SOLID-STATE CHEMISTRY
Group U2:
Kyle Demel
Keaton Hamm
Bryan Holekamp
Rachael Houk
http://www.niu.edu/chembio/faculty/directory/images/zheng_brochure.jpg
Overview
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Background
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Introduction
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3 Articles
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Conclusions
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Questions
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What is Solid-State Chemistry?
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Synthesis
Structure
Physical properties
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Composition
Atomic arrangement
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rtments/550x550/PINE-BOARD.jpg
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Examples of Solid State Devices
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LED’s
LCD
Transistors
Microprocessor chips
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ects/02/raytseng/1technology.htm
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roprocessor-athlon-64.jpg
The Holy Grail of Solid-State
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The Solid-State Hard Drive
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No moving parts
No read/write head
Very fast
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Synthesis – Article 1
Floral-like microarchitectures of cobalt iron
cyclotetraphosphate obtained by solid state synthesis
Banjong Boochonm and Naratip Vittayakorn
Floral-like microarchitectures of cobalt iron cyclotetraphosphate obtained by solid state synthesis
Potential Applications
(Article 1)
hubpages.com/hub/Copper-Pipe-Corrosion
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Background Information
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(Article 1)
Transition metal
cyclotetraphosphates (CTP)
include a P4O12-4 anion and
a combination of:
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Potentially beneficial
properties:
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www.bb.ustc.edu.cn/.../CourseHome/index.htm
Mn, Ca, Zn, Fe, Ni, Cu, Co
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Chemical
Optical
Catalytic
Magnetic
Procedure for Synthesis
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(Article 1)
Grind 1:1 mol ratio of
CoCO3 and Fe
Add H3PO4 solution
Heat at 500°C for 2 hr
Crush product and wash
with water until no
phosphate leaving
Rinse with MeOH and dry
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Product Analysis
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(Article 1)
Atomic Absorption Spectrophotometry for Co and Fe content
Colorimetric analysis of molybdophosphate complex for P content
X-ray powder
diffraction shows
homogeneous solid
solution, not mixture of
2 single metal CTPs
XRD also gave crystal
type and size
Floral-like microarchitectures of cobalt iron cyclotetraphosphate obtained by solid state synthesis
Properties of Product
(Article 1)
www.periodni.com/en/pu.html
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Floral-like microarchitectures of cobalt iron
cyclotetraphosphate obtained by solid state synthesis
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Monoclinic crystal structure
Average crystallite size of 49±20 nm
Uniform particles in floral-like
morphology
More superparamagnetic than other
morphoplogy
Superparamagnetism
Floral-like microarchitectures of cobalt iron cyclotetraphosphate obtained by solid state synthesis;
Fundamentals of Materials Science and Engineering: An Integrated Approach
(Article 1)
SEM Images of CoFeP4O12
A
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B
A= single-step method
B=acetone 2-step method
Floral-like microarchitectures of cobalt iron cyclotetraphosphate obtained by solid state synthesis;
A simple route to synthesize new binary cobalt iron cyclotetraphosphate CoFeP4O12 using aqueous and acetone media;
(Article 1)
Further Research
(Article 1)
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Testing with other metals
Application for the new materials,
based on desired properties
Other better synthesis methods
Confirm safe for use
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http://www.fz-juelich.de/nic/Publikationen/Broschuere/scientific-computing-e.html
Article 2 – Structure
Kirkendall-effect-based growth of dendrite-shaped CuO
hollow micro/nanostructures for lithium-ion battery anodes
Yingying Hu, Xintang Huang, Kai Wang, Jinping Liu,
Jian Jiang, Ruimin Ding, Xiaoxu Ji, Xin Li
Kirkendall Effect
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(Article 2)
Discovered by Ernest Kirkendoll, 1947
Proposed that molecular diffusion within solids took place not only
by direct exchange or ring mechanism, but also by vacancy
exchange.
Rejected at first by his colleagues causing Kirkendall to leave
academia
Direct exchange
Ring Mechanism
Vacancy Exchange
<http://www.tms.org/pubs/journals/JOM/9706/Nakajima-9706.html>
Experiment Procedure
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(Article 2)
1.02 g of CuCl2 dihydrate is dissolved in 200 mL distilled water and
stirred with 2 mL of acetic acid. Al foil is placed in reaction beaker
for 4 h.
