Lecture 1. Intro, Overview, And Thermal Properties 2015

8/9/2019 Lecture 1. Intro, Overview, And Thermal Properties 2015

http://slidepdf.com/reader/full/lecture-1-intro-overview-and-thermal-properties-2015 1/35

MSE 551

Materials Characterization

To understand the four course objectives

To understand the process of and assignments for the course

To understand and agree to the time frame for the course assignments

To be aware of the high level of expectations for classroom participationand course work

To be able to describe at least four aspects of material characterization



[email protected] 2

The Details

Faculty: Steve W. Martin, 4-0745, [email protected]

2220E Hoover

Course Web Page: WebCT “MSE 551 Materials Characterization”

Text: “A Guide to Materials Characterization and

Chemical Analysis,” 2nd Edition, John P.

Sibilia, Ed., VCH Publishers, 1996.

Meeting Times: M, W10:00 – 10:50 AM 1226 Howe Hall

1-4 PM W 3314, 3364 Hoover, Hach Hall

Grading: 2 Exams 300 pts.

7 laboratory reports 350 pts.

~10 quizzes 50 pts.

Total 700 pts

MSE 551 Lecture 1: Introduction to Materials Characterization

mailto:[email protected]

mailto:[email protected]



[email protected] 3

Course Objectives

To be able to select proper analytical techniques and to be able to prepare appropriate

samples for the accurate measurement of a range of physical and thermal properties

of materials. To be able to select proper analytical techniques and to be able to prepare appropriate

samples for the accurate characterization of the structure of materials

To be able to carefully and accurately analyze the resulting data from physical

property and structure measurements to better understand the relationships between

the structure, physical properties, and processing of materials

To be able to identify the inherent limits of accuracy and sensitivity of all of the

analytical techniques studied in this course




[email protected] 4

Course Outline


Course Lectures and Laboratory Assignments

Week/Dates Lectures Reading Lab Due

Section I Spectroscopy

1. 1/12

1/14

Overview of Course and Materials Characterization

Lab – Student presentations of thesis research projects

JPS 1

2. 1/191/21

1/21

No Class MLK DayInfrared Spectroscopy - Theory and Background II

Lab 1A – FT - IR Mid and Far IR spectroscopy

JPS 2 2/2 5 PMWritten lab

report

3. 1/261/28

1/28

Infrared Spectroscopy - Practice and Applications IInfrared Spectroscopy - Practice and Applications II

