director pedro prieto. prieto.pdf · 2009 aps april meeting cenm fip physics in latin america...

EXCELLENCE CENTER FOR NOVEL MATERIALS - CENM MATERIALS - CENM

Enhancing academy-industry-state ties

www.cenm.org

CENMCENM

Director Pedro Prieto

www.cenm.org

CENM2009 APS April Meeting FIP

Physics in Latin America

Physics in Andean countries: a perspective from condensed matter, novel materials, and o co de sed atte , o e ate a s, a d

nanotechnology

P. Prieto

APS FellowDirector of the Center of Excellence for Novel Materials – CENM

Universidad del Valle, Cali - Colombia

April Meeting Denver, Colorado May 2 2009

Publications in nanotechnology in the Iberian American countries

1600

1800

1200

1400

SPAIN

800

1000SPAINBRAZILMEXICOPORTUGAL

400

600PORTUGALARGENTINA

0

200

2000 2001 2002 2003 2004 2005 2006 20072000 2001 2002 2003 2004 2005 2006 2007

Publications in nanotechnology in Iberian American nations

7000

8000

9000Iberian American nations

Chile (581 publications)Colombia (311)Venezuela (291) 5000

6000

7000

Peru (50)

2000

3000

4000

0

1000

2000

* Andean Countries

Nanotech development in the regionNanotechnology activity , measured by scientific publications, has almost doubled worldwide between 2000 & 2007In Iberian America, Spain & Brazil pioneered and lead in scientific production & technological development in p g pnanotech. The remaining Iberian nations show markedly lower production for the whole period.From 2000 to 2007 Iberian America had about 20 000 From 2000 to 2007, Iberian America had about 20,000 documents in SCI. While the base total grew by 25%, during the same period articles on nanotech reached a 100% increase. Thi i 3 5% f h l # f Ib i A i bli i This is 3.5% of the total # of Iberian American publications registered in SCI for the period.

Nanotech activity in Iberian America is growing, but it is still far behind worldwide figures.

Nanotech development in the region

The main Iberian American nations have implemented active li i tit ti d h i tit ti & i t t t t policies, constituting ad-hoc institutions & instruments to support

nanotech, such as: Red NANOSPAIN, the Brazilian Initiative on Nanotechnology, and the Argentine Nanotechnology Foundation (FAN)(FAN)

The Iberian American institution with the highest participation in SCI is Spain’s Superior Council on Scientific Research (CSIC). It participates is Spain s Superior Council on Scientific Research (CSIC). It participates with 11.8% of the Iberian American production in nanotech, and reveals a marked increase of over 100% between 2000 & 2007.

Leadership of Brazil and Spain has been a result of the implementation of state policies and political will to support nanotech R&D.

Nanotech development in the region

Given the relatively small scientific community and scant financial resources in each latin American countries , only decided regional collaboration can offer the critical mass needed to render nanotech R&D the necessary sustainability.

Iberian American collaboration is greatly important inasmuch as it has increased the scientific production of smaller nations by participating increased the scientific production of smaller nations by participating with more developed nations.

Close collaboration within and with leading nations in Nanotech Close collaboration within and with leading nations in Nanotech development will bring marked growth in Latin America’s participation.

www.nanotecnologia.com.peCarlos Aguirre-Bastos ¨POLITICAS PUBLICAS PARA EL

DESARROLLO DE LA NANOTECNOLOGIA¨

Expenditure as % of GDP (2005))3.33

Expenditure as % of GDP (2005))

1.84

2.60

0.730.30

Andean Latin american Europe* United States JapanAndean Countries

Latin american Europe* United States Japan

* Includes the 27 member stateshttp://www.ricyt.org/interior/difusion/pubs/elc2008/InnovaEN.pdfINNOVATION: SOMETHING MORE THAN R&D. Latin American evidence from innovation surveys: building competitive business strategies, Guillermo Anlló (CEPAL), Diana Suárez (Centro Redes)

GDP: 130 B GDP: 165 B

Current status of R&D in Andean nations Current status of R&D in Andean nations

GDP: 130 BGERD: 0.2% (260 M)

ME: 4.4 B

GDP: 165 BGERD: 0.3%

(500 M)ME: 2 B

GDP: 41 BGERD: 0.2%

(81M)

