SOLID-STATE CHEMISTRY

Group U2:Kyle Demel

Keaton HammBryan Holekamp

Rachael Houk

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Overview

Background

Introduction

3 Articles

Conclusions

Questions

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What is Solid-State Chemistry? Synthesis Structure Physical properties

Composition Atomic arrangement

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Examples of Solid State Devices

LED’s LCD Transistors Microprocessor chips

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The Holy Grail of Solid-State

The Solid-State Hard Drive No moving parts No read/write head Very fast

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Synthesis – Article 1Floral-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)

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Background Information (Article 1)

Transition metal cyclotetraphosphates (CTP) include a P4O12

-4 anion and a combination of: Mn, Ca, Zn, Fe, Ni, Cu, Co

Potentially beneficial properties: Chemical Optical Catalytic Magneticwww.bb.ustc.edu.cn/.../CourseHome/

index.htm

Procedure for Synthesis (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 (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)

Monoclinic crystal structure Average crystallite size of

49±20 nm Uniform particles in floral-like

morphology More superparamagnetic

than other morphoplogy

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Floral-like microarchitectures of cobalt iron cyclotetraphosphate obtained by solid state synthesis

Superparamagnetism (Article 1)

Floral-like microarchitectures of cobalt iron cyclotetraphosphate obtained by solid state synthesis; Fundamentals of Materials Science and Engineering: An Integrated Approach

SEM Images of CoFeP4O12 (Article 1)

A 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;

Further Research (Article 1)

Testing with other metals Application for the new

materials, based on desired properties

Other better synthesis methods

Confirm safe for usehttp://www.nurselearn.com/info-hazcom.htm

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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 (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

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Experiment Procedure (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 vacuum- dried.

Heat is applied at varying Temperature and time duration to induce Kirkendall effect and form hollow dendrites.

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Experimental Procedure (Article 2)

Fig. 4. Schematic illustration of the growth of typical dendrite-shaped CuO hollow architectures.

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. 3. TEM images of the products prepared at 350°C for 5 min (a),15 min (b), and 40 min (c).

Sample Analysis (Article 2)

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.

This method produces dendrite shaped CuO structures composed of hollow tubes with a film interior and CuO cube exterior.

Product branch diameter is ~400 nm, and the thickness is ~350 nm

Precursor dendrites are ~3-10μm long and branch thicknesses range from 160-170 nm. They are composed of FCC Cu metals.

Results (Article 2)

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.

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.

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Article 3 – Physical Properties

Indentation induced solid state ordering of electrospun polyethylene oxide fibres

Wei Wang, Ton Peijs, and Asa H Barber

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Introduction (Article 3)

Electrospinning can manufacture thin polymer fibers 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 Stresses induce structural orientation of polymer chains Can restore properties in polymers that were heated

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Experimental Procedure (Article 3)

Polyethylene oxide is a semi-crystalline polymer soluble in water 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:

Fibers had a large surface area to volume ratio

Less polymer crystals in electrospun fibres

Experimental Procedure (Article 3)

Thermo-mechanical testing was performed using an atomic force microscope integrated with a heating chamber Measured the force required to indent the polymer surface

Took data before and after heating polymer to 50ºC AFM applied large indentations at heated temperature

Took data around and away from indentations

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Results and Discussion (Article 3)

Similar forces were applied throughout the experiment

Force vs. indentation depth curve was generated

(a) before any heating (b) after heating, near

indentation stress points (c) after heating, away from

indentation stress points

Results and Discussion (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 (Article 3)

Electrospinning improves the mechanical properties of polymers 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 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 levelhttp://www.themolecularuniverse.com/MMMGIF/buck_crystal.gif

Research Implications (Article 3)

Heating may limit the function of electrospun fibers 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 Stronger and more applicable textiles More heat-resistant fibers

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Further Research (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:

Synthesis Creating cobalt iron

cyclotetraphosphate microstructures

Structure Testing new CuO hollow

nanostructures for battery anodes

Physical Properties Improving the durability of

electrospun fibers

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Questions

Rebuttal Group from U2

Group U2: -Kyle Demel -Keaton Hamm -Bryan Holekamp -Rachael Houk

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Rebuttal from Group U2:

We disagree with the following comments:

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.

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:

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.

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

Very helpful in preparing the material with unique electrical, magnetic, optical and catalytic properties

Current Research 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 http://www.crystal.unito.it/ascs2006/

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Review of Group#2Solid State Chemistry

Group #3Phillip KellerKrista MelishMicheal JonesJames Kancewick

Review

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

Tech Review

Tech Content 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

Solid-State Chemistry

The slides were very simple and easy on the eyes. 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!

Oral Presentation and Slides

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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 long-life 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.

Technical Critique

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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 U2Critiqued by: Group U6

Critique: Oral Presentation & Slides

Slides were easy to read Good background and good size text Good transition between slides Slides kept our attention 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

Introduction explained really well – very easy to follow Presenters took audience through a good overview before going in depth

into the research papers Choice of research papers seemed relevant to topic discussed

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 Potential applications in cell phones and laptops

The paper which discussed the effects of electrospinning showed the additional strength polymers gained through the process Potential applications include improvements in synthetic fabrics

Further research on this topic was very well described 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

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Review for U2

Jung Hwan Woo

• I disagree with the statement, “the holy grail of solid-state 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?