PROGRAMME AND ABSTRACT BOOK

INSTITUTO NACIONAL DE TÉCNICA AEROESPACIAL, INTA

NATIONAL INSTITUTE FOR AEROSPACE TECHNOLOGY

Torrejón de Ardoz (Madrid, Spain)

October 20-21, 2014

2

ORGANISATION

Chairmen Institution

Sánchez-López JC ICMS-CSIC, Sevilla, Spain

Pérez-Trujillo, FJ UCM, Madrid, Spain

Scientific committee

J.M. Albella, ICMM-CSIC, Madrid, Spain

A.R. Glez-Elipe ICMS-CSIC, Sevilla, Spain

A. Conde CENIM-CSIC, Madrid,Spain

J.A. Puértolas UZA, Zaragoza, Spain

G. G. Fuentes AIN, Pamplona, Spain

J. Barriga Tekniker, Eibar, Spain

I. Jiménez ICMM-CSIC, Madrid, Spain

J.R. Ramos UMA, Málaga, Spain

A. Agüero INTA, Madrid, Spain

M. Brizuela Tecnalia, Donosti, Spain

M. Vilasi University of Lorraine, France

A.Cavaleiro University of Coimbra, Portugal

J. Esteve UB, Barcelona, Spain

J. San Román ICTP-CSIC, Madrid, Spain

J. Esteban Fundacion Jiménez Díaz, Madrid, Spain

J.L. Endrino Crandfield University, UK

Local Committee

M. Gutiérrez del Olmo INTA, Madrid, Spain

S. Mato UCM, Madrid, Spain

G. Alcalá UCM, Madrid, Spain

J. Ortiz ICMM-CSIC, Madrid, Spain

J.L. de Segovia ICMM-CSIC/ASEVA, Madrid, Spain

I. Hernández ASEVA, Madrid, Spain

Contact

J. C Sánchez-López jcslopez@icmse.csic.es

F. J. Pérez Trujillo fjperez@ucm.es

J. L. de Segovia jldesegovia@icmm.csic.es

I. Hernández aseva@icmm.csic.es

3

SPONSORED BY

Contents

Foreword 5

General information 6

Programme 9

Abstracts Monday Morning 13

Afternoon 35

Porster 47

Tuesday Morning 77

Author index 99

Participant list 101

4

5

Foreword

This book contains the Proceedings of the XtremeCOAT2014 workshop

devoted to “Surface engineering for functional applications under extreme

conditions”. The symposium is to be held on 20-21st October in Madrid (Spain),

organized by the Consolider FUNCOAT project (a joint Consortium of 17 relevant

Spanish Centres working on functional films).

The aim of the workshop is to present and discuss the current scientific and

technological advances in the field of surface engineering for applications involving

extreme or singular conditions, such as high temperature, corrosion environments,

biological fluids, severe loads and fatigue, strong erosion or abrasion, etc. Three main

sessions have been selected:

Session A: Surface engineering for energy applications

Session B: Surface engineering for mechanical applications

Session C: Surface engineering for biomedical applications

A total of 39 contributions from 6 different European countries have been

accepted among them: 3 invited lectures, 22 oral presentations and 14 poster

presentations.

We deeply thank the Spanish Ministry of Economy and Competitiveness

(MINECO) for the financial support provided within the framework of the

CONSOLIDER programme. The Institute of National Aerospace Techniques

(INTA), hosting the Workshop, as well as the Spanish Vacuum Society (ASEVA) are

also gratefully acknowledged for their valuable support to the organization of this

symposium.

Finally, we welcome and thank all the attendees for their participation and

contribution to the success of this meeting where results of very high quality and

excellent talks are expected. It is a great opportunity to establish new partnership

agreements, improve collaborative networks and open up promising perspectives for

the scientists of the protective coatings and surface engineering community.

Juan C. Sánchez-López and Francisco J. Pérez-Trujillo

Programme Chairmen

6

General Information

VENUE XtremeCOAT workshop will take place at the facilities of the Centre of Astrobiology, CAB (CSIC-INTA), located in the northern part of INTA campus (see enclosed map). INTA (National Institute of Aerospace Technology) is the National Research Organization specialized in aerospace research and technology development.

ACCESS INTA is an agency of the Ministry of Defence. The security and access control is essential and therefore visitors should stop at

the security control point to register. For the participants using the shuttle bus service, a pre-registration will be done. Those

participants that intend to take this bus must inform the organizers by sending an e-mail (xtremecoat.info@icmse.csic.es)

including full name, institution and national ID card or passport number.

Those going by their own car should stop at the security control point and register before entrance.

7

HOW TO GO TO INTA

INTA is northeast at about 25 km far from Madrid.

By car: “Take National highway A2 to Zaragoza. Leave at exit 18 and take direction AJALVIR by M-108. At km 4 there is a

traffic circle, first exit to right is INTA”.

By Shuttle bus (Included in the fees). You can take the shuttle bus offered by the organization that will depart from HOTEL

TRYP MADRID CHAMARTIN at 07:30 and drive you directly to workshop venue. At the end of the journey the bus will return to

the same HOTEL TRYP MADRID CHAMARTIN.

ACCOMODATION

The proposed hotel for the workshop participants is the Hotel TRYP Madrid Chamartín

http://www.tryphotels.com/es/tripadvisor-tryp-madrid-chamartin-hotel.html

The TRYP Madrid Chamartín hotel, totally renovated in 2012, is located in the residential area of Plaza de Castilla and at a

walking distance from the train Chamartin Station.

REGISTRATION

Registration desk will be opened on Sunday 19 at the hotel reception from 18:30 to 19:30 and on Monday from 08:30 to 9:00 at

the venue, conference room. A file with hard copy of the final programme will be given to all participants. If you are not

registered you can do it at the registration desk. Workshop fees are:

Members of the FUNCOAT: 175€

Non-FUNCOAT participant: 200€

Student (with accreditation) 125€

LUNCHES AND COFFEE BREAKS

Buffet Lunches and coffee breaks included in the fees will be served just off the conference room.

8

INTERNET

Free wireless internet access available at the conference room

INSURANCE

FUNCOAT as organizer of the workshop will not be responsible for any personal accidents or loss of as well as damage to

private property of participants and accompanying persons which may occur during the XtremeCOAT workshop. Therefore,

participants should contact their own insurance if they consider necessary.

PROGRAMME AND PRESENTATIONS

CONFERENCE LANGUAGE

The official conference language is English. All oral and poster presentations are required in English. No simultaneous

translation will be provided.

PRESENTATION

Scientific presentations will be given either as lectures or as poster. The lectures are divided in

1. Invited Lectures, duration: 45 min. per lecture

2. Oral Presentation, duration: 20 min. per presentation

The lecture duration includes 5 min. for discussion. We kindly ask you to bring along a memory stick containing your

presentation to the conference. It is also possible to use the own notebook. If you consider presenting a movie, we

recommend using your own notebook.

Presenting authors are asked to come to the respective lecture room before the session, to ensure that there is enough time

to copy the presentation or for installing the notebook. Please, check with the room attendant, whether everything is working

properly.

The Poster Presentations are given in a single session. The maximum poster size is 110 cm width and 120 cm height, i.e.

portrait format. The authors are requested to mount their poster in the morning of the day of the poster session, and to

remove it at the end of the same day.

9

Programme Monday, 20 M

onday

20

Sess

ion 1

: En

ergy

09:00-

09:15

Official Opening and Welcome Address

Prof. J.M. Albella FUNCOAT Project Coordinator Dr. A. Moratilla Resarch and Porogramme Division, INTA

ENERGY

PART I

Session 1A Chairmen: F.J. Pérez-Trujillo Complutense University

G. García-Fuentes AIN_TECH

09:15-

10:00

Invited

lecture-1

Sol gel anti-reflective coatings and thin film solar collectors for CSP applications in desert environments

Christopher Sansom, Crandfield University, UK

10:00-

11:00

10:00-

10:20

Novel Mo-Si3N4 based selective coating for high temperature concentrating solar power applications

E. Céspedes, J.A. Sánchez-García, L. Álvarez-Fraga, D. Hernández-Pinilla, R. Escobar-Galindo, O. Sánchez, J.M. Albella and C. Prieto, ICMM-CSIC, Cantoblanco, Madrid, Spain

10:20-

10:40

Cold Plasmas Used for the Fabrication of Different Components Relevant for Energy Conversion

M. Brizuela, A. Garcia-Luis, D. Gonzalez-Santamaria, F. Fernández-Carretero, P. Corengia, Tecnalia, San Sebastián (Spain)

10:40-

11:00

Sputtered apatite-type lanthanum silicate thin films for SOFCs electrolytes

F. Ferreira, J.C. Oliveira, A. Cavaleiro, University of Coimbra, Portugal

11:00-

11:30 Coffee Break

ENERGY

PART II

Session 1B Charmen: M. Brizuela TECNALIA, San Sebastian

G. Alcalá Complutense University

11:30-

13:30

11:30-

11:50

Influence of the microstructure in the high temperature corrosion resistance of CrAl(Y)N coatings deposited by PVD

S. Mato, J.C. Sánchez-López, G. Alcalá, M. Brizuela, R. Escobar Galindo and F.J. Pérez, Universidad Complutense de Madrid, Spain

11:50-

12:10

Coatings for Oxycombustion- Supercritical Steam Boilers Components

A. Agüero, I. Baraibar, V. González, M. Gutiérrez, R. Muelas and D. Plana, Instituto Nacional de Técnica Aeroespacial-INTA, Spain

12:10-

12:30

Flame spraying of Si bond coats over SiC substrates for environmental barrier coating architectures

A. Nistal, E. García, M. I. Osendi, P. Miranzo, Institute of Ceramics and Glass (ICV-CSIC), 28049, Madrid, Spain

12:30-

12:50

Comparative oxidation behaviour in water vapour between out-of-pack aluminides and slurry based aluminium-based TBCs on

Ni-based superalloys

F. Pedraza , M. Brossard, B. Bouchaud, J. Balmain and G. Bonnet, Université de La Rochelle, France.

12:50-

13:10

Surface Modification of Materials exposed to Fusion Plasma and Impact on Reactor Operation

F. L. Tabarés, A. de Castro, D. Alegre, A.B. Martin-Rojo, E. Oyarzabal and D. Tafalla, Association EURATOM-CIEMAT, Madrid, Spain

13:10-

13:30

Surface Nitriding and Ammonia formation in N2/H2 plasmas on ITER-relevant Plasma Facing Materials

A. de Castro, D. Alegre and F.L. Tabarés, Association EURATOM-CIEMAT, Madrid, Spain

13:30-

15:00 Lunch Buffet

Sess

ion 2

: B

iom

edic

al

BIOMEDICAL Session 2 Chairmen: J. C. Sánchez-lópez ICMS-CSIC

A. Conde CENIM-CSIC

15:00-

16:00

15:00

15:20

Plasma Immersion Ion Implantation for MoM prosthesis application

C. Díaz, S. Mändl, R. Pereiro, Asociación de la Industria Navarra (AIN), Ingeniería de Superficies, Pamplona, Spain

15:20

15:40

An in vitro approach for “the race for the surface” theory. First results with clinical strains of Staphylococcus aureus and

Staphylococcus epidermidis on Ti6Al4V

J. Esteban, M. Martínez-Pérez, C. Pérez-Jorge, D. Lozano, J. M. Hernandez-Lopez, S. Portal-Núñez, M. A. Arenas et al., ISS-Fundación Jiménez Díaz

Hospital, Madrid, Spain

15:40

16:00

Ti1-xAgx and TiN-Ag electrodes deposited on polymer based sensors for biomedical applications

S. M. Marques, N. K. Manninen, S. Lanceros-Mendez, A. Cavaleiro, S. Carvalho, University of Minho, Guimarães, Portugal

16:00-

16:45

Invited

lecture-2

The role of Ag on ZrCN coatings performance in harsh biological environments

Sandra Carvalho, Universities of Minho and Coimbra, Portugal

16:45-

17:05

16:45

17:05

Tribological characterization of DLC coated CoCrMo medical grade for application in Metal-on-Metal joint prostheses

J. Esteve, D. Cano, G.G. Fuentes, C. Díaz, L. Martínez de Olcoz and A. Lousa, Department of Applied Physics and Optics, University of Barcelona,

Barcelona (Spain)

Poster

Session

17:05-

18:00 Posters Poster Session and coffee break

10

Poster Session / Monday 20th

Monday 20th

17:05-18:00

POSTER SESSION

P1 High temperature oxidation in steam atmosphere of nanostructured transition metal nitrides coatings on steel