USA : GDP - 14T GERD: 2.5% (350 B) ME: 644 B

Brazil: GDP – 1T,GERD: 1.1% (11 B)

ME: 24 B

GDP: 89 BGERD: 0.1%

(90M)

ME: 1.1 B Total LA R&D expenditure is a small piece of a tiny pie

(90M)ME: 1.3 B

GDP: 10 BGERD 0 2%

Total LA ME: ~ 40 B Mega military expenditure withoutGERD:0.2%

(18M)ME: 190 MGDP: 141 B RED DE INDICADORES DE CIENCA Y

TECNOLOGIA IBEROAMERICANA E

expenditure without a clear enemy

GERD: 0.6% (850 M)

ME: 3.8 B

TECNOLOGIA IBEROAMERICANA E INTERAMERICANA RICYT

http://www.ricyt.orgAdapted from: CIA World Fact Book

2009 & IMF, World Economic Outlook Database April 2006

GDP: gross domestic productGERD: gross expenditure in R&DME: military expenditure

Nanotechnology in Nanotechnology in Andean CountriesAndean CountriesAndean CountriesAndean Countries

Some Andean nations have instituted state policies appertaining to

nanotechnology In many cases the intentions are good, but the results are

poor. If not miserable!!

Nano in EcuadorNano in Ecuador

In 2005, the National Secretariat of Science and Technology(SENACYT), through the office of the VicePresident published the document outlining the NationalPresident, published the document outlining the NationalPolicy for Science, Technology, and Innovation 2005-2010.

Among the objectives of the policy, it seeks to fund basicsciences and natural sciences, including nanotechnology.

Results are yet to be noted!!!

www.nanotecnologia.com.peCarlos Aguirre-Bastos ¨POLITICAS PUBLICAS PARA

EL DESARROLLO DE LA NANOTECNOLOGIA¨

Nano in Chile

CONICYT, created in 1967, advises the President on

Nano in Chile

scientific issues. It grants scholarships for graduate studiesand funds R&D projects. Chile has been a clear participantand is well aware of the importance of nanoscience R&Dand is well aware of the importance of nanoscience R&D.

The Center for Nanoscience in Valparaiso seeks tostrengthen activities in experimental research in fieldsstrengthen activities in experimental research in fieldsrelated to the S&T of systems at the nano scale.

http://www.conicyt.cl/573/propertyvalue-1735.htmlhttp://www.cenava.cl

Nano in Chile

CIMAT: Center for advanced interdisciplinary research in

Nano in Chile

CIMAT: Center for advanced interdisciplinary research inmaterials science was created in 1998, for a 10-yearperiod, through a national effort for advanced research inpriority areaspriority areas

Bio-related Materials

Mechanics of Complex Materials

htt // i t l/573/ t l 1735 ht l

Catalytic & Polymeric Materials

http://www.conicyt.cl/573/propertyvalue-1735.html

Nano in BoliviaNano in Bolivia

Creation of the National System for Scientific TechnologicalDevelopment, SINDECYT, 1977 Vice Ministry of Science andT h lTechnology

In Bolivia nano is truly nanoIn Bolivia, nano is truly nano



Nano in Perú

The Strategic National Plan for Science, Technology, and

Nano in Perú

g gyInnovation for Competitivity and Human Development(PNCTI) 2006-2021, includes the manipulation and designof nanomaterials as a thematic hub within the Materialsof nanomaterials as a thematic hub within the MaterialsProgram (PROMAT). [Gutarra, 2007].

The Plan expects to increase public and private investmentin nanomaterials.

Peru began with a good plan, on paper. Good plans needgood cash flow and competent human resources, stilllacking!lacking!



Nano in VenezuelaNano in Venezuela

The government launched, in 1995, the NationalPlan in Science, Technology, and Innovation(PNCTI) for 2005-2030.(PNCTI) for 2005 2030.

Venezuela wants to improve its long-termVenezuela wants to improve its long term participation in ST&I. Studies are underway. Greater percentage of the GDP is promised

for R&D.

St t d Aló id t !!!Stay tuned. Aló, presidente!!!www.mct.gob.ve

Nano in Colombia

In 2004, COLCIENCIAS selected 8 strategic areas to enhance

Nano in Colombia

In 2004, COLCIENCIAS selected 8 strategic areas to enhanceproductivity & competitivity in Colombian economy, one was“Advanced Materials & Nanotechnology”.

