• No results found

Ti AlC Thick

N/A
N/A
Protected

Academic year: 2021

Share "Ti AlC Thick"

Copied!
65
0
0

Loading.... (view fulltext now)

Full text

(1)

Linköping Studies in Science and Technology Dissertation No. 1328

Thin Film Physics Division

Jenny Frodelius

Thick

Ti

2

AlC

Coatings

(2)

© Jenny Frodelius 2010

ISBN: 978-91-7393-356-8

ISSN 0345-7524

Printed by LiU-Tryck, Linköping, Sweden

2010

(3)

A

A

A

A

A

A

A

A

b

b

b

b

b

b

b

b

s

s

s

s

s

s

s

s

t

t

t

t

t

t

t

t

r

r

r

r

r

r

r

r

a

a

a

a

a

a

a

a

c

c

c

c

c

c

c

c

t

t

t

t

t

t

t

t

This Thesis explores the deposition techniques of magnetron sputtering and high velocity

oxy-fuel (HVOF) spraying for Ti2AlC as a promising high-temperature material. Magnetron

sputtering aims at producing thin (≤1 µm) Ti2AlC films of high crystal quality for use as a

model system in understanding the material’s basic properties. HVOF is a new method for

deposition of thick (≥200 µm) coatings by spraying Ti2AlC powder, with the aim of transferring

the good bulk properties to coatings. The oxidation behavior of Ti2AlC coatings has been

investigated for temperatures up to 1200 °C in air. As-deposited Ti2AlC(0001) thin films

decompose into TiC during vacuum annealing at 700 °C by out-diffusion of Al as shown by x-ray diffraction analysis. The release of Al starts already at 500 °C in ambient air as driven by aluminum oxide formation on the film surface where the oxide initially forms clusters as

observed by electron microscopy. While sputtering from a Ti2AlC target is simpler than by

using different elemental targets, the resulting film composition differs from the target stoichiometry. This is due to differences in energy and angular distribution of the sputtered species and evaporation of Al at substrate temperatures above 700 °C. The composition can be

compensated for by adding Ti to bind the Al and obtain phase-pure Ti2AlC coatings. For

HVOF, I demonstrate how the total gas flow of a H2/O2 mixture (441-953 liter/min) and the

powder grain size (30-56 µm) determine the thickness, density, and microstructure of the coatings. High gas flow and small grain size yield thick coatings of 210 µm with a low porosity

of 2-8 % and a tensile stress of ≥80 MPa. A fraction of the Ti2AlC powder decomposes during

spraying into TiC, Ti3AlC2, and Ti-Al alloys. The coatings also contain as much as 25 at.% O

since the powder partly oxidizes during the spraying process. Increasing the powder size and decreasing the total gas flow yield a higher amount of Ti2AlC, but produces thinner coatings

with lower cohesion. Post-annealing of the coatings at 900 °C in vacuum increases the Ti2AlC

content due to a reversible phase transformation of the as-sprayed material. The high oxygen

content, however, hinders the coating to completely transform into Ti2AlC and deteriorates its

oxidation resistance. The work thus offers insights to the key parameters for optimizing Ti2AlC

(4)

(5)

P

P

P

P

P

P

P

P

r

r

r

r

r

r

r

r

e

e

e

e

e

e

e

e

f

f

f

f

f

f

f

f

a

a

a

a

a

a

a

a

c

c

c

c

c

c

c

c

e

e

e

e

e

e

e

e

The work presented in this Thesis comes from my PhD studies (2006-2010) in the Thin Film Physics Division at Linköping University. This thesis is a continuation of my Licentiate work published 2008. The aim of my research is to generate knowledge about deposition processes for MAX-phase materials, especially the Ti-Al-C system, and their microstructure/property relationships. Parts of the work have been performed in close collaboration with Chalmers University of Technology (Göteborg), University West (Trollhättan), and Kanthal AB (Hallstahammar). I have been supported by The National Graduate School in Materials Science.

(6)

IIII

IIII

n

n

n

n

n

n

n

n

c

c

c

c

c

c

c

c

l

l

l

l

l

l

l

l

u

u

u

u

u

u

u

u

d

d

d

d

d

d

d

d

e

e

e

e

e

e

e

e

d

d

d

d

d

d

d

d

P

P

P

P

P

P

P

P

a

a

a

a

a

a

a

a

p

p

p

p

p

p

p

p

e

e

e

e

e

e

e

e

r

r

r

r

r

r

r

r

s

s

s

s

s

s

s

s

Paper I Ti2AlC Coatings Deposited by High Velocity Oxy-Fuel Spraying

J. Frodelius, M. Sonestedt, S. Björklund, J.-P. Palmquist, K. Stiller, H. Högberg, L. Hultman

Surface & Coatings Technology 202 (2008) 5976

Paper II Microstructure of High Velocity Oxy-Fuel Sprayed Ti2AlC Coatings

M. Sonestedt, J. Frodelius, J.-P. Palmquist, H. Högberg, L. Hultman, K. Stiller

Journal of Material Science 45 (2010) 2760

Paper III Annealing of Thermally Sprayed Ti2AlC Coatings

J. Frodelius, E.M. Johansson, J.M. Córdoba, M. Odén, P. Eklund, L. Hultman

Submitted

Paper IV Oxidation of Ti2AlC Bulk and Spray Deposited Coatings

M. Sonestedt. J. Frodelius, M. Sundberg, L. Hultman, K. Stiller Submitted

Paper V Sputter deposition from a Ti2AlC Target: Process Characterization and Conditions for Growth of Ti2AlC

J. Frodelius, P. Eklund, M. Beckers, P.O.Å. Persson, H. Högberg, L. Hultman

Thin Solid Films 518 (2010) 1621

Paper VI Phase Stability and Initial Oxidation of Ti2AlC Thin Films at 500 °C

J. Frodelius, P. Eklund, L. Hultman In Manuscript

(7)

M

M

M

M

M

M

M

M

y

y

y

y

y

y

y

y

c

c

c

c

c

c

c

c

o

o

o

o

o

o

o

o

n

n

n

n

n

n

n

n

t

t

t

t

t

t

t

t

r

r

r

r

r

r

r

r

iiii

iiii

b

b

b

b

b

b

b

b

u

u

u

u

u

u

u

u

t

t

t

t

t

t

t

t

iiii

iiii

o

o

o

o

o

o

o

o

n

n

n

n

n

n

n

n

t

t

t

t

t

t

t

t

o

o

o

o

o

o

o

o

t

t

t

t

t

t

t

t

h

h

h

h

h

h

h

h

e

e

e

e

e

e

e

e

iiii

iiii

n

n

n

n

n

n

n

n

c

c

c

c

c

c

c

c

l

l

l

l

l

l

l

l

u

u

u

u

u

u

u

u

d

d

d

d

d

d

d

d

e

e

e

e

e

e

e

e

d

d

d

d

d

d

d

d

p

p

p

p

p

p

p

p

a

a

a

a

a

a

a

a

p

p

p

p

p

p

p

p

e

e

e

e

e

e

e

e

r

r

r

r

r

r

r

r

s

s

s

s

s

s

s

s

Paper I Ti2AlC Coatings Deposited by High Velocity Oxy-Fuel Spraying

I contributed to the planning of the project and production of the coatings. I performed a large part of the characterization of the coatings and wrote the paper.