A. Illana, M. A. Sánchez-Mancilla, M. Brizuela, J.C. Sánchez-López, F.J. Pérez and S. Mato, Universidad Complutense de Madrid, Spain

P2 Heat Treatment Diffusion Coating in SANICRO25

M. Gutiérrez, V. González and A. Agüero, National Institute of Aerospace Technology–INTA, Madrid, Spain

P3 Potential protection of YSZ thermal barrier coatings against CMAS infiltration by a sacrificial slurry based coating

V. Kuchenreuther, M. Juez-Lorenzo, V. Kolarik, H. Fietzek, Fraunhofer-Institute Chemical Technology ICT, Pfinztal, Germany

P4 Increase of steam oxidation resistance at 650ºC and 800ºC of AlSi-CVD-FBR coating on P92 steel

S.I. Castañeda and F.J. Pérez, Universidad Complutense de Madrid, Spain

P5 Anticorrosion hybrid AlPO4/Al2O3 coatings on the surface of P92 steel for oxy-fuel power plant application

L. Davydenko, M. Nazarchuk, D. Nasiedkin, Yu. Plyuto, M. Mosquera-Feijoo, M. Nofz, et al., Chuiko Institute of Surface Chemistry, Ukraine

P6 Exploring the aluminium slurry coatings limits for new aeronautic requirements

J. Mora and A. Agüero, National Institute of Aerospace Technology–INTA, Madrid, Spain

P7 Steam oxidation test for new generation steam power plants

T. El Baraka, I. Baráibar and A. Agüero, National Institute of Aerospace Technology–INTA, Madrid, Spain

P8 Ni aluminide coating on P92 for oxidation and corrosion protection

I. Baráibar, J. A. Domínguez and A. Agüero, National Institute of Aerospace Technology–INTA, Madrid, Spain

P9 Cathodic arc evaporation and characterization of CrAlON thin films

E. Almandoz, J.F. Palacio, S. Kulkarni, R.J. Rodríguez and G. G. Fuentes, Asociación de la Industria Navarra, Spain.

P10 Ag-containing diamond-like carbon coatings: on their microstructure and tribo-mechanical properties

S. Domínguez-Meister, T. C. Rojas and J. C. Sánchez-López, Instituto de Ciencia de Materiales de Sevilla (CSIC-Univ. Sevilla), Spain

P11 Tribocorrosion behavior of TiBxCy/a-C nanocomposite coating in strong oxidant disinfectant solutions

E. Gracia-Escosa, I. García, J.C. Sánchez-López, M. D. Abad, A. Mariscal, M. A. Arenas, J. de Damborenea, A. Conde, CENIM-CSIC, Madrid, Spain

P12 Development of decorative coatings resistant to high temperatures

E. Carretero and R. Alonso, Department of Applied Physics, University of Zaragoza, Spain

P13 On the deposition rate of magnetron sputtered thin films at oblique angles

R. Alvarez, J.M. Garcia-Martin, M.C. Lopez-Santos, V.Rico, F.J. Ferrer, J. Cotrino, A.R. Gonzalez-Elipe, A. Palmero, Instituto de Ciencia de Materiales de Sevilla, Spain

P14 Anisotropic in-plane conductivity in plasma assisted ITO thin films prepared by e-beam evaporation at oblique angles

J. Parra-Barranco, A. Borras, F. Garcia, M.C. Lopez-Santos, A.R. Gonzalez-Elipe, A. Barranco, Instituto de Ciencia de Materiales de Sevilla, Spain

11

Programme Tuesday, 21

Tues

day

21

Sess

ion 3

: M

ech

anic

al

MECHANICAL

PART I Session 3A Chairmen: J. M. Albella ICMM-CSIC

A. Agüero INTA

9:15-

10:00

I

Invited

Lecture-3

High performance cold gas spray (CGS) coatings for Xtreme wear damage resistance

Josep M. Guilemany, Thermal Spray Centre (CPT). University of Barcelona. Spain

10:00-

11:00

1

10:00-

10:20

Nano-multilayered and nano-composite hard PVD coatings for tool/dies at medium/high temperatures

G. G. Fuentes, E. Almandoz, Diego Otazu, Sonia Mato, F. Javier Pérez-Trujillo, Asociación de la Industria Navarra, Spain.

1

10:20-

10:40

On the nanostructure and oxidation protection of CrAlN and CrAlYN coatings

T. C. Rojas, S. Domínguez-Meister, M. Brizuela, J. C. Sánchez-López, Instituto de Ciencia de Materiales de Sevilla (CSIC-Univ. Sevilla), Spain

1

10:40-

11:00

High temperature oxidation behavior of MCrAlY laser cladding coatings

J. C. Pereira, J. C. Zambrano, M. J. Tobar, A. Yañez, V. Amigó, Instituto de Tecnología de Materiales, Universidad Politécnica de Valencia, España.

11:00-

11:30 Coffee Break

MECHANICAL

PART II Session 3B Chairmen: A. R. González-Elipe ICMS-CSIC

S. Mato Complutense University

11:30-

13:30

1

11:30-

11:50

Laser furnace surface processing of ceramics and glass

I. de Francisco, V. Rico, V. V. Lennikov, L. C. Estepa, L. A. Angurel, A. R. González-Elipe and G. F. de la Fuente, ICMA (CSIC-Univ. Zaragoza), Spain

1

11:50-

12:10

Influence of peak power on the properties of Ti-Si-N films deposited by HiPIMS in deep oscillations magnetron sputtering

(DOMS) mode

F. Fernandes, J.C. Oliveira, F. Ferreira, A. Cavaleiro, University of Coimbra, Portugal

1

12:10-

12:30

Thermal shield coatings for C/SiC materials

E. García, A. Nistal, M.A. Sainz, M.I. Osendi, P. Miranzo, F. Martín de la Escalera, Y. Essa, A. Khalifa, Institute for Ceramics and Glass (ICV-CSIC),

Madrid, Spain

1

12:30-

12:50

Raman spectroscopy of ZrCN/ZrN multilayer coatings

F. Agulló-Rueda and J. Barriga, Instituto de Ciencia de Materiales de Madrid, ICMM-CSIC, Madrid, Spain

1

12:50-

13:10

Active Screen Plasma Nitriding to improve tribology performance of Austenitic Stainless Steels with good corrosion

resistance

J. A. Sánchez-Garcia, M. Brizuela, P. Corengia, A. Larrañaga, I. Braceras, Tecnalia, San Sebastián (Spain)

1

13:10-

13:30

Enhancement of corrosion behaviour in pressure vessels weldments through silica nanoparticles addition

E. Carneiro and S. Carvalho,University of Minho, Portugal/ Equipamento Hospitalar e Serviços Associados, Maia, Portugal

13:30-

15:00 Lunch Buffet

12

13

ABSTRACTS

Monday 20 Morning

Session 1. Energy

Oral Presentations

14

NOTES

15

Sol gel anti‐reflective coatings and thin film solar collectors for CSP

applications in desert environments

C.Sansom1 and X.Tonnellier1

1 Global CSP Laboratory, Precision Engineering Institute, Manufacturing Department, Cranfield University MK43

0AL, United Kingdom

E-mail: c.l.sansom@cranfield.ac.uk

Abstract

Concentrating Solar Power (CSP) systems use large concentrators (of glass or coated polymer film) to

focus direct sunlight onto evacuated receiver tubes. Within this glass tube is a hollow steel absorber tube that

carries a heat transfer fluid at temperatures up to 550°C. The thermal energy absorbed can be used to raise

steam and drive a turbine for electrical power generation. To maximise the efficiency of solar power plants it is

normal practice to deposit anti-reflection (AR) coatings on both the outer and inner surfaces of the receiver tubes

and to deposit special high absorptance/low emittance coatings on the metal absorber tube. In this work we

describe the design of a novel machine to deposit all of these coatings using sol gel materials. The durability of the

outer AR coating on the receiver tube, and that of the concentrating reflector itself, is of considerable interest.

Since CSP plants are most often in desert regions, these surfaces experience extreme daily swings in temperature

and also are highly vulnerable to the impact from airborne particles during sand and dust storms. This work

analyses the impact of sand and dust particles from real desert locations (see Figure 1), using actual climate data,

on collector surfaces and proposes methods to minimise the effects of these in CSP plants.

References [1] S.Lui et al, Computer Animation and Virtual Worlds, 18, 259-269 (2007)

[2] J. Lee et al, Geomorphology, 105, 18-27 (2009)

[3] J.Travis, Atmospheric-Surface exchange of particulate and gaseous pollutants, 907-9, Proceedings of Symposium held at Richland,

Washington, USA (1974)

16

NOTES

17

Novel Mo-Si3N4 based selective coating for high temperature concentrating solar power applications

E. Céspedes, J.A. Sánchez-García, L. Álvarez-Fraga, D. Hernández-Pinilla, R. Escobar-Galindo, O. Sánchez,

J.M. Albella and C. Prieto

Instituto de Ciencia de Materiales de Madrid, CSIC, Cantoblanco, 28049 – Madrid, Spain

E-mail: cprieto@icmm.csic.es

Abstract

A novel selective coating material based on Mo-Si3N4 has been investigated for the first time. The design of

solar selective coatings for concentrated solar power (CSP) applications requires a precise knowledge of the

optical and mechanical behaviors of materials forming the coating. We have studied the Mo:Si3N4 cermet as the

component for absorber layers to prepare selective multilayer coatings with excellent properties. Coatings are

formed by (i) an IR-mirror metal, (ii) a double cermet and (iii) an antireflective dielectric layer.

Optical characteristics at the visible range are determined by thickness and composition of the cermet

and antireflective layers and the behavior at the IR-range is mainly determined by the nature of the metal forming

the IR-mirror, where silver is the preferred metal.

An accurate combination of the individual component layers based on optical simulations and precise

control of thickness and composition leads to high solar absorptivity (αSol = 0.926) and low thermal emissivity (ε25ºC =

0.017), resulting in a high solar thermal energy conversion efficiency. The tandem absorber is stable in moderate

vacuum at temperatures above 600 ºC (Fig. 1) showing low emissivity (600ºC = 0.109) evidencing its relevance for

high temperature applications. A full optical and thermal analysis of a parabolic trough concentrator (PTC)

system confirmed the potential of coating to be used for CSP technology [1].

1000 100000

20

40

60

80

100

300003000

Re

fle

ctivity (

%)

Wavelength (nm)

As-prepared

annealed 450C

annealed 600C

annealed 640C

300

Figure 1. Reflectance spectra of an optimized selective coating after annealing at several temperatures.

References

1. E. Céspedes, M. Wirz, J. A. Sánchez-García, L. Álvarez-Fraga, R. Escobar-Galindo and C. Prieto, Novel Mo-Si3N4 based selective

coating for high temperature concentrating solar power applications. Sol. Energy Mater Sol. Cells 122 (2014) 217.

18

NOTES

19

Cold Plasmas Used for the Fabrication of Different Components Relevant for Energy Conversion

M. Brizuela, A. Garcia-Luis, D. Gonzalez-Santamaria, F. Fernández-Carretero, P. Corengia

Tecnalia, San Sebastián (Spain)

E-mail: marta.brizuela@tecnalia.com

Abstract

Electricity-hydrogen conversion and vice versa in an energy-efficient way is of utmost importance for

going beyond simple consumption of fossil fuels.

Different technologies are available as PEM fuel cells, batteries, water electrolysis, etc.

This work will show different examples of cold plasmas used for the production of components relevant for

the aforementioned applications.

In this work, the Ion Gun Inverse Magnetron plasma polymerization technique has been used to produce

protonic conducting membranes. Plasma polymer films from siloxanes and phosphonates have been deposited.

The variation of different process parameters as gas flow, pressure, and plasma power has allowed synthesizing

polymeric films of different nature and properties. The manufactured membranes have been characterized by

optical profilometry (film thickness), Scanning Electron Microscopy (SEM) (morphology), Fourier Transform Infrared

Spectroscopy (FTIR) (chemical structure), Energy Dispersive Xray Spectroscopy (EDS) (chemical analysis),

mechanical properties by nanoindentation and ionic interchange capability. The results have been compared to

a commercial Nafion membrane. Magnetron sputtering to deposit Platinum based catalysers on electrodes for

PEM fuel cells have been investigated. Different process parameters were varied as the kind of power supplies

(DC or MF), pressure, gas flows and deposition time. Microstructure and morphology of the deposits on different

substrates has been analysed by SEM, EDS and AFM. The catalytic activity was quantified by cyclic voltametry

taking as reference the activity of a commercial electrode E-TEK with platinum charge of 0,5 mg/cm2. It was

demonstrated that the charge of platinum on the electrodes could be controlled by the plasma parameters.