Colombia still needs clear and long-term state policies tosupport Nanotech R&D Some short term work has provensupport Nanotech R&D. Some short-term work has provensuccessful, as is the case with the Excellence Center forNovel Materials



Latin American participation in innovation processes

Mere passive receptors of scientific and technological transference of knowledge.

Public & private investment do not support S&T Research Innovation & Implementation in S&T Research, Innovation & Implementation in Nanotech

Aggressive and long-term public and private investment must become state policy

In Brief

In spite of achievements, limitations persist.S di h i d li &Studies have reviewed policy, strategy, &plans, arriving at conclusions dealing with:

Limited impact Lack of real political will & decision Lack of funds Lack of culture for research and innovation O l d i t ti Only good intentions

Velho, 2004; OEA, 2004; Albornoz, 2002; BID, 2001

As a summaryMany in the region are still not convinced thatST&I should be a national priority.M h ill f hMany others are still not aware of whatnanotechnology means or what applications it mayhave.have.Some are reticent to accept ST&I as an instrumentof change.Most are sure that military spending is mostimportant.U il h l h d li i ithUntil now, we have only had nano policies with nanoinvestments for nanotech R&D; we must pave the wayfor Mega-investments and long-term commitments bystate and private entities

About CENM

The Excellence Center for Novel Materials is part of a high-priority Colombian effort supported by 19 recognizedmultidisciplinary research groups from 10 universitiesacross the nation. Additionally, the Center receivesy,international support from world-renowned institutes onmaterials research.

AFM image of Nanoindentation print -CENM

VO2 Pattern fabricated using e-beam and Photo lithography

CENM- UCSD

Materials Processes & Design - J. Torres

•Corrosion & Protection C •Photonic Materials

•Optics and signal treatment –J . Meneses

At i & M l l Ph i

•Solid State – C. Barrero

•Corrosion & Protection, C. Arroyave

Photonic MaterialsA. Flórez

•Computational Physics of Condensed matter -

J Betancurt

Physics of Novel Materials - J. Roa

•Materials Science & Engineering - N. Alba

•Atomic & Molecular Physics -J. Mahecha

J. Betancurt

Materials J. Roag g

Plasma laser and •Thin Films – P. Prieto

•Composite Materials – R. Mejía

applications -H. Riascos

•Physical Metallurgy and Phase transitions - G. Pérez

•Phase transitions in nonmetallic systems - R. Vargas

Optoelectronics -H. Ariza

•Solid state theoretical physics - J C.

•Synthesis and reaction mechanisms in Organic Chemistry -L. M. Jaramillo

E. Holguín Low-Temperature Physics

G. Bolaños

Materials science -Y. Rojas

p yGranada

National and International CollaborationsNational and International CollaborationsCENM

General Objetives and Strategies CENMg

To aid in Colombia‘s technological & scientific development throughg p gthe formation of specialized human resource working with novelmaterials technologies

o Greater R&D investment

o Acquisition of robust equipment

o Formation of young talents

o Support a knowledge-based economy for growth

CENM Immediate Strategies CENM

Establish technology transference policies from thei iti t th i d t i l tuniversities to the industrial sector

Build infrastructure to share knowledge; facilitateawareness in nanotech research and supportawareness in nanotech research and supportcommercialization of nano-products in the shortterm

Establish close ties with industry for joint researchprojects

Seek State policies to identify key interest areas forthe benefit of society, industry, and academia

Seek public and private funding to support researchand increase potential coverage

CENMSustainability Strategies

Strategic alliances Seek benefactorsStrategic alliances with industry

Seek benefactorsProject formulation & presentation to

international Strategic alliances with universities

entities

CENM Social responsibility efforts with NGOs Strategic alliances

with R&D centers

CENM

f

efforts with NGOs and government

Sell services & consultancy

Creation of CENM

Formation of new talents

Creation of CENM foundationNational & international

positioning

Areas of Research

Research work at CENM is organized around 4 InterdisciplinaryResearch Themes (IRTs):Research Themes (IRTs):

Composite Materials Advanced Coatings Nano-magnetism Solid-State Devices, Sensors, and Mesoscopic