Paper II Microstructure of High Velocity Oxy-Fuel Sprayed Ti2AlC Coatings

I participated in the planning of the project as well as production and characterization of the coatings, and commented on the manuscript.

Paper III Annealing of Thermally Sprayed Ti2AlC Coatings

I planned the project, performed most characterization of the coatings, and wrote the paper.

Paper IV Oxidation of Ti2AlC Bulk and Spray Deposited Coatings

I performed some of the characterization of the samples, contributed to the scientific discussion, and commented on the manuscript.

Paper V Sputter deposition from a Ti2AlC Target: Process Characterization and Conditions for Growth of Ti2AlC

I planned the project, synthesized the coatings, performed most of the characterization, and wrote the paper.

Paper VI Phase Stability and Initial Oxidation of Ti2AlC Thin Films at 500 °C

I planned the project, performed all experiments and most of the characterization, and wrote the paper.

(8)

R

R

R

R

R

R

R

R

e

e

e

e

e

e

e

e

l

l

l

l

l

l

l

l

a

a

a

a

a

a

a

a

t

t

t

t

t

t

t

t

e

e

e

e

e

e

e

e

d

d

d

d

d

d

d

d

P

P

P

P

P

P

P

P

a

a

a

a

a

a

a

a

p

p

p

p

p

p

p

p

e

e

e

e

e

e

e

e

r

r

r

r

r

r

r

r

s

s

s

s

s

s

s

s

b

b

b

b

b

b

b

b

y

y

y

y

y

y

y

y

t

t

t

t

t

t

t

t

h

h

h

h

h

h

h

h

e

e

e

e

e

e

e

e

A

A

A

A

A

A

A

A

u

u

u

u

u

u

u

u

t

t

t

t

t

t

t

t

h

h

h

h

h

h

h

h

o

o

o

o

o

o

o

o

r

r

r

r

r

r

r

r

Magnetron Sputtering of Ti3SiC2 Thin Films from a Compound Target

P. Eklund, M. Beckers, J. Frodelius, H. Högberg, L. Hultman Journal of Vacuum Science and Technology A 25 (2007) 1381

Homoepitaxial Growth of Ti-Si-C MAX-phase Thin Films on Bulk Ti3SiC2 Substrates

P. Eklund, A. Murugaiah, J. Emmerlich, Zs. Czigány, J. Frodelius, M.W. Barsoum, H. Högberg, L. Hultman

(9)

A

A

A

A

A

A

A

A

c

c

c

c

c

c

c

c

k

k

k

k

k

k

k

k

n

n

n

n

n

n

n

n

o

o

o

o

o

o

o

o

w

w

w

w

w

w

w

w

l

l

l

l

l

l

l

l

e

e

e

e

e

e

e

e

d

d

d

d

d

d

d

d

g

g

g

g

g

g

g

g

e

e

e

e

e

e

e

e

m

m

m

m

m

m

m

m

e

e

e

e

e

e

e

e

n

n

n

n

n

n

n

n

t

t

t

t

t

t

t

t

s

s

s

s

s

s

s

s

Thanks to my supervisors that through the years have struggled with my writings, discussed my results back and forth, and contributed to my development as a scientist.

Lars, jag ska plocka med mig en gnutta av din optimism, och en mängd av ditt tålamod. Per, det har varit ett nöje att bolla idéer med dig om både stort och smått.

Hans, jag har till sist förstått att det här är en utbildning.

The Thin Film Physics group has grown fast since I first started and it has been exciting to follow such development. To make sure that this machinery works well it is important to have competent people by the engine, så tack till Inger, Kalle och Thomas som med er erfarenhet och

kunskap gör att mycket går så smidigt. The Thin Film Physics group wouldn’t work without

you.

It is important with good co-workers that help out with ideas and support when you need it the most so thank you all PhD students and other scientists in the Thin Film Physics group.

The Thin Film Physics group has a unique situation where we have close collaboration with two other scientific groups, namely the Nanostructured Materials and Plasma Physics group. It means that we are provided with even more opportunities, resources and knowledge. To me it has been instructive and developing to be able to discuss and work with you.

My collaboration has reached outside the borders of Linköping to the west(best)coast and Hallstahammar. Marie Sonestedt och Krystyna Stiller (Chalmers), Janna Jiang, Stefan

Björklund och Per Nylén (Högskolan Väst), Jens-Petter Palmqvist (Kanthal, nu Sandvik) och Mats Sundberg (Kanthal), tack för att ni har tampats med mig. Det har inte alltid varit lätt att sitta på olika orter men det har varit lärorikt och roligt. Jag vill också tacka operatörerna på Volvo Aero i Trollhättan som med tålamod och nyfikenhet har sett till att vi har kunnat spraya en mängd olika prover.

Many of you have not ”only” been my co-workers but you have also become good friends. You have been there for me when I needed to ventilate my frustration, spread my enthusiasm or just talk about completely other things than work. You have been there through thick and thin and been an invaluable support for me.

(10)
(11)

P

P

P

P

P

P

P

P

o

o

o

o

o

o

o

o

p

p

p

p

p

p

p

p

u

u

u

u

u

u

u

u

l

l

l

l

l

l

l

l

ä

ä

ä

ä

ä

ä

ä

ä

r

r

r

r

r

r

r

r

v

v

v

v

v

v

v

v

e

e

e

e

e

e

e

e

t

t

t

t

t

t

t

t

e

e

e

e

e

e

e

e

n

n

n

n

n

n

n

n

s

s

s

s

s

s

s

s

k

k

k

k

k

k

k

k

a

a

a

a

a

a

a

a

p

p

p

p

p

p

p

p

l

l

l

l

l

l

l

l

iiii

iiii

g

g

g

g

g

g

g

g

s

s

s

s

s

s

s

s

a

a

a

a

a

a

a

a

m

m

m

m

m

m

m

m

m

m

m

m

m

m

m

m

a

a

a

a

a

a

a

a

n

n

n

n

n

n

n

n

f

f

f

f

f

f

f

f

a

a

a

a

a

a

a

a

t

t

t

t

t

t

t

t

t

t

t

t

t

t

t

t

n

n

n

n

n

n

n

n

iiii

iiii

n

n

n

n

n

n

n

n

g

g

g

g

g

g

g

g

Jag hör människor säga att ”vi lever i en materialistisk värld”. De syftar oftast

på vårt värdesättande av materiella ting vad gäller livskvalitet. Uttrycket är

möjligen negativt laddat och jag kan hålla med om att det finns annat i livet som