Finally, this work presents the optimization of CrN based coatings deposited by unbalanced magnetron

sputtering as protective coatings on AISI 316L stainless steel bipolar plates. This study includes the evaluation of

CrN coatings with Cr interlayer, Cr/CrN multilayers and the influence of the CrN coating thickness and the

previous roughness of the substrate on the corrosion resistance and the electrical resistance of the coated

stainless steel. The corrosion resistance of the samples was tested in a specific corrosion test in a solution of

phosphoric acid at 150 °C, similar to the environment of a bipolar plat in a HT-PEMFC. The interface contact

resistance (ICR) was measured, before and after the corrosion test, by means of a test configuration that simulates

the positioning of the bipolar plate in the HT-PEMFC stack, pressed between two carbon cloths. Finally, a

complete metallographic characterization of the coated samples has been performed. The results are compared

with the uncoated stainless steel and with a conductive polymeric composite commercially available for this

application.

References 1. Garcia-Luis, Alberto; Corengia, Pablo; Gonzalez-Santamaria, Daniel; et al. PLASMA PROCESSES AND POLYMERS Volume: 4 Special

Issue: 1 Pages: S766-S770 Published: APR 2007

20

NOTES

21

Sputtered apatite-type lanthanum silicate thin films for SOFCs electrolytes

F. Ferreira, J.C. Oliveira, A. Cavaleiro

SEG-CEMUC - Department of Mechanical Engineering, University of Coimbra, Portugal

E-mail: fabio.ferreira@dem.uc.pt

Abstract

Solid Oxide Fuel Cells (SOFCs) are receiving ever-increasing attention because they are among the most

efficient fuel cell electricity generators and environmentally friendly. At present, their most common electrolyte is

yttria stabilized zirconia (YSZ) which exhibits high oxide ion conductivity at temperatures in the range 850º-1000ºC

[1]. The commercial implementation of SOFCs has been hindered by these high operating temperatures which

require the use of expensive materials. Current developments concentrate on the development of intermediate

temperature Solid Oxide Fuel Cells (IT-SOFCs) that may operate at lower temperatures (500º-700ºC) without

incurring performance losses [2]. Apatite-type lanthanum silicate materials have been considered potential

candidates to decrease the operating temperature of SOFCs. These materials are pure anionic conductors with a

high oxygen transference number across a wide range of oxygen partial pressures [3]. They also have higher oxide

ion conductivity and lower activation energies at moderate temperatures than YSZ.

Magnetron sputtering is a powerful processing technique for the synthesis of homogeneous thin layers with

improved mechanical and physical properties. Moreover, the low thickness of the electrolyte produced by

sputtering will compensate resistive losses associated with the electrolyte ohmic resistance at lower working

temperatures of IT-SOFCs. In this work a study concerning the synthesis and characterization of apatite-type

lanthanum silicate thin films produce by magnetron sputtering and subsequent annealing in ambient atmosphere

was carried out. Thin films of La-Si and La-Si-O with near stoichiometric Si/(Si + La) atomic ratio were produced by

magnetron sputtering. For all compositions, the apatite-like La9.33Si6O26 phase was formed during annealing in air

at 900 ºC. In some films, a preferential orientation was developed upon annealing depending on the processing

conditions. The ionic conductivity values measured for the coatings with randomly oriented grains are similar to

those published in the literature for sintered bulk sintered apatite-type lanthanum silicate. The ionic conductivity of

the preferentially oriented films was lower as the measurements were performed in a direction perpendicular or

close to perpendicular to the c axis of the preferentially oriented grains. The highest ionic conductivity of the films

deposited without oxygen in the deposition chamber was 2.81x10-3 Scm-1 at 800 ºC for the film with Si/( La + Si)

atomic ratio of 0.36. This film also presented the lowest activation energy (Ea = 0.94 eV).

References

1. Fuel Cell Handbook (Seventh Edition), EG&G Technical Services, Inc., U. S. Department of Energy, November (2004).

2. R. M. Ormerod, Chemical Society Reviews 32 (2003) 17.

3. V. V. Kharton, F.M.B. Marques, A. Atkinson, Solid State Ionics 174 (2004) 135.

22

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23

Influence of the microstructure in the high temperature corrosion resistance of CrAl(Y)N coatings deposited by PVD

S. Mato1, J.C. Sánchez-López2, G. Alcalá1, M. Brizuela3, R. Escobar Galindo4 and F.J. Pérez1

1 Grupo de Investigación de Ingeniería de Superficies y Materiales Nanoestructurados Nº910627,

Universidad Complutense de Madrid, Facultad de Ciencias Químicas, E-28040 Madrid (Spain) 2 Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Científicas, E-28049

Madrid (Spain) 3 TECNALIA, Parque Tecnológico de San Sebastián, Mikeletegi Pasealekua 2, E-20009 Donostia-San

Sebastián - Gipuzkoa (Spain) 4 Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Científicas, E-28049

Madrid (Spain)

E-mail: msmatodi@ucm.es

Abstract

The efficiency of steam power generation plants can be improved by increasing the steam temperature

above 650oC. However, ferritic steels as P92 steel, commonly used to manufacture turbines and other main

components because of their good mechanical properties, processing ability and low price, suffer severe

oxidation above that temperature. A feasibly solution is the application of protecting coatings on the surface of

the steels.

CrAlN based coatings have widespread applications for surface protection due to their tribological

properties and thermal stability. Therefore, oxidation resistance of physical vapour deposited (PVD) CrAlN

coatings with Y additions have been tested in extreme conditions. Oxidation of coatings with and without an

adhesion layer of CrN deposited at the coating/substrate interface have been carried out at 650oC in 100%

steam atmosphere for 2000 hours.

Mass gain measurements have been recorded during the isothermal oxidation tests and characterisation

of coatings and scales after oxidation show the enhanced oxidation resistance provided by the coatings with

respect to that of the substrate. The dominant influence of the film microstructure developed due to the presence

of an adhesion interlayer of CrN at the coating/substrate interface over Y additions is evidenced. The best

performance is achieved by a CrAlN dense coating of around 6 µm without adhesion interlayer.

24

NOTES

25

Coatings for Oxycombustion- Supercritical Steam Boilers Components

A. Agüero1, I. Baraibar1, V. González1, M. Gutiérrez1, R. Muelas2 and D. Plana1

1Instituto Nacional de Técnica Aeroespacial. Ctra. Ajalvir Km 4. Torrejón de Ardoz 28850. Spain

2Ingenieria de Sistemas para la Defensa de España SA. Calle Beatriz de Bobadilla No. 3. Madrid 28040. Spain

Email: agueroba@inta.es

Abstract

The need to produce energy more efficiently and with a reduced environmental impact, has become

evident. This leads to increasingly extreme conditions imposing more demanding performances on materials, such

as higher temperatures and pressures, and more corrosive atmospheres. An alternative to facilitate CO2 capture

is the use of oxygen instead of air for combustion (oxycombustion) of any fuel in the boiler of steam power plants.

As the nitrogen presence on the combustion atmosphere is almost zero, the NOx emissions are drastically reduced

and it is then possible to separate and capture practically 100 % of the produced CO2. However, oxycombustion

atmospheres are much higher in CO2, SO2 and water vapor and under this atmosphere corrosion rates are

expected to be higher, moreover when supercritical steam conditions are required, and the components are

exposed to temperatures higher than 600º C. In fact, some boiler components such as the superheater tubes, are

exposed to both steam and fireside atmosphere corrosion at this high temperatures, and ferritic steels corrode at

very fast rates under both conditions. Unless materials with lower thermal conductivity and higher cost are used

(austenitic steel, Ni base alloys), protective coatings will be needed. A number of new coatings applied by

techniques capable of depositing both in- and outside the tubes such as slurry application and HVOF, are being

studied within the EC project POEMA. These coating techniques include slurry and thermal spraying. Aluminide

slurry coatings are already known to be very stable both under steam and fire-side corrosion at 650º C. However

degradation occurs by Al interdiffusion which may have two negative effects: 1) it causes Al depletion at the

surface, resulting in an Al content lower than the critical value require to maintain a stable protective alumina

layer and 2) it causes the precipitation of AlN, depleting the steel from N and possibly affecting the mechanical

properties of the material after long term. In order to reduce diffusion, new modified aluminide coatings have

been produced on P92. The microstructure of the new coatings will be shown and moreover, the results of

laboratory testing of these coatings both under oxycombustion model atmospheres with and without ash

deposition, as well as under pure steam at 650º C will be shown. Some of the coatings have already been tested

in a pilot boiler operating in Leon (CIUDEN) and the results are very promising. Finally, some insights regarding

preliminary results of the effect of supercritical steam pressure will be also shown and discussed. Some of the

tested coatings exhibit very stable behavior under both atmospheres.

26

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27

Flame spraying of Si bond coats over SiC substrates for environmental barrier coating architectures

A. Nistal1 E. García1, M. I. Osendi1, P. Miranzo1

1 Institute of Ceramics and Glass (ICV-CSIC), 28049, Madrid, Spain.

E-mail: andresnistal@icv.csic.es

Abstract

Silicon coatings are of interest in different technological applications as anti-corrosion layer or bond coat

in environmental barrier coating (EBC) systems. EBCs are developed for protecting against the corrosion

generated by the combustion atmosphere the SiC/SiC and SiC/C ceramic components intended for the next

generation of gas turbines engines. In these systems the first layer or bond coat prevents the substrate oxidation

and reduces the mismatch in thermal expansion coefficients. Compared to other deposition techniques, thermal

spraying methods for producing Si coatings have the advantages of efficiency and reduced cost. Different

architectures with thermal sprayed Si bond coats have been tested in oxidative and water vapour environments

and its functionality as sealing layer has been proved [1, 2].

Flame spray is the most cost efficient thermal spraying method, but surprisingly it has not been applied for

Si deposition. In this work, dense and well adhered Si coatings on SiC substrates were achieved using flame

spraying. By controlling key spraying parameters, the oxidation of Si was avoided. The elastic modulus and

hardness were measured by indentation, being comparable to those of plasma sprayed coats. The coating

adhesion was indirectly estimated by scratch and thermal diffusivity tests. For the first time, the thermal

conductivity of thermal sprayed Si coatings is reported.

Figure 1. SEM micrograph of a cross section of dense and well adhered flame sprayed Si coating on a SiC substrate.

References

1. K. N. Lee, D. S. Fox, N. P. Bansal, Rare earth silicate environmental barrier coating for SiC/SiC composites and Si ceramics, Journal of

the European Ceramic Society 25 (2005)1705.

2. J. Mesquita-Guimarães, E. García, P. Miranzo, M. I. Osendi, C. V. Cojocaru, R. S. Lima, Mullite-YSZ multilayered environmental barrier

coatings tested in cycling conditions under water vapor atmosphere. Surface and Coatings Technology 209 (2012) 103.

28

NOTES

29

Comparative oxidation behaviour in water vapour between out-of-pack aluminides and slurry based aluminium-based TBCs on Ni-based superalloys

F. Pedraza1 , M. Brossard1, B. Bouchaud1, J. Balmain1 and G. Bonnet1

1 Université de La Rochelle. LaSIE UMR 7356-CNRS. Pôle Sciences et Technologie. Avenue Michel Crépeau. 17042

La Rochelle. FRANCE

E-mail: fpedraza@univ-lr.fr

Abstract

Turbine components are exposed to particularly harsh environments at high temperatures, pressures and

corrosive gases. Their performance is usually tested in air but up to 15 vol% (37 RH%) of water vapour is released in

stoichiometric combustion of kerosene. Therefore, this work investigates the comparative isothermal behaviour at

1100°C for 50h of a conventional out-of-pack aluminide coating against a new Al-slurry based thermal barrier

coating system with increasing the water vapour. Substantiation of the actual role of water vapour will be

elucidated through tests in both dry air and argon gas atmospheres at 0, 5 and 10% RH (relative humidity). The

oxidation mechanisms and growth kinetics of the oxide scales will be compared up to 50% RH. Characterisation of

the phase transformations occurring in the coating will be performed by local Raman micro-spectrometry with

complementary analytical techniques (X-ray diffraction and FEG-ESEM/EDS). It will be shown that the role of water

vapour is negligible once the -Al2O3 scale is stabilised, in particular in the slurry coatings. However, the out-of-

pack aluminides undergo greater oxidation kinetics due to delayed transformation of the to -Al2O3 scales, the

appearance of pores and spallation when in the air + x%RH atmospheres.