Lab 1B – FT - IR IR Microscopy

JPS 2 2/2 5 PMWritten lab

report

4. 2/2

2/4

2/4

Raman Spectroscopy - Theory and Background I

Raman Spectroscopy - Theory and Background II

Lab 2A – Confocal Raman Microscopy I

JPS 2 2/16 5 PM

Extended

InterofficeMemo

5. 2/9

2/11

2/11

Raman Spectroscopy - Practice and Applications I

Raman Spectroscopy - Practice and Applications II

Lab 2B - Confocal Raman Microscopy II

JPS 2 2/16 5 PM

Extended

Interoffice

Memo

6. 2/16

2/18

2/18

NMR Spectroscopy - Theory and Background I

NMR Spectroscopy - Theory and Background II

Lab 3A – MASS-NMR 1 Dipolar Nucleii

JPS 3 3/2 5 PM

Wikepedia

chapter

7. 2/23

2/25

2/25

NMR Spectroscopy - Practice and Applications I

NMR Spectroscopy - Practice and Applications II

Lab 3B – MASS-NMR 2 Quadrpolar Nucleii

JPS 3 3/2 5 PM

Wikepedia

chapter

8. 3/2

3/4

3/4

UV/VIS/NIR Spectroscopy - Theory and Background

UV/VIS/NIR Spectroscopy - Practice and Applications

Lab 4 – UV/VIS Spectroscopy

JPS 2 3/23 5 PM

Web page

10. ` 3/9

3/11

3/11

XPS - Theory and Background

XPS - Practice and Applications

Lab 5 - XPS

JPS 10 3/23 5 PM

Web page

11. 3/16-20 Spring Break - No Classes



[email protected] 5

Course Outline


Course Lectures and Laboratory Assignments

Week/Dates Lectures Reading Lab Due

Section II Thermal Analysis12. 3/23

3/25

3/25

DTA - Theory and BackgroundDTA - Practice and Applications

Lab 5A - DTA

JPS 11 4/6 5 PMPoster

Presentation

13. 3/304/1

4/1

DSC - Theory and BackgroundDSC - Practice and Applications

Lab 5B – DSC

JPS 11 4/6 5 PMPoster

Presentation

14. 4/64/8

4/8

TGA - Theory and Background

TGA - Practice and Applications

Lab 6 - TGA

JPS 11 4/13 5 PM

Research

Proposal

15. 4/13

4/15

4/15

TMA - Theory and Background

TMA - Practice and ApplicationsLab 7A - TMA

JPS 11 4/27 5 PM

OralPresentation

16. 4/20

4/22

4/22

DMA - Theory and Background

DMA - Practice and Applications

Lab 7B - DMA

JPS 11 4/27 5 PM

Oral

Presentation17. 4/27

4/294/29

DETA - Theory and BackgroundDETA - Practice and ApplicationsLab 8 - DETA

JRM JournalArticle

18. 5/4 Final Exam - 150 pts.



[email protected] 6

A Typical Week

Two Lectures – Background and Theory of Technique

– Background

» History, Development, Limits – Theory

» Governing theory, chemical, physical, and mathematical treatment of thetechnique

Two Lectures on – Practice and Application of Technique – Sample preparation, instrument characteristics

– Data Collection and Analysis

Laboratory on Wednesday Afternoon – Practice using Technique

– Lab handouts ~ posted in advance on the course Web page

– Prelab review

– Training on instrument software – instrument control, data collection, data

analysis – Data collection on standards and known materials, calibrations

– Data collection on samples



http://slidepdf.com/reader/full/lecture-1-intro-overview-and-thermal-properties-2015 7/[email protected] 7


Materials Characterization has at least three main aspects – Accurately measuring the physical and chemical properties of materials

» Thermal properties, electrical properties, magnetic properties,mechanical properties…

» Chemical durability, flammability, corrosion resistance, reactivity,stability…

– Accurately measuring (determining) the structure of a material

» Atomic level structures

• Crystal structure, amorphous structure, short range structure,intermediate range structure…

» Microscopic level structures

• Morphologies, texture, grain size, orientation, anisotropy,isotropy…

– Materials identification

» Composition, compounds, impurities, main components

» Origin of source, starting materials, active/inactive ingredients,manufacturer, domestic/non-domestic source…





A critical part of Materials Science and Engineering is to seek

relationships between these – Properties of Materials

– Composition, Structures and Microstructures of Materials

– The Processing used to make the Material

– The Ultimate Performance of that Material in Use

[email protected] 8MSE 551 Lecture 1: Introduction to Materials Characterization



Materials Characterization – Measuring Physical Properties of Materials

Thermal Properties – What

are a few examples and how

are they measured?

– Melting point, Phase transition

temperature, Glass transition

temperature, thermal

expansion coefficient





Electrical

Properties - What

are a few examples

and how are they

measured?

– Resistivity

– Conductivity – Dielectric constant

– Permittivity

– Dielectric break

down

Dielectric Relaxation in Polymers





Magnetic Properties –

What are a few examples

and how are they measured?

– Curie point

– Hysteresis

– Magnetic susceptibility

– Diamagnetism – Paramagnetism

– Ferromagnetism





Mechanical Properties –

What are a few examples

and how are they measured?

– Mechanical Modulus

» Tensile, Bulk, Shear,

– Mechanical Strength

– Hardness




[email protected] 13

Materials Characterization – Measuring Chemical Properties of Materials

What are a few examples of

chemical properties and how are

they measured?

– Solubility

– Reactivity

» Air, water, solvents, acids, bases,

solids – Stability

» Air, water, solvents, acids, bases

– Flammability

» Atmosphere, Ignition temperature

– Corrosion resistance

» Temperature, Air, Water, Acids,

Bases, Solvents

Impingement failure of a steel pipe elbow

that was part of a steam condensate line





Materials Characterization – Determining the Structure of Materials

What are a few examples of

determining the structure of

a material and how are they

determined?