SystemsSystems

MFM image of magnetic nanoparticles CoZnFe2O4 - CENM

AFM image of nanolithography over a polymer surface - CENM

Nanocomposite Materials: GoalsGoals

o Development of new materials for construction applications appertaining to the development of civil to the development of civil engineering infrastructure in Colombia

o Active nano-powders for cementitious-based mate ials f om ind st ial aste based materials from industrial waste and industrial by-products to produce cementing materials with high-mechanical performance and mechanical performance and durability, contributing to environmental sustainability

Nano-powder in Cement Materials CENM

COATING MATERIALS: Goals: Goals:

o Development of novel materials with improved resistance to corrosion and wear with high-temperature wear, with high temperature hardness conditions:

Composite coatings (SiC and di d ti l i Ni d diamond nanoparticles in Ni and Ni-Cr matrixes and nano-sized iron oxide particles in Ni-P)

Multilayered coatings (W/WC and TiN/ZrN TiCN/TiCNbN Multilayers)

EM micrograph of a TiN/B4C/BCN/c-BN multilayered hard coating - CENM

Nanomagnetism: Goals

o Gain basic understanding of nanoscale magnetic propertiesand knowledge on improving magnetic properties for broaderand knowledge on improving magnetic properties for broaderapplications in industry

o Areas of study:

Fe- and Mn-based Magnetic systems Oxide-based magnetic thin films and Oxide based magnetic thin films and

hetero-structures Theoretical and numerical simulation

of magnetic behavior of magnetic behavior Nanocomposite and nano-structured

magnetic alloys for hard and soft magnetic materials magnetic materials

Magnetization curve of LaCoO3. CENM

Solid-State Devices, Sensors, Mesoscopic Systems: GoalsMesoscopic Systems: Goalso Performance of new materials, focusing on quaternary

i d t i i t l M S d M b d id semiconductors, ionic crystals; Mn, Sn, and Mo-based oxides o Characterization of optical, electrical, and magnetic properties

fundamental for the design of deviceso Study the effects of dimensionality reduction and the presence of

confinements on properties of materials

o Development of theoretical models and o Development of theoretical models and simulations

o Study focuses mainly on optical, electric and magnetic properties of GaInAsSb and magnetic properties of GaInAsSb quaternary systems, ionic materials, Photonic materials, VO2 thin films

Tetragonal(Rutile)

Monoclinicfilms.

Ramirez, et al. PRL 101 (2008)

Scientific production per research area research area

2%

InternationalP 183

11%

32%55%

Composite materials

Hard Coatings

Nanomagnetism Papers 183 Nanomagnetism

Solid‐state Devices

10%11%45% 11%

34%

45% Composite materials

Hard Coatings

Nanomagnetism

S lid t t D i

NationalPapers 133Solid‐state Devices Papers 133

CENMCENM IN FIGURES

Participation in Scientific EventsParticipation in Scientific EventsNationalInternationalNational International Mobility

488395National, International Mobility

Publications in International Scientific JournalsPublications in National Scientific Journals

95164104

Participation in National ConferencesParticipation in International ConferencesAgreements with Companies

1862686

Agreements with State EntitiesAgreements with Educational Entities

23

Agreements with International Educational Entities 2Agreements with International Educational Entities 2

Students supported by CENM

PhD students 4Masters students4414

Masters students PhD students graduated with CENM supportMasters students graduated with CENM support 16

Graduate students participating in projects

Young Researchers

46

6

CENMEvents held by CENM

Held in Santa Marta – Colombia, OctoberHeld in Santa Marta Colombia, October 16 to 20, 2006.

Held in Cartagena de Indias –Colombia, October 13 to 17, 2008.

Held in Cali – Colombia, November 12 to 14, 2008.

CENMEVENTS HELD BY CENM

Held in Cali Colombia A g st 8 to 10 2007Held in Cali – Colombia, August 8 to 10, 2007