Figure 1. SEM micrograph of a cross section of the Al-based slurry TBC after exposure to Ar+10% RH at 1100°C for 50h.

References

1. F. Pedraza, M. Mollard, B. Rannou, J. Balmain, B. Bouchaud, G. Bonnet, Potential thermal barrier coating systems from Al

microparticles. Mechanisms of coating formation on pure nickel Materials Chemistry and Physics 134 (2012) 700. 2. M. Brossard, B. Bouchaud, F. Pedraza, Influence of water vapour on the oxidation behaviour of a conventional aluminide and a

new thermal barrier coating system sintered from a slurry. Materials and Corrosion 64 (2013) No. 9999.

30

NOTES

31

Surface Modification of Materials exposed to Fusion Plasma and Impact on Reactor Operation

F. L. Tabarés1, A. de Castro, D. Alegre, A.B. Martin-Rojo, E. Oyarzabal and D. Tafalla

1 Association EURATOM-CIEMAT, Av. Complutense 40, 28040 Madrid, Spain

E-mail: tabares@ciemat.es

Abstract

Material properties are critical in the development of Plasma Facing Components for Fusion Research.

Unfortunately, the actual state of the surface upon exposure to the plasma may strongly differ from the selected

state on which they are introduced in the plasma. Not only sputtering process are responsible for this effect, but

material mixing and plasma fuel implantation are key parameters in setting the final surface composition,

structure and electrical properties of the materials facing a hot plasma. In a reactor, neutron irradiation has also

to be taken into account in the assessment of lifetime and performance of a reactor element. On the other hand,

some of the modifications experimentally observed offer interesting potential applications of plasma-treated

surfaces beyond the field of Fusion.

In this presentation a review of the state of the art on the topic will be given. Surface treatment processes

aimed at solving the urgent issues for a Fusion Reactor Design will be also addressed.

Figure 1. Development of fuzzy structures on W surface by He plasma irradiation in Pisces B.

32

NOTES

33

Surface Nitriding and Ammonia formation in N2/H2 plasmas on ITER-relevant Plasma Facing Materials

A. de Castro1, D. Alegre1 and F.L. Tabarés1

1 Association EURATOM-CIEMAT, Av. Complutense 22, 28040 Madrid, Spain

E-mail: alfonso.decastro@ciemat.es

Abstract

Ammonia production in N2/H2 direct current (DC) glow discharge plasmas, with nitrogen

concentrations from 1.5% to 33%, different wall materials (tungsten, stainless steel and aluminium as a proxy for

beryllium) and surface temperatures up to 350 C has been investigated. Ammonia yields and nitrogen

retention on the exposed materials have been deduced, resulting in different values depending on the wall

material, its temperature and N2 plasma content. The results indicate weak wall temperature dependence in

tungsten and stainless steel, being the ammonia yield normalized to injected nitrogen systematically lower for

tungsten. However wall temperatures above 300ºC have very clear influence on aluminium walls, as almost all

the cracked N2 was converted into ammonia. The amount of implanted N seems to have a direct impact on

the ammonia formation yield, pointing to the competition between N implantation and N/H recombination

on the walls as the key mechanism of the ammonia formation.

Figure 1. Time evolution example of ammonia formation, nitrogen retention and W wall saturation at Ip=200 mA, Twall=50ºC and

16% of N2 content.

34

35

Monday 20 Afternoon

Sessio 2: Biomedical

Oral Presentations

36

NOTES

37

Plasma Immersion Ion Implantation for MoM prosthesis application

C. Díaz1, S. Mändl2, R. Pereiro3

1Asociación de la Industria Navarra (AIN), Ingeniería de Superficies, Pamplona, Spain

2Leibniz-Institut für Oberflächenmodifizierung (IOM), Leipzig, Germany 3Universidad de Oviedo, Facultad de Química, Avda. Julián Clavería, 8,33006 Oviedo, Spain

E-mail: cdiaz@ain.es

Abstract

There has been recent concern about the increased use of prosthetic metal-on-metal total hip (MoM-THA)

as an alternative to contemporary metal-on-polyethylene total hip arthroplasty (THA-MoP), due to the release of

metallic ions inside the human body. MoM contacts may present important problems of wear, particles and ion

releasing which can lead to a shortening of the prosthesis’ lifetime [1]. In order to reduce these effects, between

both metal parts, surface plasma modifications of CoCr alloys were carried out [2,3]. Using the plasma immersion

ion implantation technique (PI3), CoCr alloys samples were modified to reduce the friction coefficient and the

wear rate by using either nitrogen, oxygen or a combination of nitrogen and oxygen ion implantation in the

temperature range between 300 and 400ºC, allowing a thermally assisted diffusion process in the near surface

region. The subsequent analysis of the wear rate was carried out in a biotribometer using bovine serum at 37ºC.

After these tests, bovine serum was collected in order to analyze the released particles and ions. Additionally,

roughness and hardness were studied, in order to analyze the influence of these parameters on the wear rate. The

results showed a strong reduction of the abrasive wear rate, with a friction coefficient similar in all studied samples.

It was observed a reduction of collected particles and ions from the plasma treated samples with respect to these

produced from untreated samples.

Figure 1. Relation between reductions in ion releasing and wear rate,

References

1. Holzwarth U, Cotogno G, Total Hip Arthroplasty, State of the Art,Challenges and Prospects, JRC Scientific and policy reports, 2012, p. 21-32.

2. C. Díaz, J.A. García, S. Mändl, R. Pereiro, B. Fernández, R.J. Rodríguez, Plasma Immersion Ion Implantation for Reducing Metal Ion Release,

AIP Conference Proceedings 1496, 2012, 284-287.

3. S. Mändl, C. Díaz, J.W. Gerlach, J.A. García, Near Surface Analysis of Duplex PIII Treated CoCr Alloys, Nucl. Instrum. Meth. B 307 (2013) 305-

309.

38

NOTES

39

An in vitro approach for “the race for the surface” theory. First results with clinical strains of Staphylococcus aureus and Staphylococcus epidermidis on

Ti6Al4V

M. Martínez-Pérez1, C. Pérez-Jorge1, D. Lozano1, J. M. Hernandez-Lopez2, S. Portal-Núñez1, M. A. Arenas2,

J.J. de Damborenea2, A. Conde2, P. Esbrit1, E. Gómez-Barrena3, J. Esteban1

1IIS-Fundación Jiménez Díaz Hospital, Madrid, Spain 2Centro Nacional de Investigaciones Metalúrgicas CENIM/CSIC, Madrid, Spain

3IdiPaz-Hospital la Paz, Madrid, Spain.

E-mail: martamp8@gmail.com

Abstract

The use of biomedical implant devices is growing in parallel to the advances in medicine, as well as to the

aging population. Thus, prosthesis infection carries more and more health and economic impact and is a matter

of concern of biomaterials research laboratories. According to “the race for the surface” theory1, if bacterial

adhesion occurred first infection took place, while if cell integration happened before, biomaterial integrates in

host tissues. Using a competitive assay between osteoblastic cells and bacteria, we have evaluated different

clinical and collection strains of Staphylococcus sp. in order to analyze their behaviour regarding bacterial

adherence.

Bacterial adherence study was carried out using a surface of chemically polished Ti6Al4V (CP) and several

S. aureus (collection strain 15981 and 2 clinical isolates) and S. epidermidis (ATCC 35984 collection strain and 2

clinical isolates). Clinical strains were isolated from patients with prosthetic joint infections. 1:10 serial bacterial dilutions (108-103 CFU/mL) were made. Dilution of murine osteoblastic MC3T3-E1 cells was made in α-MEM

medium+0.5 % of fetal bovine serum, to a final concentration of 100,000 cells/ml. CP surfaces were covered with 4

mL of a mixed solution (2 mL of a bacterial dilution and 2 mL of osteoblastic cells solution) and incubated 6 hours

at 37ºC in 5% CO2. Bacterial, cellular and negative controls were used. For each dilution, 8 pictures were taken at

40x magnification, and other 8 pictures at 20x magnification. We determined the minimal concentration of

bacteria needed to detect adherence. The experiment was performed in triplicate.

Osteoblastic cells adherence was observed in all dilutions. Both collection strains had a minimal

adherence concentration of 105 CFU/ml. However, for clinical strains a lower concentration was detected in most

of them: <103 for S. aureus P2, 103 for S. aureus P1 and S. epidermidis P55, and 105 for S. epidermidis P33.

In this study we have detected that most clinical strains need lower amount of bacteria than collection

strains in order to adhere to Ti6Al4V surface in presence of osteoblastic cells. We have previously demonstrated a

different behavior of clinical strains compared to collection strains in an adherence study on UHMWPE2. The need

of lower concentrations can be due to the presence of pathogenic factors that are lacking in laboratory-

adapted bacteria. However, further studies are needed; the use of clinical strains in adherence studies is essential

because of the differences detected with laboratory-adapted collection strains.

Figure 1A Figure 1B

Figure 1. Images at 40X (1A) and 20X (1B) from the adherence experiment using strain P1 (106 CFU/ml concentration)

References 1. Gristina AG, Costerton JW. Bacterial adherence and the glycocalyx and their role in musculoskeletal infection. Orthop Clin North

Am. 1984 Jul;15(3):517-35.

2. Gómez-Barrena E, Esteban J, Molina-Manso D, Adames H, Martínez-Morlanes MJ, Terriza A, Yubero F, Puértolas JA. Bacterial

adherence on UHMWPE doped with Vitamin E: an in vitro study. Journal of Materials Science: Materials in Medicine. 2011. Jul; 22(7): 1701-6.

40

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41

Ti1-xAgx and TiN-Ag electrodes deposited on polymer based sensors for biomedical applications

S. M. Marques1, N. K. Manninen2, S. Lanceros-Mendez3, A. Cavaleiro2, S. Carvalho1,2

1GRF-CFUM, Physics Department, University of Minho, 4800-058 Guimarães, Portugal

2SEG-CEMUC Mechanical Engineering Department, University of Coimbra, 3030-788 Coimbra, Portugal

3Physics Department, University of Minho, 4700-057 Braga, Portugal

E-mail: mariana.marques@fisica.uminho.pt

Abstract

Piezoelectric materials are interesting for the development of sensors and actuators for biomedical

applications in areas such as smart prosthesis, implantable biosensors and biomechanical signal monitoring,

among others. For acquiring or applying the electrical signal from/to the piezoelectric material, suitable

electrodes can be produced from Ti based coatings with tailored multifunctional properties: conductivity and

antibacterial characteristics through Ag inclusions. This work reports on Ti1-x Agx electrodes and TiN-Ag electrodes

deposited by d. c. and pulsed magnetron sputtering at room temperature on poly(vinylidene fluoride)(PVDF). In

the first system (Ti1-x Agx electrodes), silver content was varied from 0-100 at. %. For the second system (TiN-Ag

electrodes), the nitrogen content changed between 0 to 40.3 at. % by increasing the nitrogen gas flow between

0 sccm and 15 sccm and the ratio Ti/Ag changed from 13.4 to 2.2 being clearly the visible the decrease on the Ti

content in the reactive mode.

The X-ray Diffraction (XRD) results revealed that the deposition conditions preserve the polymer structure

and suggested the presence of crystalline Tiβ phase in pure titanium coating and fcc-Ag phase in pure silver

coating for the Ti1-xAgx system. For the TiN-Ag system is possible to detect a fcc TiN structure and fcc Ag phase.

According to the results obtained from scanning electron microscopy (SEM) analysis, the coatings are

homogeneous and only in TiN-Ag electrodes it was possible to see clusters; since β-PVDF is anisotropic, the

deposited coatings replicate the underlying substrate surface. Sheet resistivity values show a typical behavior of a

binary alloy system for the Ti1-x Agx electrodes. The sheet resistivity changes between 0.12 and 28.5 Ω/sq from the

Ti1-xAgx systems. For the second system the sheet resistivity decrease with the nitrogen content from 12.0 Ω/sq with

0 at. % to 2.8 Ω/sq for 40.3 at. % of N. The piezoelectricity of the different samples show similar values, showing

values from 19.6 to 27.6 pCN-1 for the Tix-1Agx system and 13.6 pCN-1 as minimum for the TiN-Ag system, achieved

for the highest N content. However any value compromise the piezoelectric response and clearly a good

electrode response could be obtained.