är viktigare än att t.ex. ha den senaste mobiltelefonen. Men som forskare inom

materialfysik så ställer jag motfrågan om vi kan leva i en icke-materialistisk

värld. D.v.s. skulle vi kunna avhålla oss ifrån att utveckla produkter? Nej, det

tror jag inte, för det ligger i människans natur att vara nyfiken. 1947 insåg tre

herrar (Bardeen, Shockley, och Brattain) vikten av halvledarmaterialens

egenskaper och uppfann därmed transistorn. Tack vare transistorn har vi idag

mobila telefoner, bärbara datorer och solceller m.m., och visst är de

användbara? Nyfikenheten handlar om tillfredsställelsen av att upptäcka något

nytt och förhoppningsvis bättre. Den drivkraften tror jag alltid kommer att finnas

hos oss och kanske är det därför som vissa väljer att bli forskare. När jag får

frågan vad jag arbetar med svarar jag att jag forskar om material. Ibland

märker jag att mitt svar inte är tillräckligt konkret. Nu ska jag ta chansen att

ordentligt förklara vad min forskning handlat om.

Material kan generellt delas in i tre grupper; keramer, metaller och polymerer. Dessa har vitt skilda egenskaper. Keramer är allmänt hårda, spröda och leder varken värme eller elektricitet särskilt bra. Metallerna är däremot bra på att leda värme och elektricitet. De är också lättare att bearbeta och har lägre smälttemperatur än keramer. På 1990-talet blev Michel Barsoum och

Tamer El-Raghy nyfikna på Ti2AlC (titanaluminiumkarbid). Enligt en kemisk definition är det

en keram, men de insåg att denna keram även har vissa egenskaper likt en metall. Som exempel

har Ti2AlC hög värme och elektrisk ledningsförmåga. Ti2AlC kan dessutom utsättas för

temperaturer över 1000 °C utan att brytas ner. Vid så hög temperatur kryper lite aluminium ut på ytan och bildar ett skyddande skikt av aluminiumoxid, som hindrar nedbrytning av det underliggande materialet av Ti2AlC. Om man istället för att tillverka en hel kropp (bulk) av

Ti2AlC, kan belägga ytor med det så skulle det kunna skydda olika typer av produkter mot

oxidering och korrosion vid höga temperaturer.

Jag var först med att undersöka möjligheterna med att spreja Ti2AlC-beläggningar med ”termisk

(12)

som delvis smälter pulvret så att det fastnar på ytan, därav namnet – termisk sprutning. Dessa beläggningar blir uppåt en millimeter tjocka och man kan täcka stora ytor. Dessutom är det lätt att reparera skador då man bara behöver ta bort och spruta på ny beläggning på just det skadade

området. Jag har arbetat med att spreja Ti2AlC-pulver med målet att få tjocka och täta

beläggningar med bra vidhäftning till ytan. Beläggningarna får en komplicerad struktur med

Ti2AlC och områden med bland annat titankarbid och aluminium. Det beror på att Ti2AlC delvis

omvandlas i flamman. Jag har visat att man kan återbilda Ti2AlC om man värmer beläggningen

till 900 °C.

En annan beläggningsmetod som jag använt ger tunnare beläggningar, som oftast inte är mer än en mikrometer (en tusendels millimeter). De kallas därför för ”tunna filmer”. Metoden kallas för ”sputtring” och man belägger i princip ett atomlager i taget. Därmed kan man få en välstrukturerad (kristallin) beläggning ofta med en slät och spegelblank yta. Dessa kristallina filmer har jag använt för att studera materialet på atomnivå (en miljondels millimeter), för att förstå hur kristallerna växer och vad som händer när materialet utsätts för höga temperaturer och oxiderande miljö. De olika atomslagen som bygger upp filmen (titan, aluminium och kol) kommer oftast från var sin källa. För att förenkla den här syntesprocessen så har jag undersökt möjligheten att använda en enda källa som innehåller alla tre atomslagen. För att få rätt sammansättning så innehåller källan dubbelt så mycket titan som aluminium och kol. Det visade sig dock att sammansättningen i de tunna filmerna blev en annan med för mycket kol och för lite aluminium. Detta beror bland annat på själva beläggningsprocessen där atomerna slås ut från källan med hjälp av bombarderande argon-gas. Detta kan jämföras med biljard där det vita klotet med en viss hastighet och riktning träffar ett annat klot. I kollisionen överförs energi som får det andra klotet att röra sig med en annan riktning och hastighet. Titan, aluminium och kol påverkas olika av kollisionen med argon eftersom de har olika storlek och massa. Därför sprids titan, aluminium och kol vilket gör att mer kol når ytan som ska beläggas. Dessutom så har atomerna olika energi vilket påverkar förmågan till att binda till ytan. Jag föreslog en lösning där man tillsätter extra titan som hjälper till att binda upp aluminium och konkurrera ut kolet så

att man kan bilda Ti2AlC.

Jag har även undersökt vad som händer dessa beläggningar i oxiderande miljö. Om tunna filmer av Ti2AlC inte har möjlighet att bilda ett skyddande oxidskikt så sönderfaller de redan vid

700 °C. Oxidationsmotståndet hos de sprejade beläggningarna försämras om beläggningarna

innehåller annat än Ti2AlC, t.ex. titankarbid, som inte har samma goda oxidationsmotstånd som

Ti2AlC. För att Ti2AlC-beläggningar ska vara stabila vid högre temperaturer krävs det alltså att

(13)

Revolutionerande forskning som uppfinnandet av transistorn är givetvis inspirerande, men den största drivkraften fann jag i vardagen genom min forskning. Jag har spänt väntat på vad resultaten ska visa, fått adrenalinkickar av att lösa problem som dagen innan verkat omöjliga, och framför allt känt tillfredsställelsen av att lära mig något nytt.

Figuren visar a) en beläggning sprejad med b) termisk sprutning och c) en tunn film belagd med d) sputtring.

