
[0025] FIG. 4B illustrates a Rietveld whole profile analysis of the
diffraction pattern for the AlN sample derived from almond after
pyrolising in a nitrogen atmosphere followed by treatment in air at
800.degree. C.
[0026] FIG. 5A illustrates Raman spectra of AlN derived from
pistachio showing the different Raman active modes.
[0027] FIG. 5B illustrates Raman spectra of AlN derived from almond
showing the different Raman active modes.
[0028] FIG. 5C illustrates FTIR spectra of AlN derived from
pistachio showing a broad band of 699 cm.sup.-1.
[0029] FIG. 5D illustrates FTIR spectra of AlN derived from almond
showing a broad band of 698 cm.sup.-1.
[0030] FIG. 6 illustrates EDX of AlN derived from almond nut shell
after pyrolysing in N.sub.2 and followed by heat treatment in
O.sub.2 to remove excessive carbon.
DETAILED DESCRIPTION OF THE INVENTION
[0031] A method of making Aluminum Nitride Synthesis from Nut
Shells.
[0032] Here, the inventors have discovered a method of forming pure
AlN by carbothermal reduction of Al.sub.2O.sub.3 with raw nuts of
almonds, coconuts, macadamia, pistachios, and walnuts in the
presence of a N.sub.2 atmosphere to produce nano-tubes and
nanoparticles previously not formed by other processing then
purified in an O.sub.2 atmosphere in a Al.sub.2O.sub.3
crucible.
Example 1
[0033] The production process involves preparing samples from
powders of raw nuts of almonds, coconuts, macadamia, pistachios,
and walnuts after mixing them with nanocrystalline Al.sub.2O.sub.3
powder using ball milling with a SPEX 8000M including stainless
steel milling media.
Example 2
[0034] The Al.sub.2O.sub.3 sample along with the specific nut shell
was combined and milled to obtain a uniform powder. A hydraulic
press was used to pressurize the homogenous powder into 1 cm
diameter disks with a 2.5-3 mm depth.
[0035] The pellets were heat treated (pyrolised) in a conventional
furnace at temperatures exceeding 1400.degree. C. for an interval
of 5-6 hours in a nitrogen atmosphere.
[0036] In order to eliminate the residual carbon, the pellets were
then placed in air at 670.degree. C.
Example 3
[0037] XRD scans were obtained using a Rigaku 18 kW rotating anode
generator and a high resolution powder diffractometer. The
diffraction scans were collected using monochromatic CuK.alpha.
radiation.
[0038] Raman spectra were collected on an inVia Raman Microscope
(Renishaw) using a 514 nm laser line.
[0039] Scans were obtained at ca. 15 mW laser power at the sample
and an integration period of 30 seconds.
[0040] Fourier Transform Infrared (FTIR) spectra were collected
using Thermo Scientific Nicolet FT-IR spectrometer with Diffuse
Reflectance Infrared Transform Spectroscopy (DRIFTS) accessory.
Example 4
[0041] In order to conduct the TEM analysis, ethyl alcohol was
mixed with the pyrolyzed sample; the mixture was then set in an
ultrasonic cleaner.
[0042] A carbon covered 200 mesh copper grid was submerged into the
mixture to collect AlN particles.
[0043] A FEI Tecnai G2 TEM was utilized to examine the sample at
300 kV.
[0044] Nuts have very little SiO.sub.2 uptake from the ground but
still is a carbon source. Therefore nuts are a great candidate to
mix with oxides to form a carbide and/or a nitride with further
processing. The result is a pure nitride (in this case AlN) that is
made in a simple cost effective process.
[0045] AlN made from nuts such as almonds, pistachios, walnuts,
cashew, coconuts, macadamia etc. can be made fully dense without
the use of other dopants like AlN made in other ways. This provides
a more pure bulk form of AlN.
[0046] Due to its unique properties, it is extremely useful for the
Navy. AlN its applications have been developed mainly for
aeronautics and transport fields.
[0047] Other applications of AlN lie in refractor composites for
handling of aggressive molten metals, and high efficiency heat
exchange systems.
[0048] The formation of pure AlN from nut shells offers a simple
route as compared to complicated reactions currently being used
involving carbon rich agents and at elevated temperatures.
[0049] Moving to more environmentally greener processes is
important. This process should become the standard processing for
obtaining Pure AlN.
[0050] The above examples are merely illustrative of several
possible embodiments of various aspects of the present disclosure,
wherein equivalent alterations and/or modifications will occur to
others skilled in the art upon reading and understanding this
specification and the annexed drawings. In addition, although a
particular feature of the disclosure may have been illustrated
and/or described with respect to only one of several
implementations, such feature may be combined with one or more
other features of the other implementations as may be desired and
advantageous for any given or particular application. Also, to the
extent that the terms "including", "includes", "having", "has",
"with", or variants thereof are used in the detailed description
and/or in the claims, such terms are intended to be inclusive in a
manner similar to the term "comprising".
* * * * *