42

NOTES

43

The role of Ag on ZrCN coatings performance in harsh biological environments

S. Carvalho1,2

1 GRF-CFUM, University of Minho, Campus of Azurém, 4800-058 Guimarães, Portugal

2 SEG-CEMUC Mechanical Engineering Department, University of Coimbra, 3030-788 Coimbra, Portugal

E-mail: sandra.carvalho@fisica.uminho.pt

Abstract

The necessity of improving the performance of existing biocompatible materials promotes the investigation of new

approaches to solve biocompatibility problems caused by low chemical stability and poor mechanical

performance of implanted materials. Envisioning those problems, this work is focused on the deposition of ZrCN

coatings with embedded silver nanoparticles onto 316L stainless steel, to provide the material with enhanced

mechanical, electrochemical and biocompatibility properties, as well as introducing an antibacterial agent [1].

The coatings were produced by D.C. dual unbalanced magnetron sputtering and characterized in terms of

chemical, structural [2], mechanical and electrochemical properties [3] to optimize the performance of the

system. The optimization processes revealed that the best performance was achieved when stoichiometric

ZrC0.5N0.5 was the main phase in the coatings with low amounts of silver (<8 at. %), mainly explained due to the

electrochemical stability of the ceramic phase. Furthermore, in these conditions very good tribological

performance against high molecular weight polyethylene (UHMWPE)

was obtained. The hardness of the films was found to be mainly

controlled by the ratio between the hard (ZrCxN1-x) and soft (Ag and

amorphous carbon) phases, fluctuating between 7.4 and 20.4 GPa.

The coefficient of friction was governed by the films roughness and

hardness. Only very small changes in the UHMWPE wear rate were

identified, attributed to a protective layer of albumin formed during the

tests whose properties depended on the hydrophobic/hydrophilic

surface character, as well as on the silver content.

Finally, the electrochemical properties were largely affected by the

content of silver in the films, improving their corrosion resistance up to 8

at.% Ag, point for which the corrosion resistance decreases until

reaching that of the steel. Parallel biological studies on ZrCN with 11 at.

% Ag revealed low silver ion release, explained due to the formation of

nanometric protective layers of phosphates, sulfates and proteins for

the case of HBSS, HBSS+A and TBS, which block the paths for electrolyte

to penetrate further in the films, ionizing only the silver on the top of the

material. In order to increase the antimicrobial activity a new silver activation mechanism was developed.

References [1] S. Calderon V, R.E. Galindo, J.C. Oliveira, A. Cavaleiro, S. Carvalho, Surface and Coatings Technology, 222 (2013) 104-111.

[2] S. Calderon V, R.E. Galindo, N. Benito, C. Palacio, A. Cavaleiro, S. Carvalho, Journal of Physics D: Applied Physics, 46 (2013) 325303.

[3] S. Calderon V, V. Lopez, C.F. Almeida Alves, A. Cavaleiro, S. Carvalho, Corrosion Science, 80 (2014) 229-236.

Fig.1. Functional properties vs silver

content on Ag-ZrCN coatings

44

NOTES

45

Tribological characterization of DLC coated CoCrMo medical grade for application in Metal-on-Metal joint prostheses

J. Esteve1, D. Cano1, G.G. Fuentes2, C. Díaz2, L. Martínez de Olcoz and A. Lousa1

1 Department of Applied Physics and Optics, University of Barcelona, Barcelona (Spain) 2 Center of Advanced Surface Engineering, AIN, Cordovilla-Pamplona, E-31191, Spain.

E-mail: joan.Esteve1@gmail.com

Abstract

CoCrMo alloys are the most widely used metals for joint prostheses (hip, knee, shoulder, spinal), due to their

optimal mechanical and toughness properties, which are very close to the bone itself, among other medical

grade metals (AIS316L, Ti6Al4V). These alloys have additionally, an excellent corrosion resistance due to the

presence of Cr, which produce a Cr2O3 passive oxide layer [1]. DLC coatings thicker than one micron were

deposited by magnetron sputtering on highly polished CoCrMo substrates. The substrates have been previously

prepared with three different surface conditions: 1) no treated; 2) PIII nitriding and 3) PIII oxidising.

Friction and wear measurements were carried on a Ball-on-Disk tribometer by sliding a DLC coated ball (6

mm diameter) against a DLC coated CoCrMo flat plate. The load was adjusted for the contact pressure to be

similar to that of a human hip system. All the tribological tests were done in bovine serum (FBS) immersion at a

constant temperature of 37º C and with a cycle frequency of 1 Hz.

In these tests, the measured wear rate values were remarkably low ≈ 2x10-8 mm3/Nm [2] despite the

extreme test conditions.

The excellent corrosion resistance of the CoCrMo substrate, together with the low wear rates of DLC

coating, and also the good coating to substrate adhesion, make this arrangement a good candidate for

prosthetics applications.

Figure 1. Micrographs of : a) DLC coated WC ball. b) DLC coated CoCrMo substrates after a wear test.

References

1. Smith DC et al. J. Biomed. Mat. Res. 25 (1991). 1069-1084

2. Geoffrey Dearnaley, Surface & Coatings Technology 200 (2005) 2518 – 2524

a

) b)

a

46

47

Monday 20 Afternoon

Posters Presentations

48

NOTES

49

High temperature oxidation in steam atmosphere of nanostructured transition metal nitrides coatings on steel

A. Illana1, M. A. Sánchez-Mancilla1, M. Brizuela2, J.C. Sánchez-López3, F.J. Pérez1 and S. Mato1

1 Grupo de Investigación de Ingeniería de Superficies y Materiales Nanoestructurados Nº910627, Universidad

Complutense de Madrid, Facultad de Ciencias Químicas, E-28040

Madrid, Spain 2 TECNALIA, Parque Tecnológico de San Sebastián, Mikeletegi Pasealekua 2, E-20009 Donostia-San Sebastián,

Gipuzkoa, Spain 3 Instituto de Ciencia de Materiales de Sevilla (CSIC-US), Avda. Américo Vespucio 49, E-41092 Sevilla, Spain

E-mail: ailla01@ucm.es

Abstract

Electric generation power plants search to increase thermal efficiency of conversion processes in steam

turbines, to reduce fuel consumption and emissions of greenhouse gases such as CO2, SO2, and NOx [1]. This

requires developing materials able to resist steam conditions at 650-700°C since ferritic-martensitic steels, which

were commonly used so far due to their excellent mechanical properties at high temperature, show limited

oxidation resistance. Although high temperature alloys, as nickel-based alloys, can be used at the mentioned

temperature regime, coatings have been of interest in recent decades [2,3]. Following this approach the surface

characteristics of substrate are changed in order to prolong its service life at extreme conditions.

In this work, transition metal nitride coatings with varying concentration of alloying elements have been

deposited by PVD on 9–12% chromium steel (P92). The long-term oxidation resistance of the coatings was

evaluated at 650 °C in 100% steam atmosphere. Weight change measurements and characterisation of the

coatings after oxidation and developed oxide scales have been provide experimental evidences of the

breakthrough in the energy field industry.

Figure 1. Scanning electron micrograph of a cross section and chemical analysis profile of CrAlSiN coating after exposure to 100% steam

atmosphere at 650 °C for 1200h.

References

1. P. J. Ennis, A.C. Filemonowicz, Creep resistant steels for power plant. OMMI, Vol. 1, 2002, p. 1-27. 2. S. Mato, G. Alcalá, M. Brizuela, R. Escobar Galindo, F.J. Pérez, J.C. Sánchez-López, Long-term high temperature oxidation of CrAl(Y)N

coatings in steam atmosphere. Corrosion Science, Vol. 80, 2014, p. 453-460.

3. T. C. Rojas, S. El Mrabet, S. Domínguez-Meister, M. Brizuela, A. García-Luis, J.C. Sánchez-López, Chemical and microstructural

characterization of (Y or Zr)-doped CrAlN coatings. Surface and Coatings Technology, Vol. 211, 2012, p.104-110.

50

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51

Heat Treatment Diffusion Coating in SANICRO25

M. Gutiérrez1, V. González1 and A. Agüero1

1 National Institute of Aerospace Technology–INTA, Madrid, Spain

E-mail: gutierrezdom@inta.es

Abstract

A goal in power generation is to reduce CO2 emissions from coal-fired steam power plants with by raising

steam temperatures to 700ºC and therefore increasing thermal efficiency. New materials for critical components

are therefore required as the presently used ferritic steels cannot be used at such high temperatures due to lack

of creep strength. Sandvik has developed an austenitic alloy, Sanicro 25, with enough strength and corrosion

resistance based on an economical compositional balance of alloys. However it is not clear if this material will be

able to withstand fire-side corrosion, in particular when employing oxicombustion atmospheres with higher water

vapour, CO2 and SO2 content. Slurry aluminide coatings constitute an alternative to protect this material from

both steam and fire-side corrosion. The microstructure of these coatings depend on the diffusion heat treatment

at which they are subjected. In order to obtain a stable, crack-free microstructure, slurry coated Sanicro 25 has

been exposed to different heat treatment process. The resulting microstructures have been characterized and

thermal stability test at 700º C has been carried out. The results allowed to choose the optimal heat treatment. The

resulting microstructure is shown in figure 1.

Figure 1. SEM micrograph of a cross section of a slurry aluminide coating deposited after exposure to argon at 1050 °C for 3 h.

References

1. Diese Seite ist nur in den folgenden Sprachen verfügbar: Englisch Sanicro 25 (Tube and pipe, seamless) SANDVICK

2. Guocai Chai1, Patrik Kjellström and Magnus Boström, Creep and fracture behaviors of an advanced heat resistant austenitic

stainless steel for A-USC power plant, proceedings of 13th International Conference on Fracture, June 16–21, 2013, Beijing, China

52

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Potential protection of YSZ thermal barrier coatings against CMAS infiltration by a sacrificial slurry based coating

V. Kuchenreuther, M. Juez-Lorenzo, V. Kolarik , H. Fietzek

Fraunhofer-Institute Chemical Technology ICT, Pfinztal, Germany

E-mail: maria.juez-lorenzo@ict.fraunhofer.de

Abstract

Thermal barrier coatings (TBC) from yttria stabilized zirconia (YSZ) are widely used to reduce the metal

surface temperature of components in the hot area of power generation turbines. One of the causes of TBC

failure is the degradation by molten deposits, mostly calcium-magnesium-alumina-silicates (CMAS), which enter

the turbine from the environment. It infiltrates the pores and cracks, reacts with the YSZ and leads to its phase

destabilization.

The present research investigates to which extent the attack by molten CMAS can be reduced by

crystallizing it using an alumina sacrificial coating.

A model CMAS, composed of 38 mol% CaO, 6 mol% MgO, 5 mol%Al2O3, 50 mol% SiO2 and 1 mol% Fe2O3,

ultra-milled, molten two times for 4 h at 1400°C and milled again, was deposited on the surface of a free standing

sample from a commercial APS TBC. The samples were exposed to 1240°C for 200 hours in air and were analyzed

by X-ray diffraction with micro-focus (µ-XRD) and by field emission SEM.

Scans by µ-XRD stepwise across the coating from the surface to the bond coat interface show

considerable portions of the monoclinic phase in the uncoated sample. The alumina coated sample exhibits a

notable reduction of the monoclinic phase although in the micrographs an infiltration is observed. Depositing an

alumina coating on top of the TBC by an approach on slurry basis a notable reduction of the CMAS infiltration

and TBC destabilization was achieved. The XRD analysis reveals the formation of anorthite, which has a higher

melting temperature and leads to a reduction of molten CMAS phases.

Figure 1. SEM micrograph and Linescan of a cross section of an APS YSZ TBC caoted with Al2O3 after CMAS-attack at 1240°C after 50 hours.