(14)

(15)

C

C

C

Contents

ontents

ontents

ontents

Abstract ... 1 Preface... 3 Acknowledgements ... 7 Populärvetenskaplig sammanfattning ... 9 1.Introduction ... 15 2.The Ti-Al-C System ... 17 2.1 Ternary Phases ...18 2.2 Binary Phases...21 3.Deposition of Coatings ... 25

3.1 Thermal Spraying: Thick Coatings ...26

3.2 Vapor Deposition: Thin Films ...29

4.Characterization Techniques with Related Results... 37

4.1 X-ray Diffraction (XRD) ...39

4.2 Electron Microscopy (EM) ...42

4.3 Ion Beam Analysis ...46

4.4 X-ray Photoelectron Spectroscopy (XPS)...48

4.5 Mechanical Characterization ...50

4.6 Plasma Analysis ...52

5.Comments on the Results and Contribution to the Field... 57

References ... 61

Paper I-VI

(16)
(17)

1

1

1

1

IIII

IIII

n

n

n

n

n

n

n

n

t

t

t

t

t

t

t

t

r

r

r

r

r

r

r

r

o

o

o

o

o

o

o

o

d

d

d

d

d

d

d

d

u

u

u

u

u

u

u

u

c

c

c

c

c

c

c

c

t

t

t

t

t

t

t

t

iiii

iiii

o

o

o

o

o

o

o

o

n

n

n

n

n

n

n

n

This Thesis covers the exploration of new deposition processes for Ti2AlC coatings and studies

of their phase stability and oxidation.

Ti2AlC belongs to the MAX-phase family of ternary carbides and nitrides; the majority of which

was discovered by Jeitschko and Nowotny in the 1960’s [1]. These phases are identified by their nanolayered crystal structure of a carbide or nitride alternated with one atomic layer of a third element, in this case Al. This third element results in a new crystal structure and a drastic change of the properties compared to the binary carbides and nitrides. In the 1990’s a renewed

interest in MAX phases (especially Ti3SiC2) appeared, thanks to the studies of Barsoum and

El-Raghy [2]. They realized that these ceramics have certain metallic properties including thermal shock resistance [3], thermal and electrical conductivity [4] and machinability [5]. Barsoum as well as Nowotny synthesized MAX phases by sintering processes. Several sintering methods have been employed in an attempt to increase the purity of the material [6], lower the synthesis temperature [7], and adapt to industrial needs [8].

MAX phases have been of interest as thin films and coatings since 1972 when Nickl et al. [9]

synthesized the archetypical phase Ti3SiC2 using chemical vapor deposition (CVD). Nowadays,

the most popular technique used in research on MAX phase thin films is magnetron sputtering. These studies were initiated at Linköping University in 2002 by our group [10] with Ti3SiC2

using various target combinations. Ti2AlC thin films were first synthesized by Jansson’s group

at Uppsala University [11,12], who used Ti, Al, and C sources. Using three elemental sources demands three times more parameters than using just one source. Simplified processes are more lucrative for industrial purposes and therefore sputtering from a single compound target would be preferred. Schneider’s [13] group at RWTH-Aachen investigated the possibilities of

sputtering from a Ti2AlC compound target. Their work showed that this synthesis route has

connected problems of obtaining the right stoichiometry of the films. I was challenged by that phenomenon to investigate what determines the final stoichiometry of the film, and if any deficient element(s) can be compensated for.

(18)

A main part of my work has been developing and exploring high velocity oxy-fuel (HVOF)

spraying as a brand new deposition process for Ti2AlC. HVOF is otherwise a well-established

thermal spray technique in, e.g., the aerospace industry. In 2001, a patent was filed for spraying MAX-phase powder with thermal spray techniques [14]. This Thesis presents the first

optimization study of spraying MAX-phase powder (Ti2AlC - crushed and sieved MAXTHAL®

211 material) followed by an investigation of how the microstructure and phase content of the

resultant coatings can be tailored for best results. My aim was to make Ti2AlC available as thick

coatings with good mechanical and thermal properties.

Ti2AlC has a desirable oxidation resistance. Extended studies have been made on bulk Ti2AlC to

understand its thermal properties in connection with oxidation and decomposition. It has thus been found that Ti2AlC works well at elevated temperatures [15] where it forms a dense and

passivating Al2O3 scale. The material can even go through thousands of temperature cycles

without breaking since the oxide is well adherent to Ti2AlC [16]. Li et al. have showed that it is

possible to attach pieces of bulk Ti2AlC through oxidation in a low oxygen pressure [17]. This

is, in my opinion, a good example of the fascinating relation between Ti2AlC and Al2O3.

Oxidation-resistant materials would clearly be interesting as a coating to protect parts operating at elevated temperature.

Since Ti2AlC is a high temperature material, I was interested in understanding the phase

stability at elevated temperatures of the sprayed coatings as well as magnetron-sputtered thin films. The aim was to determine the phase stability of Ti2AlC and the relation between this

MAX phase and other related binary phases that often co-exist. Next, I studied some details of

the oxidation properties of these coatings, not at least the relation between Ti2AlC and Al2O3.

The Thesis consists of a series of chapters that offer a background to the appended papers. Chapter 2 introduces Ti2AlC and related phases in the Ti-Al-C system. Chapter 3 describes the deposition techniques of high velocity oxy-fuel and magnetron sputtering. In Chapter 4, the different characterization methods used are presented along with illustrative results in addition to the Papers. Finally, in Chapter 5, I summarize my work and thoughts about the contribution that this Thesis might offer to the scientific and engineering fields of MAX phases. My Papers are collected at the end of this Thesis.

(19)

2

2

2

2

T

T

T

T

T

T

T

T

h

h

h

h

h

h

h

h

e

e

e

e

e

e

e

e

T

T

T

T

T

T

T

T

i

i

-

-

A

A

A

A

A

A

A

A

l

l

----

----

C

C

C

C

C

C

C

C

S

S

S

S

S

S

S

S

y

y

y

y

y

y

y

y

s

s

s

s

s

s

s

s

t

t

t

t

t

t

t

t

e

e

e

e

e

e

e

e

m

m

m

m

m

m

m

m

In this section, you will be introduced to the phases of the Ti-Al-C system that are

in focus of this Thesis. First, the ternary phases in the system are described with

focus on the MAX phases, the model materials in my research. Second, the

binary phases are considered, which in one way or another play an important

role for the properties in the thin films and coatings. A phase diagram of the

Ti-Al-C system is shown below to give an idea about the relations between these

three elements.