Precursors form on surface of foil that are filtered and vacuumdried.
Heat is applied at varying Temperature and time duration to induce
Kirkendall effect and form hollow dendrites.
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m/gifs/cupric-chloride-dih.jpg>
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Experimental Procedure
Fig. 3. TEM images of the products prepared at 350°C
for 5 min (a),15 min (b), and 40 min (c).
(Article 2)
As the samples are heated, exterior Cu
particles come into contact with
atmospheric oxygen and oxidize into
CuO. Remaining interior Cu particles
diffuse outward as voids form and
merge, hollowing out the structure.
Overexposure to heat can cause the
hollow to crystallize.
Fig. 4. Schematic illustration of the growth of typical dendrite-shaped CuO hollow architectures.
Sample Analysis
(Article 2)
This method produces dendrite shaped CuO structures
composed of hollow tubes with a film interior and CuO
cube exterior.
Precursor dendrites are ~310μm long and branch
thicknesses range from 160170 nm. They are
composed of FCC Cu
metals.
Product branch diameter
is ~400 nm, and the
thickness is ~350 nm
Fig. 2. FESEM images of Cu dendrites at (a) low magnification and (b) high magnification and
typical CuO hollow structures at (c) low magnification and (d,e) high magnification.
Results
The CuO hollow structures
as anode materials for
lithium-ion batteries exhibit
a high initial discharge
capacity of 1503.9mAh/g
with the average Coulombic
efficiency of 97.0% for the
next 50 cycles over the
potential range 0.02–3.0 V
at a current rate of 0.5C at
room temperature.
(Article 2)
Technological Implications
(Article 2)
The small primary particles that compose
dendrite-shaped CuO and large space in the
hollow structure are expected to improve the
performance of the Li-ion cells. This
Kirkendall-effect-based approach is proven
to be an effective method to prepare
excellent hollow electrode materials for Li-ion
batteries.
http://ret.coe.drexel.edu/Portals/0/Images/lCylindrical%20Lit-ion-battery%28HSW%29.jpg
Article 3 – Physical Properties
Indentation induced solid state ordering of electrospun
polyethylene oxide fibres
Wei Wang,
Ton Peijs, and
Asa H Barber
http://nano.mtu.edu/images/Electrospinning_alt.jpg
Introduction
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Electrospinning can manufacture thin polymer fibers
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(Article 3)
Fiber diameters range between 100 nm and 10 µm
Fibers have improved mechanical properties over bulk isotropic polymer
Improved mechanical performance due to polymer chain alignment
Sufficient heating degrades mechanical properties
Solid-state deformation processing improves mechanical properties
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Stresses induce structural orientation of polymer chains
Can restore properties in polymers that were heated
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Experimental Procedure
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(Article 3)
Polyethylene oxide is a semi-crystalline polymer soluble in water
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Fibers were created using electrospinning
Fiber diameter was 500 ± 30 nm
Fiber Tm was 64°C
Isotropic PEO Tm is 69°C
Explanations for Tm difference:
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Fibers had a large surface area to
volume ratio
Less polymer crystals in electrospun
fibres
Experimental Procedure
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(Article 3)
Thermo-mechanical testing was performed using an atomic force
microscope integrated with a heating chamber
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Measured the force required to indent the polymer surface
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Took data before and after heating polymer to 50ºC
AFM applied large indentations at heated temperature
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Took data around and away from indentations
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Results and Discussion
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Similar forces were applied
throughout the experiment
Force vs. indentation depth
curve was generated
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(a) before any heating
(b) after heating, near
indentation stress points
(c) after heating, away from
indentation stress points
(Article 3)
Results and Discussion
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(Article 3)
The indentation depth (δ) and force (F(δ))are used to calculate the
elastic modulus (Ef) of the electrospun fiber
The values for the elastic modulus show the effects of heating and
indentation on the mechanical properties of the polymer
Experiment Conclusions
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Electrospinning improves the mechanical properties of polymers
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Bulk PEO has an elastic modulus of 0.20 GPa
Electrospun PEO has an elastic modulus of 1.39 GPa
Indentation helps retain mech. properties in post- heated polymers
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(Article 3)
Around an applied stress, the elastic modulus was 0.53 GPa
Away from an applied stress, the elastic modulus was 0.22 GPa
Changes in mechanical properties are based on solid-state
rearrangements at the nano-scale level
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Research Implications
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Heating may limit the function of electrospun fibers
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(Article 3)
The mechanical properties of heat-treated electrospun polymers approaches
the properties of normal bulk polymers
Further research could yield better property retention in nano-fabrics
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Stronger and more applicable textiles
More heat-resistant fibers
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Further Research
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(Article 3)
Which electrospun fibers are susceptible to heat-induced strength
degradation other than polyethylene oxide?