Ca

Al

Si

Zr

54

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55

Increase of steam oxidation resistance at 650ºC and 800ºC of AlSi-CVD-FBR coating on P92 steel

S.I. Castañeda and F.J. Pérez

Universidad Complutense de Madrid. Research Group of Surface Engineering and Nanostructured materials

Facultad de Ciencias Químicas. 28040 Madrid. Spain

E-mail: sicastan@quim.ucm.es fjperez@quim.ucm.es

Abstract

The ferritic-austenitic steels of 9-12% chromium (P91, P92, HCM12, etc.) are commonly used for power

plants with advanced steam oxidation conditions and they are candidates for future coal combustion

power plants. These materials are good for the steam resistance at temperatures up to 600ºC [1-3]. In order

to increase operation temperature of steam turbines, Al-Si coating was deposited on the ferritic P92 steel

at 580ºC by chemical vapour deposition in a fluidized bed reactor (CVD-FBR) for 1.5h followed by a

diffusion heat treatment at 700ºC for 2h. Study of Thermogravimetric measurements (TG) and Mass

spectrometry (MS) of the initial stages of oxidation at 650ºC and 800ºC in Ar+40%H2O for 150h of the P92

steel with and without Al-Si coating were performed. TG measurements at 650ºC for 150h of steam

oxidation of the samples have indicated that the coated sample with Al-Si had not gained weight with

respect to the uncoated P92 steel; that it had gained 5.25mg/cm2. While, the coated sample oxidized at

800ºC in steam had gained 0.83164mg/cm2. The coated sample during oxidation was better protected;

on the coating were formed some protective oxides, (i.e.) the silica (SiO2) and alumina (Al2O3). These

layers have avoided or delayed catastrophe of oxidation and corrosion of P92 steel. Thermodynamic

simulations in the equilibrium were performed in order to find a first approximation of MS database. All

theoretical calculations with the Thermo-calc program in a range of temperature between 500 and 900ºC

were done. Morphology, composition and structure of coatings were characterized by means of scanning

electron microscopy (SEM); electrons emission secondary and electron back-scattered diffraction

(EBSD)/energy dispersive X-ray spectroscopy (EDX) and X-ray diffraction (XRD) techniques, respectively.

References

1. R. Viswanathan, J. Sarver, j.M. Tanzosh, Journal of Materials Engineering and Performance; 15(3) (2006) 255.

2. F. Masuyana, New Developments in Steels for Power Generation Boilers, in Advanced Heat Resistant Steels for Power Generation, R.

Viswanathan and J.W. Nutting, Ed.; IOM Communications Ltd., London 1999; 33-48.

3. P.J. Ennis, W.J. Quadakkers, International Journal of Pressure Vessels and Piping, 84 (2007) 82.

56

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Anticorrosion hybrid AlPO4/Al2O3 coatings on the surface of P92 steel for oxy-fuel power plant application

L. Davydenko1, M. Nazarchuk1, D. Nasiedkin1, Yu. Plyuto1, M. Mosquera-Feijoo2, M. Nofz2,

R. Sojref2, I. Dörfel2, R. Saliwan-Neumann2, A. Kranzmann2 and F.J. Pérez3

1 Chuiko Institute of Surface Chemistry, Ukraine

2 Federal Institute for Materials Research and Testing, Germany 3 Complutense University of Madrid, Spain

E-mail: davydenko@isc.gov.ua, maria.mosquera-feijoo@bam.de

Abstract

Currently, the oxy-fuel combustion process is considered to be a promising technology to attain efficient

and clean coal utilization on power plants. Due to suitable mechanical properties, P92 steel is believed to be a

good candidate for boiler, tubes and pipes under operation temperature of 650 oC. Nevertheless, high sulphur

dioxide partial pressure in the flue gas is hostile for constructive materials (the components) as well as protective

coatings on their surface. Therefore, the development of thermally and chemically stable coating capable to

withstand under oxy-fuel conditions and to supply high anticorrosion protection of the power plant components is

of interest.

According to preliminary thermodynamic simulation, the oxide layers (mostly alumina and chromia) may

react with SO2 at 650 oC thus inducing the coating degradation and causing the substrate corrosion. In contrast,

interaction of aluminium phosphate with SO2 is forbidden above 410 oC. Therefore, AlPO4 was studied as SO2

resistant top-coat for sol-gel alumina coatings which effectively diminished high temperature corrosion of steels [1,

2].

Alumina base-coats were applied by dipping P92 substrates into

ethanolic boehmite sols followed by heat treatment at 650 °C for 30

min. Aluminium phosphate top-coats were applied by dipping alumina

coated substrates in aqueous aluminium dihydrogen phosphate

followed by heat treatment at 650 °C for 30 min. The resulting

amorphous well adhered hybrid coating of up to 2.5 micrometers

thickness consisted of three zones with different element compositions

(fig. 1).

The results of testing of the coated and uncoated P92 substrates in

air oxy-fuel atmosphere (60CO2 – 30H2O – 2O2 – 1SO2 – 7N2, vol. %; flow

rate 3*10-2 m/s, 1 bar) at 650 °C for up to 300 h demonstrated the

enhancement of corrosion protection of alumina coated P92 steel by

application of aluminium phosphate top-coat. The developed hybrid

coatings demonstrated neither spalling failure nor cracking and

exhibited very low mass gain.

Acknowledgement The work was supported by the European Community in the frame of FP7 Collaborative Project NMP3-SL-2012-

310436 “Production of Coatings for New Efficient and Clean Coal Power Plant Materials” (POEMA).

References

1. W. Schulz, M. Nofz, M. Feigl, I. Dörfel, R. Saliwan-Neumann, A. Kranzmann, Corrosion of uncoated and alumina coated steel

X20CrMoV12-1 in H2O-CO2-O2 and air at 600 °C. Corrosion Science 68 (2013) 44.

2. W. Schulz, M. Feigl, I. Dörfel, M. Nofz, A. Kranzmann, Influence of a sol-gel alumina coating on oxidation of X20CrMoV12-1 in air up

to 650 °C. Thin solid films 539 (2013) 29.

Figure 1.SEM micrograph of a cross section of

hybrid Al2O3-AlPO4 coating.

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Exploring the aluminium slurry coatings limits for new aeronautic requirements

J. Mora2 and A. Agüero1

1 Instituto Nacional de Técnica Aeroespacial. Ctra. Ajalvir Km 4. Torrejón de Ardoz 28850. Spain

2 Ingeniería de Sistemas para la Defensa de España S.A. Calle Beatriz de Bobadilla No. 3. Madrid 28040. Spain

E-mail: jmora@isdefe.es

Abstract

The protection against corrosion in aeronautic metallic structures is a very important issue, with many relevant

safety and economic implications. Sacrificial coatings have been widely used for decades, and there is a large

number of protective coatings in the market for aeronautic applications.

The requirements of these applications are increasing, and several technical factors must improve. Cadmium

coatings presents excellent corrosion and lubricity properties, but because of their toxicity, their use is regulated.

Aluminium slurries are a non-toxic, economic, and easy to apply alternative. However, up to present, these

coatings required a too high thickness, not allowing their use in aeronautic components.

The curing temperature is another important point to deal with, so it could generate important limitations in the

use of heat sensitive materials.

In this work, two aeronautic steels (SAE 4130, and AISI E4340) have been coated with an aluminium slurry

optimized by INTA, obtaining thicknesses from 15 to 30 micrometres (25-50% of that obtained in previous works).

These coatings have passed the requirements indicated in the High Strength Steel Joint Test Protocol (HSSJTP), and

the qualification tests of the MIL-DTL-83488 specification, regarding adhesion (Tape test, and Bend test), corrosion

(salt spray fog chamber, SSFC), and hydrogen embrittlement & re-embrittlement tests (ASTM-F519).

A different deposition process has been developed, including a significant decrease in the curing temperature, so

that these coating can be applied with heat sensitive materials.

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Steam oxidation test for new generation steam power plants

T. El Baraka 1, I. Baráibar1 and A. Agüero1

1Instituto Nacional de Técnica Aeroespacial. Ctra. Ajalvir Km 4. Torrejón de Ardoz 28850. Spain

E-mail: agueroba@inta.es

Abstract

Nowadays, thermal power generation plants are the main sources of electricity in many countries. Major

components of these thermal power plants are expected to be exposed to higher temperatures which causes a

number of issues. Indeed, for equipment operating at high temperature, there are many ways of degradation as

for instance oxidation or corrosion, which can greatly lower the life time of boiler components. For this reason,

plenty of studies are carried out in order to better understand and prevent high temperature degradation in

Power Plants. An important aspect is the design of laboratory tests and conditions that can simulate the real

operation conditions as close as possible. Although extensive work has been done in this area, there are no

standards and no clear information and systematic studies such as how different test parameters as pressure, flow

rates, alloy surface finish, etc. affect the oxidation rates of the tested materials.

This poster reports the results of a study made on different steels: P22, P92, FB2 and MARBN when exposed

to steam at 650º C. The effect of both surface finish (grounded and sandblasted) as well as of the steam flow rate

(1cm/min and 25cm/min) on the scaling behavior of stainless steel in steam at 650ºC has been studied for a

period of 500 hours.

The results show that the surface finish has an influence on the rate of oxidation for two of the studied

alloys. In case of MARBN and P92 a difference between samples grounded and sandblasted was observed and,

in both cases, we notice a higher weight increased for the sandblasted samples. Furthermore, the weight gain of

the grounded sample of MARBN is very negligible despite having only 9 wt. % in Cr. However, we can see that the

surface finish (grounded – sandblasted) has no effect on the mass change of samples of FB2.

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63

Ni aluminide coating on P92 for oxidation and corrosion protection

I. Baráibar1, J. A. Domínguez1 and A. Agüero1

1Instituto Nacional de Técnica Aeroespacial. Ctra. Ajalvir Km 4. Torrejón de Ardoz 28850. Spain

E-mail: baraibargmi@inta.es

Abstract

The tendency for energy production is to increase the performance and efficiency of power plants,

leading them in the searching of new working environments which result aggressive towards the materials used in

the different components of the plants. Such changes in working conditions lead to increased corrosion of the

metallic parts involved in different stages of the process.

In the way of addressing these new demands on materials, and in order to protect them from oxidation

and hot corrosion, the current trend is to apply coatings on the metallic alloys.

Slurry aluminide coatings are known to be very protective in this environments by the exhibit through

thickness cracks and degrade by interdiffusion with the substrate. In this work, the results of a Ni aluminide coating

on P92, a commonly used substrate in steam power plants in order to reduce diffusion and to avoid the presence

of cracks. This coating is produced by plating with nickel by means of electroless deposition followed by the

application of an Al slurry and a diffusion heat treatment. Electroless nickel plating is used to deposit nickel without

the use of an electric current. The coating is deposited by an autocatalytic chemical reduction of nickel ions by

hypophosphite or borohydride compounds. This process allows the deposition of continuous coatings with a

constant thickness on a very large range of substrates including non-metallic materials, rendering a very

homogeneous alloy layer of Ni-P, which is deposited over surfaces with many different geometries. It is a very

simple, inexpensive and easy to apply process that produces a Ni coating which, after heat treatment,

interdiffuses with the steel substrate. In a further step of the process, a layer of Al is added by applying an slurry

which, after heat treatment, diffuses into the deposited Ni layer producing Ni-Al intermetallic compounds (Ni

aluminides), highly protective and less brittle than Fe-Al aluminides so that the formation of cracks typical of the

FeAl coatings is avoided. Moreover, a lower Al inward diffusion rate should also be reduced. Trials with both Ni-P

and Ni-B electroless layers have been carried out as well as testing under steam at 650º C.

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Cathodic arc evaporation and characterization of CrAlON thin films

E. Almandoz1, J.F. Palacio2, S. Kulkarni1, R.J. Rodríguez2 and G. G. Fuentes1

1 Asociación de la Industria Navarra, 31191 Cordovilla, Spain.

2 MIASA Mecanizados Industria Auxiliar. 31012 Pamplona, Spain.

E-mail: ealmandoz@ain.es

Abstract

This work reports on the chemical, microstructural, mechanical and tribological performance of cathodic

arc evaporated CrAlO based coatings for applications in the hot forming industry. CrAlO coatings have attracted

a strong interest due to the possibility to synthesise at low temperature (400 ºC – 500ºC) corundum-like (CrAl)2O3

hard coatings. Whereas sputtering or ion beam assisted deposition methods allow the synthesis of these chemical

formulation [1], arc evaporation of oxide coatings produces a fast poisoning of the cathodes, excessive micro-

droplet formation and electrical screening of the growing films.

In this study, we have developed alternating CrAlO/CrAlN layers by cathodic arc evaporation in the

presence of a reactive O2/N2 atmosphere. The presence of N2 even during the growth of CrAlO has shown to

have beneficial effects to mitigate the poisoning of the cathodes, in agreement to Najafi et al [2].