Held in Cali – Colombia, FebruaryHeld in Cali – Colombia, April 8 to 10, 2008

Held in Cali Colombia, February 25 to 27, 2010

CENMEVENTS HELD BY CENM

Held in Bogotá – Colombia, g ,

Event will be held inBarranquilla – Colombia onOctober 21 – 23, 2010

Held in Bogotá – Colombia, on April 22 and 23, 2009

CENMRobust Equipment acquired by CENMby CENM

Physical Property Measurement System – PPMS Quantum Design™


Mastersizer Laser Granulometer

Attrition Mill


Universal Hystron Press


Atomic Force Microscopy- AFM ASYLUM RESEARCH


MICRO-RAMAN Jobin Yvon, Model Labram HR


Desktop Scanning Electron Microscope – PHENOM - FEI p g p


SPECTROPHOTOMETER Jasco Modelo V 7200SPECTROPHOTOMETER Jasco. Modelo V 7200


DILATOMETER

Cooperation Agreements

2006 20092006 - 2009 2006 - 2008

Centro de Investigaciones en Instituto Superior Politécnico

2006 - 2008 2007 - 2010

gTecnología Aeronáutica

José Antonio Echeverría

2007 2007 - 2010

Arrocera la Esmeralda

Cooperation Agreements

2009 - 2010

2006 - 2008

2008

2006 2008

CAJAS DE CARTON CORRUGADO

CARTONES AMERICA S.A.2008 - 2010

Universidad deSan Buenaventura2007 -2010

Universidad del

2006 - 2008

Universidad delTolima

Centro Nacional de AsistenciaTécnica a la Industria

2007

CENMProject carried out with Resortes HérculesResortes Hércules

Determination of optimal parameters of the tempering process of SAE6150 steel as an alternative for the manufacture of leaf springs.

Ch t t

Leaf spring quality was clearly improved withSAE 6150 steel in calibers greater than 20 mm.

Charpy test

606570

)

Jominy test

Hardness

Ferrite

PerlitaPerlite

Ferrite

2530354045505560

Du

reza

(HR

C)

Distancia (mm)

A process was begun between the university and the enterprise to support research projects

CENMProject carried out among CDT ASTIN – CENM – AGRAF S.A.

Immediate application of B4C/BCN/c-BN multilayers

“Improvement of the design of cutting blades atAGRAF S.A via the application of

B4C/BCN/c-BN, TiN/ZrN, and TiN/TiAlNbN multilayers”/ / , / , / y

General Objective: to increase the useful life of cutting blades by at least 35% at the paper conversion plant in AGRAF S.A., i i fi i id d i li b 70% b i increasing profits in said production line by 70% by using

TiN/TiAlNbN, TiN/ZrN, and B4C/BCN/c-BN multilayered hard coatings

Projected savings in production costs at the AGRAF S.A. paper conversion plant for the first year: $96,286,000Projected savings for the first year for Cartón Colombia:90 hours of additional cutting153 tons of additional paper$382,500,000

Exchange Bias in [La1/3Ca2/3MnO3/La2/3Ca1/3MnO3 ] superlattices

600300

200

400-300

0

m3 )

0

200-8 -4 0 4 8

HC1 HC2Hexem

u/cm

-400

-200C1 C2ex

M (e

-3 -2 -1 0 1 2 3-600

-400

P. Prieto et al.; J. Appl. Phys. 99 08C106 (2006)

3 2 1 0 1 2 3H (kOe)

VO2 at nano‐scale200 nm

VO2 Pattern fabricated using200 nm usingE-beam and Photo lithography T h iTechniques.

200 nm gap

1m 2 m

4 m

5310m

Sharoni, Ramirez, Schuller. PRL 101 (2008)

MOCVD growth of TiO2 nanotubes and nanomembranes

Co

C b lt

Si (100)Co

Ti(OC3H7)4

= Cobalt clusters (101)

(010)Fe(C5H5)2

TiO2

TiO2membranes

( )

(100) Si substrate

2tube

es

HRTEM0,15

0,18

0,21

ax (m

m) WC

n = 1 n = 50 n = 200 120

140

160

n = 200= 15 nm

WC/[TiCN/TiNbCN]nTurning Test144%

133%122%

100%e (%

)

0 500 1000 1500 20000,00

0,03

0,06

0,09

0,12

Flan

k W

ear V

B m

a

-50 0 50 100 150 2000

20

40

60

80

100 n = 50= 60 nm

n = 1

Unc

oted

(WC

)