How are the mechanical properties of the polymer affected by
multiple heating or stress cycles?
How can the electrospun fibers be stress-induced at the
macroscopic level?
What are the safety considerations
involved?
How much will stress treating cost?
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Conclusions
Three Aspects of Solid State Chemistry:
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Synthesis
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Structure
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Creating cobalt iron cyclotetraphosphate
microstructures
Testing new CuO hollow nanostructures
for battery anodes
Physical Properties
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Improving the durability of electrospun
fibers
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Questions
Rebuttal Group from U2
Rebuttal from Group U2:
Group U2:
-Kyle Demel
-Keaton Hamm
-Bryan Holekamp
-Rachael Houk
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We disagree with the following comments:
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Repeat Information – One of the critiques stated that we used the same articles as
a previous group. The student who wrote this false accusation is either completely
clueless or did not check the website to verify that all of our articles are unique and
not repeats. We believe this student was referring to the third article that
concerned using solid-state chemistry to analyze physical properties. The article
discussed using solid-state techniques at the nanoscale level to investigate how
the physical properties of electrospun fibers are affected by heat and stress. Our
presentation builds off of the introductory material to electrospun fibers that
Group U6 presented. Apparently, we did not make this distinction clear enough.
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Understanding = Bad – Another student praised us for making a presentation that
was easy to understand and follow. That student then decided to dock us points in
the respective category with no further rationale to follow. Either
the student thinks we’re playing golf (where a low score is good)
or was carping over the fact that the presentation did not allow
him/her to feel perplexed, confused, flummoxed, or bruised.
While a normal human being would have followed up the
comment with a good score, this classmate of ours is apparently
a disappointed mental masochist.
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We agree with the assessments concerning:
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Introduction – Many of the critiques mentioned the introduction being
insufficient to cover the topic presented. While the group still stands by the
statement that a comprehensive discussion of solid-state chemistry would be
time-consuming and unnecessary for this class, we agree that the introduction
should have included more detail. Initially, the group believed that focusing on
the overall topics covered by solid-state chemistry would steal too much time from
elaborating on specific applications. After reviewing the critiques, the group now
concurs that more time should have been allotted to the introduction.
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Slide Lay-out – We were pleased that most of the audience members commented
on the great slide lay-out. The group put in the effort to make all the text,
headings, and formatting consistent throughout the
presentation. The included figures were all large and
clear enough for easy interpretation. The figures
were also pertinent to the presentation as a whole,
and nearly every slide had at least one visual.
Equations were manually typed to ensure legibility.
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REVIEW: U1
SOLID STATE CHEMISTRY BY U2
Definition:
Study of synthesis, structure
and physical properties of
the solid materials
Characterization:
• Optical property
• Mechanical property
• Electrical property
• Catalytic property
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WHAT WE LEARN?
Important of Solid State Chemistry
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Very helpful in preparing the material
with unique electrical, magnetic,
optical and catalytic properties
Current Research
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numerous scientific areas including
Materials Science and Engineering,
Ceramics, Chemistry, Chemical
Engineering, Mineralogy/Geology, and
Condensed Matter Physics
Further Research
Enhancing the properties of materials
like polymers to increase their
susceptibility to multiple heating and
stress
New method of developing and testing
these solid state chemicals
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Group #3
Phillip Keller
Krista Melish
Micheal Jones
James Kancewick
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Slides
 Nice pictures, not all were explained but gave the
report a good picture to text ratio
 The pictures and laser pointer use was done well,
for the most part one presenter did wave it at the
screen which was distracting
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Tech Review
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Potential applications “was rushed”
for the corrosion resistant coatings
The beginning of the presentation
started with good solid examples
relating macroscopic examples to
microscopic instances.