– Atomic level structures

» Coordination numbers,

bond lengths, bondangles, bond type,

chemical composition

compound formula),

Coordination structure

Crystalline quartz structure






Single crystal structure

– Space group, point group,Unit cell type, Unit cell

dimensions

FCC Unit cell

Hard Sphere Reduced Sphere

Aggregate of

many atoms






Polycrystalline materials

– Texture

– Microstructure

– Grain size

– Grain boundary sizes

(thicknesses)

– Phase number – Secondary phases

– Impurity phases

– Porosity, Density

– Open pore volume

– Closed pore volume

Large grained Al2O3






Non-Crystalline materials

– Short range structure, bond

lengths, bond angles, bondtype,

– Intermediate range structure,

ring sizes, ring types

Structure of Glassy A2O3





Materials Characterization – Materials Identification

Composition

– Compounds,

Elements, Impurityelements, Main

elements

Origin of source,

starting materials,active/inactive

ingredients,

manufacturer,

domestic/non-

domestic source…

AlN

x-ray powder pattern of

AlN and Al2O3 mixtures





Materials Properties, Structure, Processing, Performance

Performance is the ultimate end

use function of the material

It results from the proper set of

properties

And is achieved by the

optimization of the

composition, atomic level and

micro structural levels of the

structure of the material

Being prepared and

manufactured using a carefullycontrolled and optimized

synthesis and processing route





H2-O2 Proton Exchange Membrane Fuel Cell

CPCM

Backing Layer

(Cathode)

Membrane Backing Layer

(Anode)

Porosity

Electrodes

P r o t o n

C o n d u c t i n g

M e m b r a n e

H2O2

H2O

H+

H+

Anode “Half -Reactions”

H2 2H+ + 2e-

Cathode “Half -Reactions”

½ O2

+ 2e- O=

Overall cell reaction

H2+ ½O2 H2O

Load2e-

2e-





Selection of Specific Test Compositions

Important Characteristics:

– Strong glass forming tendency, Large solubility of protons

– Chalcogenide (sulfide) chemistry, Relatively high softening point (>300oC)

– Cheap and available starting materials, Good processability

Of the sulfide glass formers:

– GeS2 and B2S3 are among the strongest of glass formers

– No crystallization even for periods of months – Relatively cheap, elemental Ge, B, and S

– Tg ~ 300oC

– Large solubility, up to 50 to 80%M2S are still glass forming

– Easily processed at 50 grams at time

xH2S + (1-x)B2S3, xH2S + (1-x)GeS2 base glass compositions: – B2S3 and GeS2 provide glass forming “network”

– H2S provides source of mobile protons





Fast Proton Conducting Membranes

Can similar order of magnitude increases in conductivity be

achieved for protons?

Can the very low proton conductivity of oxide glasses be

increased by using a sulfide glass chemistry?

If so, can these glasses be used as proton conducting

membranes?

– Application in fuel-cells, reformers and separators

– Achieve high proton conductivity in inorganic phases

– Stable at higher temperatures that will enable higher efficiencies

– Will decrease fuel cross-over that is observed with hydrated polymer

membranes – Increase electrical, chemical, and mechanical durability of the membrane





200 600 1000 1400 1800 2200 2600 3000

c-(HBS2)

3

- - -

- - - - - - - - - - - - - - - - B

3 S

6 H

3

- - -

- - - - - B S

2 / 2

S H

- - - H - S

- - - -

IR spectrum

Raman spectrum

A b s o r p t i o n / I n t e n s i t y ( a . u . )

Wavenumber (cm-1)

3H2S + 3B2S3 2H3B3S6 Thioboric Acid – Raman and IR Spectra

B

B

B

S

S

SS

S

S

H

H

H





B2S3 + (HBS2)3 Glasses – IR Spectra

Glass forming for

0 < x < 0.25

Glass ceramics for

0.3 < x < 0.4

Ceramics for

0.4 < x

Progressive

formation of six-

membered rings

with three terminal

non-bridging

sulfurs600 1000 1400 1800 2200 260

0

1

2

3

4

5

6

0.2

x = 0.0

0.1

0.250.33

0.4

0.45

x = 0.5

B S

2 / 2

S H B

S 3 / 2

B 3 S

3 S

3 / 2

r i n g

- -

H - S

B2S

3

(HBS2)