(20)

2.1

2.1

2.1

2.1 Ternary

Ternary

Ternary

Ternary P

P

Phases

P

hases

hases

hases

2.1.1 MAX Phases

There are two MAX phases in the Ti-Al-C system, namely Ti2AlC and Ti3AlC2. MAX phases

are a family of ternary carbides and nitrides. The name Mn+1AXn describes the elements

included where M is a transition metal, A is mainly a group 13 or 14 element, and X is C or N. The stoichiometry can vary (n = 1, 2, or 3) leading to M2AX, M3AX2 or M4AX3 phases. The

crystal structure of Ti2AlC and Ti3AlC2 is hexagonal with space group P63/mmc* and is

illustrated in Figure 2.2. The crystal structures contain TiC layers interleaved with single Al

layers. The stacking sequence depends on the stoichiometry where Ti3AlC2 has one Al layer for

every third TiC layer, and Ti2AlC, has one Al layer for every second TiC layer. The TiC is built

up by Ti octahedrons connected in each edge with C atoms filling the octahedral sites. The TiC layers are twinned with the Al layers as the mirror plane, as seen in Figure 2.2.

Figure 2.2. Crystal structure of Ti2AlC and Ti3AlC2.

The atomic binding character in the MAX phases has been shown to be a combination of metallic, ionic, and covalent [18]. The covalent-ionic Ti-C bonds are comparable to the bonds in the binary TiC and are stronger than the metallic Ti-Al bonds present in the ternary structure [19]. The relatively weak bonds between the TiC and Al layers in the basal planes contribute to an anisotropic character of the material leading to kink-band formation and delaminations along the basal planes upon deformation [20], seen in Figure 2.3.

* A hexagonal primitive unit cell (P) with 3 six-fold screw axes (63) and two mirror planes, where the first

(21)

Figure 2.3. Ti2AlC powder grain with visible layers of basal planes that have formed kinks from

the powder process.

Due to the combination of TiC bonds and metallic Al-Al bonds, Ti2AlC exhibits both ceramic

and metallic properties such as low density of 4.1 g/cm3 and a high electrical conductivity for

being a ceramic (3·106 Ω-1m-1) [18,21]. The bulk modulus of 186 GPa for Ti2AlC is lower than

for the binary TiC that has a bulk modulus of 240 GPa [19,22]. Further, Ti2AlC is ductile and

machinable [23] and has high thermal shock resistance [21].The hardness is ~5.5 GPa [21] for

bulk material, while for thin films it has been measured to 20 GPa [11]. The difference in hardness between bulk and thin film is affected by for instance the difference in indent depth. It is also possible that the thin film, which could have a preferred orientation compared to a polycrystalline bulk material, show anisotropic hardness between different crystal orientations.

The homogeneity range for synthesis of the MAX phases is relatively narrow where a small change in stoichiometry results in a different phase from what was aimed for. The difficulty of

obtaining the right stoichiometry when synthesizing Ti2AlC is discussed in Paper V. Once the

phase is formed it can, however, sustain a large understoichiometric Al content [24,25]. It is also possible to dissolve O on C vacancies [26].

An interesting feature of the phases Ti2AlC and Ti3AlC2 is their oxidation resistance. Optimal

oxidation results in the formation of an Al2O3 scale with a TiO2 scale on top. The formation of

TiO2 takes place on top of the α-Al2O3 scale due to outward diffusion of Ti through the Al2O3

grain boundaries [27,28]. The density of the Al2O3 scale is high, which will slow down diffusion

of oxygen through the oxide scale to the MAX phase and therefore prevent further oxidation [29]. Al2O3 adheres very well to Ti2AlC and does not peel off during thermal cycling even

though the lattice parameters are quite different (α-Al2O3: a = 4.76 Å [30], Ti2AlC: a = 3.04 Å

(22)

Al2O3[1100] as shown in Figure 2.4. Nevertheless, in Paper V, additional crystallographic

relationships are found when growing Ti2AlC onto single-crystal Al2O3 substrates. The well

adherent oxide scale on bulk Ti2AlC is explained by the condition that the thermal expansion

coefficient of α-Al2O3 is in the same range as Ti2AlC [30,23].

Figure 2.4. Illustration of the epitaxial relationships between Ti2AlC(0001) and Al2O3(0001).

Optimal oxidation of Ti2AlC and Ti3AlC2 forming dense and protective oxide scales is obtained

at temperatures ≥1000 °C [16,27,29,32]. However, at lower temperatures a mixed oxide is

formed containing both Al2O3 and TiO2 which is not preferable for a protective oxide scale

[33,34]. Also, TiO2 can form both rutile and anatase. The increasing density (and thereby

decreasing volume) of the TiO2 as it transforms from anatase to rutile results in cracks in the

scale, which then easily peels off.

2.1.2 Perovskite

Ti3AlC is an inverse perovskite structure with an Al cubic structure, Ti on its face-centered

positions, and C on the body-centered position. It has shown to be difficult to synthesize pure Ti3AlC material thus most report about Ti3AlC as a precipitation [11,35]. To this point no

experimental data of its properties have been found. There are, however, simulations of its electronic structure and elastic properties [36,37].

(23)

2.1.3 Phase diagram

One should be careful to interpret the Ti-Al-C phase diagrams that are available today. For example, all three ternary phases are present at the isothermal section at 1300 °C [38,39]. At

temperatures down to 700 °C, however, Ti3AlC2 is not present in the reported phase diagrams.

Phase diagrams represent a system in thermodynamic equilibrium. Yet, experimental work has

shown that Ti3AlC2 can form under thermodynamic equilibrium at temperatures below 1000 °C

[40]. More important though, is that the stability of the MAX phases relies on that the protective oxide scale forms on the surface. Without this oxide layer the MAX phases are prone to decompose below 1000 °C by releasing the Al (kinetic and not thermodynamic process [41])

and form TiC. This is shown in Paper VI where I annealed Ti2AlC thin films in vacuum, where

the oxidation is limited. The decomposition mechanism is not exclusive for the Tin+1AlCn

(n=1,2) MAX phases, but has also been observed for Ti3SiC2 (thin films) by releasing of Si at

temperatures just above 1000 °C [42]. Furthermore, in Paper III it is discussed how the decomposition of the MAX phases is affected by the presence of binary phases such as TiC and Ti-Al alloys.

2.2

2.2

2.2

2.2 Binary

Binary

Binary

Binary P

P

P

Phases

hases

hases

hases

2.2.1 T

i

C

TiC is among the hardest materials known. It has also attracted attention because of its high melting point and wear resistance. It is widely used as protective coatings for cutting, molding and milling tools, coatings for ball-bearings and spray gun nozzles as well as for fusion-reactor applications. TiC has a face-centered cubic close packed crystal structure (NaCl), as shown in Figure 2.5, and the space group is Fm3m†. TiC belongs to the group of interstitial carbides where carbon occupies the (interstitial) octahedral sites between the close packed Ti atoms. This

structure is a building block in the Tin+1AlCn (n=1,2) crystal structure, discussed above.