Scanning electron microscopy (SEM), glancing incidence X-ray diffraction (GIXRD) and glow discharge

optical emission spectroscopy (GD-OES) have been used to analyse the coatings. The mechanical properties

such us nano-indentation hardness, adhesion strength and wear at room and high temperature will be discussed

and correlated to the microstructural design of the coatings in terms of bilayer period and thickness ratio of the

oxide/nitride bilayer.

Figure 1. Cross-section of a CrAlOx coating on Si.

References

1. Stüber et al. Thin Solid Films 519 (2011) 4025-4031

2. Najafi et al. Surface & Coatings Technology 214 (2013) 46-52

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Ag-containing diamond-like carbon coatings: on their microstructure and tribo-mechanical properties

S. Domínguez-Meister1, T. C. Rojas1 and J. C. Sánchez-López1

1Instituto de Ciencia de Materiales de Sevilla (CSIC-Univ. Sevilla), Avda. Américo Vespucio 49, 41092-Sevilla, Spain

E-mail: s.dominguez@csic.es

Abstract

Silver-containing diamond-like carbon (Ag-DLC) is a promising material for biomedical implants due to its

excellent combination of antibacterial and tribo-mechanical properties. In this work, a series of pure DLC samples

was firstly deposited by dc-pulsed magnetron sputtering under different frequency and duty cycle conditions to

determine the best experimental parameters in terms of tribological performance. Then, a set of Ag-DLC coatings

with different Ag contents ranging from 2.5 to 18 at. % was deposited using the determined optimum conditions

and a carbon target with silver nuggets on its surface. The study of Ag-DLC series by scanning electron

microscopy (SEM) and transmission electron microscopy (TEM) techniques revealed a columnar structure with Ag

nanoparticles embedded (Fig. 1). A heterogeneous Ag particle size distribution between 1.5 and 100 nm was

found (Fig. 2). The Ag particles were mainly located in the columnar boundaries (Figs. 1 and 2) and sometimes

segregated to the surface. Raman analysis of the D and G peaks showed a similar disordered carbon structure,

with no significant variation when Ag is introduced. The study of the tribological properties in air conditions

showed a small decrease in the friction coefficient (0.22→0.17) and slight increase in the wear rate (1.6·10 -7→3·10-

7mm3/Nm) when the Ag is present regardless its concentration. With the aim of simulating the human body

environmental conditions, tribological tests were carried out using fetal bovinum serum as surrounding medium

and a constant temperature of 35ºC. The results showed a small decrease of the wear rate (~1·10-7 mm3/Nm)

indicating that the behaviour is optimum in the biological environment. To investigate the mechanical properties,

nanoindentation studies were made over three representative samples: carbon reference, low and high amount

of silver. The results showed a decrease of the hardness when the silver is introduced (17→13 GPa) that can

explain the observed slight decrease of film wear resistance.

NOTES

Figure 1: SEM image showing columnar structure of the

Ag-DLC.

Figure 2: HAADF image showing Ag

particles.

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Tribocorrosion behavior of TiBxCy/a-C nanocomposite coating in strong oxidant disinfectant solutions

E. Gracia-Escosa1, I. García1, J.C. Sánchez-López2, M. D. Abad2, A. Mariscal2, M. A. Arenas1, J. de

Damborenea1, A. Conde1

1CENIM-CSIC, Surface Engineering, Corrosion and Durability department, Av. Gregorio del Amo 8, E-28040

Madrid, Spain

2Instituto de Ciencia de Materiales de Sevilla, (CSIC-US), Av. Américo Vespucio 49, E-41092 Sevilla, Spain

E-mail: elenagracia@cenim.csic.es

Abstract

Corrosion and tribocorrosion studies of a TiBxCy/a-C coating deposited on AISI 316L steel have been

performed in an aqueous solution of 0.26 vol.% acetic, 0.16 vol.% peracetic and 0.18 vol.% hydrogen peroxide.

The corrosion current density of the TiBxCy/a-C coating ranges in the same order than the bare steel but

decreasing significantly the friction coefficient (0.1 vs. 0.6) and wear rate (~ 10 times lower). The chemical stability

and the compact microstructure of the coating prevent the onset of the corrosion attack, while maintaining an

excellent tribological behaviour in strong oxidant solutions. The results show, that TiBxCy/a-C nanocomposite

material is an interesting protective tribological coating for biomedical and food sectors where the asepsis is a

demanding requirement and therefore, they are periodically submitted to this strong oxidant media

Figure 1. SEM cross-sectional view of the TiBxCy/a-C coating

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Development of decorative coatings resistant to high temperatures

E. Carretero1 and R. Alonso1

1 Department of Applied Physics, University of Zaragoza, Spain

E-mail: ecarre@unizar.es

Abstract

Glass-ceramic is used in hobs as cooking surface. At present transparent glass-ceramic panels allow us the

differentiation of aesthetic aspects by multilayer optical coatings. Coating design and production by sputtering

(PVD) can provide different aesthetic aspects to glass-ceramic panels [1]. However, the PVD coatings as well as

the suitable optical properties must have the mechanical and thermal stability to allow their use in induction

cooking under use conditions, because coatings require less colour change than human eye sensitivity after

exposure to air at 400ºC for 1 hour.

In this work we show different materials and multilayer structures, as well as the resistance of coating to

high temperatures. Some transparent dielectric and metallic light absorptive materials are studied by visible

spectrophotometry to determine their optical properties. Results show the need to use materials with a low oxygen

diffusion coefficient on the different films with the aim to avoid coatings degradation. Several colour coatings are

developed and tested.

Figure 1. Visual appearance of different coatings developed.

References

1. J.A. Dobrowolski, L. Li, R.A. Kemp, “Metal/Dielectric transmission interference filters with low reflectance. I design.” Applied Optics

34, 5673-5683 (1995).

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73

On the Deposition Rate of Magnetron Sputtered Thin Films at Oblique Angles

R. Alvarez, J.M. Garcia-Martin, M.C. Lopez-Santos, V.Rico, F.J. Ferrer, J. Cotrino, A.R. Gonzalez-Elipe, A.

Palmero

Instituto de Ciencia de Materiales de Sevilla (CSIC-Universidad de Sevilla). c/ Americo Vespucio 49, 41092

Seville, Spain

E-mail: alberto.palmero@icmse.csic.es

Abstract

We describe the magnetron sputtering deposition of thin films at oblique angles. A general relation

between the deposition rate of the film and experimental parameters such as gas pressure or substrate tilt angle is

deduced and experimentally tested. The model also permits the direct determination of the thermalization mean

free path of the sputtered particles in the plasma gas, a key magnitude defining the balance between ballistic

and diffusive flows in the deposition reactor. The good agreement between experimental and calculated results

supports the validity of the description to explain the main features of the magnetron sputtering deposition of thin

films at oblique angles. A comparison between calculations and experimental results is shown in Figure 1.

Figure 1. Deposition rate dependence on the tilt angle of the substrate (lineal scale). Dots correspond to experimental data, whereas

lines depict the theoretical prediction according to eq. (2). Note the different scales used for the low and high-pressure cases.

References

Rafael Alvarez,* Jose M. Garcia-Martin, Maria C. Lopez-Santos, Victor Rico,, Francisco J. Ferrer, Jose Cotrino, Agustin R. Gonzalez-

Elipe, Alberto Palmero, Plasma Proc. Polym. 2014, DOI: 10.1002/ppap.201300201

74

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75

Anisotropic in-plane conductivity in plasma assisted ITO thin films prepared by e-beam evaporation at oblique angles

J. Parra-Barranco, A. Borras, F. Garcia, M.C Lopez-Santos, A.R. Gonzalez-Elipe, A. Barranco,

Instituto de Ciencia de Materiales de Sevilla (CSIC- Univ. Sevilla). Avda. Américo Vespucio 49, 41092 Sevilla (Spain)

E-mail: arge@icmse.csic.es

Abstract

ITO thin films have been prepared by electron beam evaporation in an oblique angle (OA) configuration

both directly or by assisting their growth by interacting with a downstream plasma. The microstructure of the

evaporated films consisting of isolated and tilted nanocolumns was significantly modified by plasma interaction. In

these plasma assisted films, the tilting angle of nanocolumns decreases and they became associated in the form

of bundles in a direction perpendicular to the arrival direction of the flux material during deposition (Figure 1).

After annealing in air the ITO films were transparent and conductive. In the OA deposited films sheet and cross

section measurements of conductivity depict quite different values in agreement with the nanocolumnar

microstructure of thin films. These measurements at macroscopic level are confirmed by scanning electrical

measurements at the individual nanocolumns. In addition, for the plasma assisted OAD thin films, two different

sheet resistance values could be determined by measuring in the direction of the bundles or perpendicular to

them. This anisotropic in-plane conductivity is utilized to tailor the plasmon resonance of electrochemically

deposited gold nanoparticles for the fabrication of dichroic thin films with a distinct response towards polarized

light.

Figure 1.- SEM cross section micrograph of a ITO bilayer prepared by OAD , where the bottom layer has

been prepared in the absence of plasma and the top layer by assisting the growth with a plasma of oxygen.

76

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Tuesday 21 Morning

Session 3: Mechanical

Oral Presentations

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High performance cold gas spray (CGS) coatings for Xtreme wear damage resistance

J.M. Guilemany, S. Dosta, M.Couto, I.Garcia-Cano

Thermal Spray Centre (CPT). University of Barcelona. Spain

E-mail: jmguilemany@cptub.eu

Abstract

The interest of WC-Co coatings is well established in the worldwide industry because they provide excellent

and lasting resistance to different types of wear, erosion and corrosion under aggressive environments. Combining

these properties and adding them to specific working parts has been a major improvement in the life of

aeronautical, automotive, mining and oil drilling parts during the last years.

WC-Co coatings are usually produced by conventional thermal spray techniques, such as Air Plasma

Spraying (APS) and High Velocity Oxy-fuel (HVOF) spraying, which use high temperatures to melt the powder

particles and form a coating. However, this approach causes decarburization of the powder. Also, concern has

been raised about reducing the particle size of the WC-Co powders currently used as spraying materials, despite

knowledge that a reduction in particle size (from micrometric to submicrometric to nanometric) until a specific

lower limit imparts improved performance in terms of hardness and wear resistance properties. The effect of

reducing the average particle size leads to a higher particle velocity and, consequently, a lower gas/particle

temperature is required. The drawback of using these powders in conventional thermal deposition techniques is

that the process temperatures lead to undesirable effects in addition to decarburization, such as the formation of

W2C, W and/or fragile η phases, dissolution of WC and Co and residual stresses, and thus the loss of certain

mechanical and electrochemical properties.

In this scenario, Cold Gas Spray (CGS) has positioned itself as a leading technology able to build-up such

cermet coatings through a procedure that requires brief times of operation. CGS propels powder particles in solid

state towards a substrate where are plastically deformed and mechanically anchored. This technique is a solid-

state deposition process where no melting of the powder particles occurs in a supersonic jet of compressed gas

which deposits them on a substrate, where they deform and rapidly bond together, to build up a thick layer of

material.

WC-Co cermet coatings with different contents in Co matrix (25, 17 and 12%) can be successfully

deposited onto two types of substrates, low carbon steel and Al7075-T6, using Cold Gas Spray. Proof of concept

with different wear and electrochemical tests demonstrated that the CGS cermet coatings act effectively when

under abrasive wear, friction wear and corrosion.

.

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Nano-multilayered and nano-composite hard PVD coatings for tool/dies at medium/high temperatures

G. G. Fuentes1, E. Almandoz1, Diego Otazu2, Sonia Mato3, F. Javier Pérez-Trujillo3

1 Asociación de la Industria Navarra, 31191 Cordovilla, Spain.

2 MIASA Mecanizados Industria Auxiliar. 31012 Pamplona, Spain. 3 Surface Engineering Group, Universidad Complutense, Madrid, Spain.

E-mail: gfuentes@ain.es

Abstract

Nanostructuring of industrial hard coatings is one of the present technological challenges of the protective

thin film sector. Nano–composites and nano-multilayered thin films have been widely investigated at laboratory

scale since the 90’s. Nano-structuring has shown important improvements of the mechanical properties of the

films such as hardness, fracture toughness and wear resistance. However, still the up-scale to industrial production

has not been fully achieved.

In this presentation, we report on the mechanical, tribological and thermal stability of a series of nano-

multilayered (Cr/Ti,Al,Si,N), and TiN/CrN films deposited in an industrial arc-PVD unit. The films have been tested

using conventional nano/ultramicro indentation techniques, friction and wear under a ball on disc configuration

at RT and at 400-500ºC, and oxidation kinetics under aggressive atmospheres.