Perf

orm

ance

Cutting Length (m) Bilayer Number

TiCN/TiNbCN Multilayer System with Enhanced T ib l i l P ti

J. C. Caicedo, C. Amaya, M. E. Gómez

Tribological Properties

Thin Film Group, Department of Physics, Universidad del Valle, Cali, Colombia

L. Yate, A. Lousa, J. Esteve ÓDepartment de Física Aplicada i Óptica, Universitat de Barcelona, Catalunya, Spain

P. PrietoExcellence Center for Novel Materials – CENM - Cali, Colombia

Universidaddel Valle


Outline

Motivation l l Experimental Details Film Characterization: Film Characterization:XRD, TEM, nanoindentation, pin-on-disc wear testdisc, wear test Analysis of Tribological propertiesy g p p Conclusions

Our motivation for producing TiCN/TiNbCN multilayers is Motivation

Our motivation for producing TiCN/TiNbCN multilayers is aimed at producing tough (less brittle) wear-protective films with low-friction coefficients, increased hardness, as well as a corrosion protective coatings in machining tools (WC and 4140 corrosion protective coatings in machining tools (WC and 4140 Steel) Our goal is to improve the mechanical properties for possible industrial applications in high-performance and aggressive environments WC

Substrate

W

CC

Nb

TiN

TiCN/TiNbCNMultilayered

WTiN

WC Insert

MotivationPrevious results of multilayer coatings

33 253 )

Previous results of multilayer coatings

24

27

30

220

231

242

253

s (G

Pa)

ulus

(GPa[TiN/ZrN]n

18

21

24

176

187

198

209

Har

dnes

Hardness (H) astic

Mod

u

0 1 2 3 4 5 6 7 8 9

15 176

Bilayers Number

Elastic Modulus (Er)

Ela

[TiCN/TiNbCN]n multilayers ,(n = 1 to 200)

3.0 μm

• Total thickness around 3 µmi t t b t ltil

• We analyzed the effect of number of bilayers on hardness, wear resistance, adhesionto substrate, and other tribological properties

remains constant, but multilayerperiod Λ changes

Corrosion properties in TiCN and TiNbCN single layers

7500

10000 TiNbCN-0V TiNbCN-20V TiNbCN-50V TiNbCN-100V

120

py) Ti-C-N

Ti-Nb-C-N

5000

7500

ag (o

hms)

Acero 4140

60

80

100

ion

rate

(m

0

2500-Zim

20

40

Cor

rosi

Enhancement of corrosion resistance in TiNbCN layers

0 2500 5000 7500 10000Zreal (ohms) 0 20 40 60 80 100

0

r.f. Negative bias voltage(V)

Magnetron SputteringExperimental Details

48Laboratorio de Recubrimientos duros física - Universidad del Valle


Substrates on

Magnetron Sputtering System

Four Magnetrons

(Bias Voltage)Substrates onrotation system

Four Magnetrons(Ø 4 Inch)

Heater (700 °C)Four-ChannelFluxometersFluxometers

2 r.f. power2 d c power

CDT ASTIN SENA and CENM Colombia

2 d.c. power

Magnetron SputteringOurs Industrials Result

[Al O /YSZ][TiN/ZrN]n [Ti/TiN]n

[Al2O3/YSZ]n

46CDT ASTIN SENA

[TiN/ZrN]n [TiN/TiAlN]n [CrN/ZrN]n

Ours Industrials Result Magnetron Sputtering

[Ti/TiN] [C /C N][Ti/TiN]n

[Ti/TiN]n [Cr/CrN]n[Ti/TiN]n

47CDT ASTIN SENA

[TiN/TiAlN]n [Zr/ZrN]n[B4C/BCN/c-BN]n

Magnetron Sputtering System Setup

TiCNTiC Target

Gas mixture (Ar/N2)

TiNbCNNb Target

Gas mixture (Ar/N2)

Deposition Parameters for [TiCN/TiNbCN] Multilayers[TiCN/TiNbCN]n Multilayers

Targets Titanium Carbide and Niobium

Deposition system Magnetron sputtering r.f. Reactive

Power density (W/cm2) 80 TiC and 70 NbPower density (W/cm ) 80 –TiC and 70-Nb

Bias r.f. voltage (-V) 50

Target to substrate distance (cm) 7Target to substrate distance (cm) 7

Gas mixture (Ar/N2) 76/24 (%)

D iti (A +N ) ( b ) 6x10-3Deposition pressure (Ar+N2) (mbar) 6x10

Substrate Si (100), AISI 4140 steel and WC insertsWC inserts

Substrate temperature (°C) 300

Structural and mechanical characterization

WC/TiCN/TiNbCN

Low-angle diffraction patterns of TiCN/TiNbCN multilayers deposited on silicon substratesmultilayers deposited on silicon substrates