Interstitial carbides have partly ionic and covalent bonds, but with a metallic character that causes a relatively low electrical resistivity of 50 µΩcm, compared with Ti of 40 µΩcm [43]. The strong ionic bonds between Ti and C are due to the great difference in electronegativity of 1.0. TiC exhibits Young’s modulus of ~450 GPa, a melting point around 3000 °C, and a density

of 4.9 g/cm3 [43]. The hardness is ~25 GPa [44], while for TiC thin films it can be as high as

~30 GPa [45] depending on lattice defects.

(24)

Figure 2.5. NaCl crystal structure of TiC with interstitial C at the octahedral sites.

TiC is stable over a broad range of compositions. This makes TiCx a non-stoichiometric carbide

where a large amount of carbon vacancies may be present. The C content can vary between 32 and 49 at% [30]. This will cause a variation in cell parameters and consequently also variations

in properties for TiCx. It has been shown that if the C vacancies in the TiC structure are ordered,

Al can fill the spaces to form a MAX phase [40,46]. The oxidation properties are poor for TiC [47,48]. One way of improving the oxidation properties is to introduce Al [49].

For both the thermal spraying and magnetron sputtering technique, TiC is a competing phase for

the synthesis of Ti2AlC coatings. However, to improve the crystal quality of Ti2AlC, a TiC seed

layer is used as a template between the MAX phase film and the Al2O3 substrate.

2.2.2 T

i

-A

l

alloys

Ti-Al alloys have a combination of properties such as low density of ~4 g/cm3, good creep

resistance and high strength [50]. This has made them interesting as structural materials at high temperature, which is useful within the aerospace and automotive industry. According to the

phase diagram [51], the different Ti-Al intermetallic phases range from Ti-rich (Ti3Al) via TiAl

to Al-rich (Al3Ti) phases. Ti3Al has a hexagonal crystal structure while both TiAl and Al3Ti

have a face-centered cubic crystal structure.

The properties of Ti-Al such as electrical resistivity and creep resistance depend on its microstructure as well as composition [52,53]. For instance, Ti-Al thin films have a lower friction coefficient and a lower hardness with increasing Al content [54]. At high temperatures Ti-Al forms Ti- and Al-oxides. The formation of oxides is complex and depends on phase

(25)

composition, temperature, and oxygen pressure [55,56,57]. Higher Al content (>50 at%) or introduction of other metals such as Cu or Cr will improve the oxidation resistance [58,59].

In this work, Ti-Al alloys act as binding phases in HVOF-sprayed Ti2AlC coatings and are thus

also of importance for the density and adhesion of the coatings.

(26)

(27)

3

3

3

3

D

D

D

D

D

D

D

D

e

e

e

e

e

e

e

e

p

p

p

p

p

p

p

p

o

o

o

o

o

o

o

o

s

s

s

s

s

s

s

s

iiii

iiii

t

t

t

t

t

t

t

t

iiii

iiii

o

o

o

o

o

o

o

o

n

n

n

n

n

n

n

n

o

o

o

o

o

o

o

o

f

f

f

f

f

f

f

f

C

C

C

C

C

C

C

C

o

o

o

o

o

o

o

o

a

a

a

a

a

a

a

a

t

t

t

t

t

t

t

t

iiii

iiii

n

n

n

n

n

n

n

n

g

g

g

g

g

g

g

g

s

s

s

s

s

s

s

s

Coatings are used to improve and complement the properties of bulk materials.

Examples of such properties are hardness, resistivity, oxidation resistance, and

appearance. These properties, on the other hand, cannot be claimed to be good

or bad unless we associate them with some sort of application. A DVD, for

instance, needs a coating that reflects the laser in a DVD player, while

eye-glasses can make use of an antireflective coating to provide a better optical

performance, not to mention decorative coatings on the frames. These

applications also make use of scratch resistant coatings to extend the product’s

lifetime. If you start to look around, you will see that many products are

improved by or rely on coatings. In this section, I will describe the two

deposition techniques that I have had the opportunity to work with during my

PhD. These techniques differ in every way from the principle of deposition to

properties of the resulting coatings.

(28)

3.1

3.1

3.1

3.1 Thermal Spray

Thermal Spray

Thermal Spray

Thermal Spraying

ing

ing

ing: Thick Coatings

: Thick Coatings

: Thick Coatings

: Thick Coatings

Thermal spraying is a family of established industrial techniques, which are used to deposit coatings of thicknesses around 100 µm. These techniques use thermal energy to melt and soften particles, which are then accelerated (sprayed) by process gases towards a substrate. Powder, wire or rods are the most used feedstock for thermal spray, however, gas and liquids can also be used. The materials span ceramics, polymers, and metals. Thermal spray was invented in the beginning of the 1900’s, but did not enter commercial use until a half century later. The thermal spray family is divided into three main spraying techniques; plasma, electric arc, and flame.

Plasma spray creates thermal plasma by an electric field, which sustains a current as the free

electrons move through the ionized gas. The heavy ions transfer kinetic energy in the gas upon collisions. Common energy sources for the plasma are dc or rf. Plasma spray is a hot spraying technique, which creates plasma temperatures exceeding 15 000 °C [60] depending on the gas character. The generated particle temperature reaches 3800 °C [60]. The high kinetic energy of the particles and high degree of melting generate coatings with a higher density and adhesion to substrate comparable to both flame and electric arc processes. Oxides will, however, always be present in plasma sprayed coatings. To avoid this, vacuum plasma techniques have been developed.

Electric arc uses a dc electric arc, which is struck between two wires of spraying material that

melts. A fine distribution of molten metal droplets is transported by a high-velocity air jet, which is introduced behind the intersection of the wires. The wires are continuously fed closer as the material is consumed. Unlike flame and plasma spray, the droplet cools down immediately as the droplets leave the arc zone and the substrate only get heated by sprayed particles. This enables spraying on substrates such as polymers, wood, and even paper.

Flame spray was the first invented technique and is mainly used for spraying metals and alloys.

The sprayed material is heated by combustion of fuel gases, most often a mix of acetylene and oxygen. The melted material is then accelerated by the expanding gas flow. Flame spray generates the lowest particle velocity of only 80 m/s before impact. The jet temperature is around 3200 °C [60] and is controlled by the fuel/oxygen ratio. Either side of stoichiometry will cool the flame, but vary between oxidizing (oxygen rich) or reducing (fuel rich) of the feedstock material. The characteristics for flame sprayed coatings is a density ranging from 85 to 98 % and relatively high oxide content. Flame spray has, however, developed during the years. The focus here is on high velocity oxy-fuel (HVOF), which is the technique used in Paper I-IV. This technique offers higher gas velocities and consequently coatings with properties that differ from regular flame spraying.