The battery paper and nanofiber
paper also were covered in sufficient
detail. This lead to even a lack of
question for the nanofiber article.
Review of Group U2 by Group U4
 The slides were very simple and easy on the eyes.
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There was not an overabundance of text on each
slide, and that really helped to keep the audience
focused on the presenters’ speech as opposed to
simply reading the slides the whole time.
Excellent pictures especially in the dendrite
formation slides.
Excellent slides overall with a good balance of
text/images and large enough text/images to easily
read.
Presenters spoke clearly and loudly through the
presentation, and were all involved in the Q&A
session at the end.
A little too much reading off slides at portions of
the presentation.
Thank you for citing all pictures on every page.
Credit should be given where it is due.
Thank you group for the food!
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Technical Critique
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Good introduction overall involving types of solid-state devices and uses; however, it was a little dry in
the explanation of what solid-state chemistry is.
Even though each of the papers dealt with the synthesis, structure, and properties of solid-state
chemistry devices, we would have like to see a little more depth to those in the introduction.
First article gave a good review of the synthesis of a certain solid-state chemistry application, but we
would have liked to see more stress on the importance of superparamagnetism since that is the
ultimately desired property of the chosen material.
We really enjoyed the 2nd paper. It was presented very clearly and gave us insight to the future of longlife batteries, and the upgrades that are currently being researched to make them last longer and
charge more quickly.
Very educational end to this exciting presentation! With this paper the audience finally learns the
reason why research and money should be poured into this field. Would have liked to see elaboration
on the heat effects of nanospun fibers.
Overall, an excellent presentation with each group member offering an interesting view of the concept
of solid-state chemisty applications and properties.
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Solid-state chemistry
 Review of Team U2 by
Team U5 – Jaynesh
Shah, Greg Pudewell,
Edwin L. Youmsi Pete
and John Pack.
Oral and Quality of Slides
Review
 The speakers did a great job
of speaking in a paced, clear
manner.
 They were confident and
knowledgeable on the
subject.
 There were a few times
when filler words were a bit
distracting.
 Good use of the
microphone.
Technical Review
 The presentation was
technically sound
 Spent too much time
on the introduction
 Introduction was too
elementary for the
level of student in that
class
 Researched three
different papers
 Outstanding!
SOLID STATE CHEMISTRY
Presented by: Group U2
Critiqued by: Group U6
Critique: Oral Presentation & Slides
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Slides were easy to read
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Good background and good size text
Good transition between slides
Slides kept our attention
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Very professional looking – good effort put in preparing the presentation
The use of illustrations complimented the text – would have liked to see more use of
graphs though to show results of experiments
The illustrations were cited and found on every page – they were relevant to the
topic and helped illustrate points
The outline slide in the beginning as well as the conclusion slide at the end of the
presentation were very helpful
Excellent flow of topics in the introduction
The speakers did a good job in presenting. There were a few times when too many
filler words were used to not enough eye contact was made. One speaker could
have practiced a little bit more to make their speech flow better.
Liked that group members dressed up for presentation – looks professional
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Critique – Technical Content
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Introduction explained really well – very easy to follow
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Choice of research papers seemed relevant to topic discussed
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Potential applications include improvements in synthetic fabrics
Further research on this topic was very well described
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Potential applications in cell phones and laptops
The paper which discussed the effects of electrospinning showed the
additional strength polymers gained through the process
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Three papers discussed which gave a good range of information on current
research
The motivation for each paper given at the beginning – something we
really liked
The paper on the lithium battery was the most interesting
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Presenters took audience through a good overview before going in depth into
the research papers
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The presenters went in depth of the topics covered by each of the research
papers
Would have liked to see potential long term impact of the research
presented
Review for U2
Jung Hwan Woo
• I disagree with the statement, “the holy grail of solidstate device is solid-state hard drive.” I consider a CPU
a far more sophisticated product than a SSD since a
CPU contains much more engineering, although they
both use similar fabrication techniques.
• Maybe the introduction could dig into more detailed
physics instead of just showing examples.
• The three articles were organized and presented very
well.
• Why does cobalt iron cyclotetraphosphate have highly
variable size as indicated by the average crystallite size
of 49 ±20 nm. If the average crystallite size can be as
small as 29 nm and as large as 69 nm, is the actual
range of crystallite size for this material much broader?