1011

108

109

1010

10

)sin(sin2)(

nm

nm

b. u

nit.)

n = 1n = 30n = 50n = 70n = 150n = 200

No of bilayers

Bilayer Period (nm) calculated

from the deposition rate

Bilayer Period (nm) extracted from LA-XRD measurements

104

105

106

107

ctiv

ity (a

rb n = 200

E = 60 nmE = 100 nmE = 1.5 m

deposition rate

1 1500 -

30 100 96.6

50 60 59.9

0 1 0 1 2 0 2 3 0 3 4 0 4 0101

102

103

10

m

Ref

lec

E = 15 nm

E = 20 nm

E = 43 nm

XRR n

70 43 41.1

150 20 19.7

200 15 14.6

0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5 5,0

2()

Interference peaks due to the multilayer formationInterference peaks due to the multilayer formationGood agreement between nominal modulation and bilayer period obtained from LA XRD

High angle Diffraction patterns of TiCN/TiNbCN films deposited on silicon substrate

N 1

11

N 2

00

N 2

20

N 3

11

N 2

22

CN

111

CN

200

CN

220

CN

311

CN

222

[TiCN/TiNbCN]n

Satellite peaks

unit)

n = 1 n = 30 n = 50 n = 70

TiC

N

TiC

N

TiC

N

TiC

N

TiC

N

TiN

b

TiN

b

TiN

b

TiN

b

TiN

b

unit.

)

ity (a

rb. u n = 150

n = 200 = 20 nm

= 15 nm

n =150

n = 200

sity

(arb

.

= 43 nm n = 70

Not Satellite peaks

Inte

ns = 60 nm n = 50

Inte

ns

n = 30 = 100 nm

= 1.5 m n = 1

33 34 35 36 37 38

2 (degree)

30 40 50 60 70 80

2degree

Satellite peaks as a consequence of the formation of sharp interfaces shifted from the diffraction peaks to high-angle probably due to the presence of compressive stress

Cross-section TEM Analysis TEM n = 30 Λ = 100 nm TEM n = 200 Λ = 15 nm TEM n = 30, Λ = 100 nm TEM n = 200, Λ = 15 nm

TiNbCN

TiCNTiCN

Cross-section TEM image of a TiCN/TiNbCN multilayer with 200 bilayers(Λ = 15 nm) (a) and multilayer with 30 bilayers (Λ = 100 nm). Clear interfaces areobserved in all multilayers

HR TEM

5 nm

STEM (EELS) [TiCN/TiNbCN]n100 nm100 nm

n = 30, Λ = 100 nm

100

70

80

90

100

ition

(%) C Content (%)

Ti Content (%) N Content (%) Nb Content (%)

40

50

60

70

com

pos

10

20

30

Rel

ativ

e

0 100 200 300 4000

Scan lenght (nm)

SIMS [TiCN/TiNbCN]30

8,0x10756Fe+

[TiCN/TiNbCN]3048Ti+

6,0x107

Fe

93Nb+

(c/s

)

4,0x107

12 +ensi

ty (

2,0x107 14N+

12C+

Inte

0 30 60 90 120 150 180 2100,0

0 30 60 90 120 150 180 210

Sputter time (min)

Mechanical PropertiesHardness and Elastic Modulus of [TiCN/TiNbCN] multilayersHardness and Elastic Modulus of [TiCN/TiNbCN]n multilayers

10

n = 1(a)

Better mechanical performance

6

8

(mN

)

n = 1 n = 30 n = 50 n = 70 n = 150n = 200

2

4

Load

( n = 200

0 30 60 90 120 150 1800

2

Displacement (nm)

Values of elasticity modulus E and hardness H

Atomic Force Microscopy (AFM) Asylum Research MFP-3D®

Values of elasticity modulus E and hardness H were obtained by using Oliver and Pharr’s method

Mechanical PropertiesHardness and Elastic Modulus of [TiCN/TiNbCN]n multilayers

420

Pa) (b) = 15 nm44 (a)

380

400

ulus

(GP ( )

= 20 nm

384042

= 20 nm

= 15 nm

GPa

)

(a)

340

360

tic M

odu

= 43 nm

= 60 nm30323436

= 43 nm

= 60 nm

rdne

ss (G

0 40 80 120 160 200

320Elas = 100 nm

= 1.5 m

0 40 80 120 160 200

262830

Har

= 1.5 m

= 100 nm

0 40 80 120 160 200Bilayer Number Bilayer number

Hardness increased from 26 GPa to 42 GPa and Elastic modulus from 318 GPa to 410GPa. Probably due to the nanometric thickness of individual layers in the multilayeredstructure.