(29)

3.1.1 High Velocity Oxy-Fuel (HVOF)

HVOF uses the heat and velocity from combusted gases. The use of a combustion chamber and confined nozzles results in supersonic particle velocities. With such high velocity, the HVOF process exhibits noticeable shock diamond patterns in the gas jet [61]. A drawback of HVOF is the noise level which is in the range of 125+ to 133+ dBA [60] and therefore requires noise reducing spraying booths for the equipment. The high particle velocity generates coatings with high density and good adhesion. The particle temperature is lower than for plasma spray, which reduces the melting, decomposition, and oxidation. Figure 3.2 shows a schematic drawing of a high velocity oxy-fuel gun with its combustion chamber connected with a confined nozzle. The combustion chamber is air- or water-cooled to prevent oxidation of the gun components. Oxidation would be damaging for the spraying process as it reduces the cooling effect further causing powder build-up and the nozzle to melt. The powder is borne by a carrier gas and fed into the nozzle. Common gases are hydrogen, propane, kerosene or acetylene mixed with oxygen. Different shapes of the nozzle create different shapes of the spray pattern.

Cooling in Cooling out Oxygen Powder Fuel Combustion chamber Shock diamonds Cooling in Cooling out Oxygen Powder Fuel Combustion chamber Shock diamonds

Figure 3.2. Schematic drawing of a High Velocity Oxy-Fuel gun. The different parts are not drawn to scale.

Ti2AlC coatings have been deposited with HVOF and characterized in Paper I-IV. A mix of

hydrogen and oxygen gas was used to spray Ti2AlC (MAXTHALTM 211) powder.

3.1.2 The effect of gas and powder parameters

The spraying process depends on several parameters. Two main ingredients are the powder and gas parameters. They affect the temperature and velocity of the sprayed particles. The particle temperature and velocity will determine the characteristics of the coating such as adhesion,

(30)

between them will affect the gas temperature. Both gas velocity and temperature varies greatly in the spray stream, where for instance the core is hot compared to the relatively cold surrounding. There are both radial and axial gradients of the gas temperature and velocity. Therefore values of dwell time (the time a particle spends in the flame) and temperatures are reported as average values for the distributions in the flame. Longer dwell time, in general, results in higher concentrations of oxide inclusions. There are pyrometer techniques, which can determine the particle temperature and velocity in the flame. This information is useful to understand the characteristics of the coatings and for optimizing parameters. The measured temperature is, however, only representing the surface of the particle. This can be misleading if, for instance, the particle has oxidized in the flame. The measurement is based on an average of particles and the analysis is therefore material-consuming. The thermal and physical characteristics of the powder are also important, i.e., a solid particle melts slower than a porous granule. In Papers I and II, I have investigated how the total gas flow and the powder size affect

the microstructure as well as the phase content of coatings sprayed with Ti2AlC powder.

3.1.3 Structure of Thermally Sprayed Coatings

A thermally sprayed coating is built up by molten or heated particles that spread out and solidify very fast upon impact, so called splats [63], see Figure 3.3. The fast cooling rate gives an opportunity to form amorphous and metastable phases. The build-up of splats may yield a lamellar microstructure and often a very rough surface, which for certain applications are machined off. The substrate surface is sand-blasted to create a rough surface in which the splats can hook, resulting in good adhesion, mainly of mechanical character rather than chemical [64]. The degree of melting of the particles affects the splat formation and determines the cohesion and porosity of the coating.

Figure 3.3. SEM cross section image of a coating sprayed with Ti2AlC powder, which shows a typical microstructure of a HVOF

(31)

Porosity leads to poor cohesion within the coating, low wear resistance, low hardness, and high corrosion rate. Open porosity means that a corroding agent can reach the substrate. On the other hand, the porosity can be utilized to produce oil-impregnated coatings and is also desirable as an insulating effect for thermal barrier coatings (TBC).

Oxides are formed in most thermally sprayed coatings and can often be seen as dark elongated strings parallel to the substrate. The oxides are formed during spraying when heated particles and the surface of the coating interact with the surrounding. They have a high hardness and therefore often contribute to increase the average hardness of the coating, but also cause brittleness. Thus, oxides formed during spraying are usually not wanted, but there are cases where oxides are desired because they increase the wear resistance or lower the thermal conductivity.

3

3

3

3....2

2

2 Vapor Deposition:

2

Vapor Deposition:

Vapor Deposition:

Vapor Deposition: Thin Film

Thin Film

Thin Film

Thin Films

s

s

s

Vapor deposition techniques use vapor of either molecules or atoms to grow thin films of up to ~10 µm. The deposition rate depends on the technique, but is in general lower than thermal spray processes. The two main groups of vapor deposition techniques are chemical vapor

deposition (CVD) and physical vapor deposition (PVD). CVD uses volatile gases which react at

the substrate surface to grow the coating at conditions near thermodynamic equilibrium. This technique offers deposition of complicated geometries at relatively high rate. Disadvantages are the use of high substrate temperature, which limits the choice of substrate material, and that some of the gases used are hazardous. In comparison, PVD makes use of vaporization of solid or liquid material that condenses on the substrate surface. It can only deposit line-on sight, but typically operates at much lower temperatures than CVD. The low temperature and low pressure offer deposition far from thermodynamic equilibrium and therefore potential growth of metastable phases. There are several ways to vaporize a solid material. Pulsed laser deposition (PLD) vaporizes the material with a high energy laser. Cathodic arc deposition and magnetron

sputtering are two techniques that instead utilize a plasma. All techniques demands high or ultra

high vacuum (HV or UHV) chambers, which provides a process with very low contamination level.

3.2.1 Magnetron Sputtering

In PVD processing, condensation of a material takes place in a vacuum chamber to control the growth and obtain high purity of the films. The sputtering process uses a source of material (target) with applied negative voltage that attracts relatively heavy ions (from a plasma) and

(32)

knocks out atoms from the target. These atoms are deposited one by one to grow a well-defined coating. The target can consist of a metal, a ceramic or a composite material of different phases. In most cases argon or another noble gas is used, but reactive gases can also be introduced. Oxygen and nitrogen are two common reactive gases. The corresponding process is called reactive sputtering. The magnetron sputtering process is illustrated in Figure 3.4 and will be described in more detail below.

Figure 3.4. Schematic of the magnetron sputtering process.

As a plasma is ignited, sputtering and deposition can take place. By the use of a magnetron where magnets are mounted behind the target, a magnetic field is applied to gather electrons. A high electron density is preferred close to the target to amplify the ionization of the plasma and increase the sputter rate. The argon ions must have enough momentum upon impact to break bonds in the target material and to transfer sufficient kinetic energy to the outgoing atoms. These atoms travel through the plasma and the probability of an atom to hit argon ions depends on the pressure. Some sputtered atoms will reach the substrate without interacting with other plasma species, but most atoms will undergo collisions and lose some of their kinetic energy. Many sputtered atoms will lose all of their initial kinetic energy and move randomly. These atoms are called thermalized.