3

A b s o r b a n c

e ( A . U . )

Wavenumber (cm-1)





Soft Chemistry Synthesis of Alkali Thio-hydroxometallates

Cs

O

S

H

Ge

xMSH + MOz + H2O

(MS)xM’(OH)z-x yH2O

xCsSH + GeO2 + H2O (CsS)xGe(OH)4-x yH2O

Stir in water at ~ 65-80 oC

Remove water through drying – Acetone speeds drying

– Slow evaporation can be used to produce single

crystals (weeks) – Rapid drying produces amorphous hydrates (minutesto hours)

Any combination of alkali, alkaline earth with anycombination of metal oxide from all oxide to allsulfide

Mixed systems of alkali and alkaline earth metals

with mixed metal centers Optimize properties by optimizing chemistry





IR spectra can show the effect of temperature - K 2GeS2(OH)2• yH2O

As seen for the Rb phases,evolution of molecular water

occurs with increasing

temperatures

Repeated cycling by exposing the

sample air at RT regenerates the

original hydration level in the

material

Repeated cycling shows that the

material regains a constant level of

hydration after heating at elevated

temperatures





H2S + GeO2 – Direct reaction to produce protonated sulfides

Production of

– SH modesindicates

reaction

Decrease in

GeO2 modes

indicates

reaction of

GeO2

IR spectra

indicates high

purity H2

S +

GeS2 phase

from an oxide

starting

material4000 3500 3000 2500 2000 1500 1000 500

0

1

2

3

4

5

67

8

9

10

11

GeO2

1wk H2S

2wk H2S

4wk H2S

A b s o r b a n c

e

Wavenumber cm-1

4H2S(liq., 25oC) + GeO2 >> H4GeS4 + 2 H2O

-SH -Ge-S-

-Ge-O-





Raman Spectra easily shows low wavenumber region of spectra

100 200 300 400 500 600 700

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4wk H2S

2wk H2S

1wk H2S

GeO2

A r b i t r a r

y I n t e n s i t y

Raman Shift (cm-1)

H2S + GeO2 at 25oC

-Ge-S-

-Ge-O-





Combined optical and Raman spectroscopy – Raman Microscopy

0.0

0.5

1.0

1.5

2.0

2.5

1 23

45

6200 400 600 800 1000 1200

Point

I n t e n s i t y ( 1 0 4

C P S )

Wavenumber (cm-1)

GeO2 + GeS2 Glasses





Combined optical and Raman spectroscopy – Raman Microscopy

(1) (2) (3) (4) (5) (6) (7) (8) (9)

0.0

0.5

1.0

1.5

2.0

123

45

67

89

200 400 600 800 1000 1200

I n t e n s i t y ( 1 0 4

C P S )

Wavenumber (cm-1)

GeO2 + GeS2 Glasses





Example of Materials Processing, Synthesis, Properties and Performance

Twin Gemini

TelescopesHawaii &

Chile


M i l P i d S




Materials Properties and Structure

Adding the more refractory,higher bond strength TiO2 reduces

the expansion coefficient


M i l P f d P i




Materials Performance and Processing

Mirror must be made of material

with an extremely small, optimally

zero, thermal expansion coefficientso mirror dimension, hence focus,

does not change with time

Material Selection

– TiO2 doped SiO2 Ultra-low

expansion glasses synthesized byCorning Glass Works

– xTiCl4 + (1-x)SiCl4 + O2 >>

xTiO2+(1-x)SiO2(glass) +

2Cl2(g)

O2

SiCl4 TiCl4


M i l P i




Materials Properties

Thermal Expansion

coefficient goes to zero at

~7.5 wt% TiO2 added tovitreous silica

Creates a glass substrate that

will not change its dimension

with change of temperature Produces thermally and

mechanically stable mirror

blank


M t i l P ti d C iti



Materials Properties and Composition

Most materials expand as they are

heated

– Some more than others

Refractory metals and ceramics

– Expand less

Polymers

– Expand more

Some materials expand very little

– SiO2 and TiO2+SiO2 glasses

– b-spodumene, Li2O.Al2O3.4SiO2

Complex systems with more than one

material must have matched or

compensated thermal expansions

Documents

Lecture 1. Intro, Overview, And Thermal Properties 2015