Analysis of Friction Results0,50 0,40

ent

n = 1 0,30TI C N

Tribometer Microtest,

0 300,350,400,45

0 200 400 600 800 10000,000,050,100,150,200,250,300,35

Fri

ctio

n co

effic

ie

TiCN TiNbCN

n = 70 n = 150

200

n = 1 n = 30 n = 50

ffici

ent

0 21

0,24

0,27

effic

ient

TI-C-N

Ti-NbC-N = 1.5 m

MT 4001

0,150,200,250,30 0 200 400 600 800 1000

Sliding distance (m) n = 200

ctio

n co

ef

0,15

0,18

0,21

ctio

n co

e

= 100 nm

= 60 nm

= 43 nm

0 200 400 600 800 10000,000,050,10

[TiCN/TiNbCN]nFric

(a)0 40 80 120 160 200

0,09

0,12

Fric

(b)

= 20 nm

= 15 nm

Sliding distance (m) Bilayers numbern = 1 Λ = 1.5 mn = 1 Λ = 1.5 m n = 200 Λ = 15 nmn = 50 Λ = 60 nm

Optical Interferometry of coating wear resistance, after 2 h pin-on-disk sliding

Analysis of Adhesion Results0 75

0 75

0,45

0,60

0,75

ffici

ent Lc2 = Adhesive failure

(c)Lc2

0 4

0,60

0,75

Lc2

Lc2 = Adhesive failure

effic

ient

LC1 = Cohesive Failure

0,15

0,30

,

rictio

n co

e

(b)n = 200 = 15 nm

0,30

0,45

ctio

n co

e

Lc1

LC1 Cohesive Failure

0 10 20 30 40 50 60 70 80 900,00

Fr

Load (N)

Lc1(a)

0 15 30 45 60 75 900,00

0,15

Load (N)

n = 1 = 1.5 mFr

i

Load (N)

Scratch Test Microtest MTR2

Load (N)

Analysis of Adhesion Results85

L Adhesi e fail re

70

75

80

oad

(N)

Lc2 = Adhesive failure = 15 nm

= 20 nm(e)

(f)

55

60

65 C

ritic

al l

= 43 nm

= 60 nm(a)(b) (c)

(d)

0 40 80 120 160 20045

50

B ilayers num ber

60

= 100 nm = 1.5 m

(a)

B ilayers num ber

Conclusions

Micro & nanometric TiCN/TiNbCN multilayered coatingssuccessfully deposited by r.f. magnetron sputtering with bilayerperiods ranging from 1.5 μm to 15 nm.

Highest hardness & elastic modulus, 42 & 408 GPa, respectively,Highest hardness & elastic modulus, 42 & 408 GPa, respectively,observed for TiCN/TiNbCN deposited with number of bilayersat 200 and modulation at 15 nm.

Low friction coefficients observed in multilayered coatingsmaybe due to carbon content and to the interface effect.Furthermore, high hardness combined with carbon contentlubricant presence make the TiCN/TiNbCN multilayered systema good candidate for use as a hard and low friction coating ina good candidate for use as a hard and low friction coating incutting tools.

CENMContribution to Local & National Development, Scientific and Technological CapacityCapacity Work done with 19 highly qualified research groups

throughout the nation has strengthened student and throughout the nation has strengthened student and researcher participation in the international scientific community.

CENM has placed scientific & technological knowledge at the highest international levels.

The Center has done research in key areas for the The Center has done research in key areas for the nation’s academic, scientific, and economic benefit.

CENM research will lead to developing environmentally friendly manufacturing practices and devicesfriendly manufacturing practices and devices.

Our research represents important potentials in electronics, biomedicine, metallurgy and construction, among others.

Th k f ki d tt tiThank you for your kind attention


director pedro prieto. prieto.pdf · 2009 aps april meeting cenm fip physics in latin america...

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