Some elements are easier to sputter (knock out from the target) than others. The sputter yield is a parameter that states how many sputtered atoms you get from one incoming ion, in other words, the efficiency of sputtering. Values usually range from 0.1 to 10 [65]. Of special interest

(33)

to this Thesis are the sputtering yields of Ti, Al, and C. Sputtering with 0.5 keV Ar ions results in a sputtering yield of 0.51 for Ti, 1.05 for Al, and 0.12 for C [65]. During sputtering from an alloy target of many elements, the difference in sputtering yield will be compensated for by the build-up of a composition difference at the surface of the target until steady-state is reached

[65]. If this can be applied to a Ti2AlC target it would lead to a surface containing less of the

elements that are easy to sputter, i.e., Al, and more of the elements that are harder to sputter, i.e., Ti and C when equilibrium is reached. As a result the out-flow from the target has a content of Ti, Al, and C representing the nominal composition of the target. There are, however, additional effects that have to be considered when sputtering from a compound target [66,67,68]. The angular distribution (see Figure 3.5 a) and energy of the sputtered atoms differ between elements. In general, heavier atoms are sputtered out at a higher angle, but lower energy than lighter atoms. The scattering angle in the plasma as the atoms collide with other species also depends on the mass of the element, see Figure 3.5 b). Heavier atoms do not scatter as much and lose less energy upon a collision as lighter atoms.

Figure 3.5. Illustration of a) the angular distribution, θ, during sputtering of a compound target and b) the scattering for different elements.

The substrate is most often heated to increase mobility of the arriving atoms. Most materials can be used as substrates as long as they can withstand the temperature required for deposition. A negative voltage (bias) applied to the substrate can cause different effects depending on its magnitude. A low voltage increases the mobility of the arriving atoms. A voltage around 100 V makes it possible to etch or sputter the surface. Higher voltage in the range of 1000 V will readily implant atoms into the coating or substrate.

(34)

In Paper V and VI, direct current magnetron sputtering has been used to deposit Ti-Al-C thin

films in an UHV chamber. Paper V is an investigation of the option of sputtering from a Ti2AlC

compound target, while the thin films studied in Paper VI were sputtered from three elemental targets; Ti, Al, and C.

3.2.2 Plasma physics

There are four common states of matter; solid, liquid, gas, and plasma. A plasma can be described as a cloud of positive and negative charges. The net charge is zero, meaning that there are just as many positively charged ions as negative electrons. We have many kinds of plasma around us, for instance in northern lights and the sun. Plasma is also used in many different applications. Its fascinating light is used for neon signs and energy lamps. High-energetic plasma is used for thermal spraying, as cutting tools or in disinfection processes. For the sputtering process, plasma is used as a tool for depositing thin films. The ignition of a plasma in a gas is called plasma breakdown. Ar gas is introduced into the vacuum chamber and an electric field is applied between the chamber (anode) and the target (cathode). Due to background radiation, there is always a number of ions and electrons present. The electrons will accelerate towards the chamber walls and the ions are attracted to the target. When ions get close to the target, electrons from the target tunnel and neutralize the ions. Energy corresponding to the ionization energy is released. If this energy is greater than the work function of the electrons in the target, secondary electrons will be released, which will be transported to the plasma and ionize more argon atoms. A plasma of ions and electrons is now sustained.

3.2.3 Film Growth

There are important mechanisms that are common to any kind of film growth, for example, the adsorption to the surface of the incoming atoms and the following nucleation. Then there are different modes describing the evolution of thin film growth, which might result in different microstructure, such as a single crystal or polycrystalline film. Film growth can be modified by using the right combination of parameters such as temperature, pressure, substrate etc. This section will briefly discuss these mechanisms starting with adsorption of atoms to the surface.

Incoming atoms with an energy of a few electron volts (eV) adsorb to the surface. Some atoms attach to the surface with Van der Waals bonding. This is called physisorption and implies a local polarization resulting in an attractive force between the atom and the surface, meaning that no exchange of electrons takes place. There is no energy barrier to overcome and the energy required to adsorb or desorb is small. That is not the case for chemisorbed atoms, which are

(35)

chemically bonded to the surface by ionic or covalent bonding. A higher energy of the incoming atom is needed to overcome the energy barrier for breaking existing bonds and create new ones between the incoming atom and the surface atoms. The magnitude of the energy barrier is dependent on the character of the surface and incoming species.

There are more and less favorable sites for atoms to bond. For instance, there is a higher probability that an atom bonds to a step-site or corner than on a plane-site. Moreover, an atom rather combines with another atom or clusters of atoms before it adsorbs. As a result, nuclei are formed.

When a nucleus is formed there is a change in the total free energy, ∆G:

4

3

42

1

4

4

4

4

4

3

4

4

4

4

4

2

1

interface Vapor Substrate 2 2 Nucleus 2 2 2 1 3 3 −

+

+

=

G

a

r

G

V

a

r

γ

vf

a

r

γ

fs

a

r

γ

vs (3.2)

The change is related to the free energy per volume unit, ∆GV, and the surface energies, γfv, γfs,

and γsv. The subscripts f, v, and s stand for film, vapor, and substrate, respectively. The

geometric constants a1, a2, and a3 together with the nucleus radius, r, describe the surfaces of

the film-vapor and film-substrate interfaces, respectively, as well as the volume of the nucleus. The relation between the surface energies is demonstrated in Figure 3.6. Be aware of that the

sign of ∆GV is negative and that nucleation will take place when ∆G is negative. The formula

describes the change in energy when an interface between substrate and vapor breaks up to form two new interfaces and a volume, namely a nucleus.

References

Related documents

All recipes were tested by about 200 children in a project called the Children's best table where children aged 6-12 years worked with food as a theme to increase knowledge

This article will provide just such a consideration of Shakespeare's final play, The Tempest (1611), providing a critical review of the play's ecocritical studies thus far, and

With a reception like this thereʼs little surprise that the phone has been ringing off the hook ever since, and the last year has seen them bring their inimitable brand

registered. This poses a limitation on the size of the area to be surveyed. As a rule of thumb the study area should not be larger than 20 ha in forest or 100 ha in

Hence, the manufacturer embeds items as sensory cues based on brand-related stimuli in the value proposition to offer value for sense-making, where the brand

It has also shown that by using an autoregressive distributed lagged model one can model the fundamental values for real estate prices with both stationary

46 Konkreta exempel skulle kunna vara främjandeinsatser för affärsänglar/affärsängelnätverk, skapa arenor där aktörer från utbuds- och efterfrågesidan kan mötas eller

Department of Physics, Chemistry, and Biology (IFM) Linköping University,