The results exhibit a clear improvement of the hardness, fracture toughness, scratch resistance, and

thermal stability of the nanostructured coatings, with respect to those of consisting of monolayers. Several of these

films have been deposited on mechanical components, and their performances tested under real conditions of

operation. Generally speaking, there is a good correlation between the lab test observations and the

performance recorded during the industrial trials.

Figure 1. Inserts after 100.000 injection operations of mobile inserts. Left: Commercial AlTiN. Right: AlTiSiN.

82

NOTES

83

On the nanostructure and oxidation protection of CrAlN and CrAlYN coatings

T. C. Rojas1, S. Domínguez-Meister1, M. Brizuela2, J. C. Sánchez-López1

1Instituto de Ciencia de Materiales de Sevilla (CSIC-Univ. Sevilla), Avda. Américo Vespucio 49, 41092-

Sevilla, Spain 2TECNALIA, Mikeletegui Pasealekua, 2, 20009 Donostia-San Sebastián, Spain

*contact e-mail: tcrojas@icmse.csic.es

Abstract

CrAlN and CrAlYN coatings with variable composition (5% and 20 at.% Al) and (2 at.% Y) were

deposited by direct current reactive magnetron sputtering on silicon and M2 steel substrates using metallic targets

and Ar/N2 mixtures under different target composition (Al, Cr, Y or mixed Al/Cr) and configurations. The samples

have been heated to 1000ºC in air during 2h to study their protective properties. In this work electron microscopies

coupled with spatially resolved microanalysis techniques and FIB specimen preparations are used to investigate

the nanostructure, constituting phases and the chemical elemental distribution of the as-prepared samples and

after heating. The as-prepared coatings present always a multilayered columnar architecture (cf. Fig.1) where the

metals are distributed periodically along the structure (cf. Fig. 2). For low Al content (5 at.%), nanovoids filled with

molecular nitrogen were found embedded in amorphous (Al and/or Y) nitride layers [1], but these features do not

appear when Al content is 20 at.%. The target composition and distribution in the deposition chamber produce

changes in the elemental distribution. These changes led to different oxidation resistance properties when heating

in air to 1000ºC. A good oxidation protection is obtained for CrAlN (both Al contents) and CrAlYN only if Al and Y-

rich regions are well separated by crystalline Cr(Al)N layers. An exhaustive study of the CrAlN (20 at.% Al) and

CrAlYN (20% Al, 2 at.%Y) samples grown on M2 steel after oxidation enabled us to determine the differences in

the oxidation mechanism. In the CrAlN the multilayer architecture was retained with CrN and h-AlN crystals and a

low oxygen content (3-5 at. %). However, in the heated CrAlYN (20 at.% Al, 2 at.%Y), a top layer of Cr2O3 of

around 500 nm and a polycrystalline homogenous structure mainly comprised by Al2O3, and Cr2N crystals is

formed. These results indicate the influence of yttrium atoms in the ion transport processes and oxide growth

mechanism that will be studied and discussed.

Figure 1. HAADF-STEM image

showing the columnar and multi-layered

microstructure.

Figure 2. Cr (a) and N (b) EFTEM

elemental mapping distribution obtained

from a sample CrAlYN (8% Al) . Al and Y

distribution along the marked profile

perpendicular to the columnar growth

obtained by EDS (c).

Reference

1. T.C. Rojas, S. Domínguez-Meister, M. Brizuela, A. García-Luis, A. Fernández, J.C. Sánchez-López, A nanoscale characterization with

electron microscopies of multilayered CrAlYN coatings: a singular functional nanostructure. Microscopy and Microanalysis. 20, (2014)14-24.

Acknowledgements

The Spanish MINECO (projects Nº MAT2011-29074-C02-01/-02, CONSOLIDER FUNCOAT CSD2008-00023), CSIC (20160I041) and European Union

(CT-REGPOT-2011-1-285895 AL-NANOFUNC ) are acknowledged for financial support.

200 nm

1

1)

2

2)

84

NOTES

85

High temperature oxidation behavior of MCrAlY laser cladding coatings

J. C. Pereira1,2, J. C. Zambrano2, M. J. Tobar3, A. Yañez3, V. Amigó1

1 Instituto de Tecnología de Materiales, Universidad Politécnica de Valencia, España.

2 Centro de Investigaciones en Mecánica, Facultad de Ingeniería, Universidad de Carabobo, Venezuela. 3 Departamento de Ingeniería Industrial II, Universidade da Coruña, Campus Ferrol, España.

E-mail: jpereira@uc.edu.ve

Abstract

The development of coatings has become a technologically significant aspect in many industries. A

common approach in high temperature applications is the production of new thermal barrier coatings (TBCs) [1].

The Laser cladding (LC) can be an alternative method to thermal spraying for the production of high quality bond

coats in TBCs [2]. In this work, dense coatings with adequate metallurgical bond with the substrate by overlap

coaxial laser cladding were obtained. The oxidation behavior of the coatings specimens was assessed by air

furnace oxidation tests at 1100 °C for up to 200 h. The coatings microstructure is composed of a γ matrix phase

and β dendritic phase, confirmed by DRX. At high temperature, the growth and formation of oxides layers provide

protection of the underlying coating and substrate from oxidation at elevated temperature. The possible

formation and morphology of oxides on the oxidized surface has been evaluated by Scanning Electron

Microscopy (SEM) and Atom Force Microscopy (AFM). The evaluation of thickness and phases presents in

thermally grown oxide scale was evaluated by Field Emission Scanning Electron Microscopy (FESEM) and Energy

Dispersive Spectroscopy microanalysis (EDS), with previous cut by Focused Ion Beam Ga Column (FIB) method.

Figure 1. FIB-FESEM micrograph of a cross section in NiCoCrAlY laser cladding coating (10 h at 1100 ºC)

References

1. U. Schulz, A. Leyens, K. Fritscher, Some recent trends in research and technology of advanced TBCs”, Aerospace Science and

Technology. 2003; 7(1): 73-80.

2. F. Vollertsen, K. Partes, J. Meijer, State of the art of laser hardening and cladding, proceding of WLT Conference: Lasers in

Manufacturing, 2005: 281-305.

86

NOTES

87

Laser Furnace Surface Processing of Ceramics and Glass

I. de Francisco1, V. Rico2, V. V. Lennikov1, L. C. Estepa1, L. A. Angurel1, A. R. González-Elipe2 and G. F. de la

Fuente1

1 ICMA (CSIC-Universidad de Zaragoza), Zaragoza, España

2 ICMSE (CSIC-Universidad de Sevilla),Sevilla, España.

E-mail: xerman@unizar.es

Abstract

A patented device known as a Laser Furnace [1] has been applied to modify ceramic and glass substrate

surfaces in order to attain optical aesthetic effects under extreme conditions. This device enables reaching very

high temperatures within a surface layer of the substrate, without damaging its volume, even when the suface

temperatures surpass the limits of the substrate significantly. In this manner, soda-lime (window) glass may be

modified reaching surface temperatures well above 1000 ºC, while its volume is kept at or below 470ºC. In a similar

fashion, ceramic substrates are kept at volume temperatures ranging between 450ºC and 1000ºC, while their

surfaces may be laser treated above 2000ºC. This patented method will be overviewed by correlating recently

obtained results in terms of material type, volume temperature and laser irradiation parameters used, with the aim

of highlighting its most obvious advantages and potential aesthetic products developed.

Figure 1. Laser Furnace prototype designed and built within the LIFE/ENV ES560 CERAMGLASS Project. A 10x10 cm2 ceramic tile is being

processed with Laser line scanning at high temperature.

References

1. V. V. Lennikov et al., In-situ synthesis of composite MTiO3-Al2O3 coatings via Laser Zone Melting, Solid State Sciences 9 (2007) 404-409.

2. I. de Francisco et al., In-situ synthesis of rare earth aluminate coatings in the system Ln-Al-O (Ln = Y, Gd), Solid State Sciences 13

(2011) 1813-1819.

88

NOTES

89

Influence of peak power on the properties of Ti-Si-N films deposited by HiPIMS in deep oscillations magnetron sputtering (DOMS) mode

F. Fernandes, J.C. Oliveira, F. Ferreira, A. Cavaleiro

SEG-CEMUC - Department of Mechanical Engineering, University of Coimbra, Portugal

E-mail: joao.oliveira@dem.uc.pt

Abstract

Since Veprek et al. [1] reported the extremely high mechanical properties of nanocomposite TiSiN coatings

deposit by CVD, an extensive body of research works has been focused on the study and deposition of this

system. Depending on the deposition conditions, these coatings have been reported consisting of: i) nano-sized

TiN crystallites surrounded by an amorphous matrix of Si3N4 displaying very high hardness values, or ii)

substitutional solid solution of Si in TiN structure (not predicted by the Ti-Si-N phase diagram). The hardness of the

films have been shown to increase with increasing silicon content up to an optimal concentration and to

decrease with further silicon addition. Following the model proposed by Patscheider et al. [2], the maximum

hardness corresponds to the formation of the nanocomposite phase with optimized dimensions of both the TiN

crystallites and the Si3N4 amorphous matrix.

Substrate biasing has been shown to also influence the structure and mechanical properties of the TiSiN

films deposited by PVD [3]. In fact, energetic ion bombardment of the growing film can promote the formation of

the nanocomposite structure [4]. In the last decade, new magnetron sputtering deposition techniques have been

developed to produce highly ionized fluxes of sputtered material and, hence, to allow an increased control over

the energy and direction of the deposited species. One of the most recent developments is High Power Impulse

Magnetron Sputtering (HIPIMS) [5], also known as High-power Pulsed Magnetron Sputtering (HPPMS). In this work Ti-

Si-N thin films with similar Si content were deposited by Deep Oscillation Magnetron Sputtering (DOMS) [6], a

variant of HIPIMS. The effect of peak power on the structure, morphology and mechanical properties of TiSiN

coatings with similar Si content was studied. Comparison with coatings deposited by DC reactive magnetron

sputtering (DCMS) was also carried out.

References

1. S. Veprek , S. Reiprich, A concept for the design of novel superhard coatings, Thin Solid Films, 268 (1995) 64.

2. J. Patscheider, T. Zehnder , M. Diserens, Structure–performance relations in nanocomposite coatings, Surface and Coatings Technology,

146-147 (2001) 201.

3. F. Vaz, L. Rebouta , Ph. Goudeau , T. Girardeau , J. Pacaud , J.P. Riviere , A. Traverse, Structural transitions in hard Si-based TiN coatings: the

effect of bias voltage and temperature, Surface and Coatings Technology 146–147 (2001) 274.

4. Y. Zhang, Y. Yang, Y. Zhai, P. Zhang, Effect of negative substrate bias on the microstructure and mechanical properties of Ti–Si–N films

deposited by a hybrid filtered cathodic arc and ion beam sputtering technique, Applied Surface Science 258 (2012) 6897.

5. K. Sarakinosa, J. Alamib, S. Konstantinidisc, High power pulsed magnetron sputtering: A review on scientific and engineering state of the

art, Surface & Coatings Technology 204 (2010) 1661.

6. J. Lin, B. Wang, W.D. Sproul, Y. Ou, I. Dahan, Anatase and rutile TiO2films deposited by arc-free deep oscillation magnetron sputtering,

Journal of Physics D: Applied Physics 46 (2013) 084008.

90

NOTES

91

Thermal shield coatings for C/SiC materials

E. García1, A. Nistal1, M.A. Sainz1, M.I. Osendi1, P. Miranzo1, F. Martín de la Escalera2, Y. Essa2, A. Khalifa2

1 Institute for Ceramics and Glass (ICV-CSIC), Madrid, Spain

2 Aernnova Engineering Solutions Ibérica, Madrid, Spain

E-mail: garcia@icv.csic.es

Abstract

In nuclear and aerospace applications, materials must withstand high thermal and-mechanical loads. Due

to their good thermo-mechanical properties at high temperature, C/C or SiC-based composites are relevant for

these applications. The main drawbacks of these materials are their oxidation at temperatures above 500 C

which confines their use to inert or vacuum environments. Among the different approaches to reduce the loss of

inherent properties caused by oxidation, the more promising is the design of multi-layered coatings that fulfil the

whole requirements, such as chemical and mechanical compatibility with the substrate, low oxygen permeability

and thermal expansion coefficient close to that of C/C and SiC for reducing the level of residual thermal stresses.

In this context, glass-forming compositions are considered as potential candidates with the benefit of acting as

crack healing agent at service temperatures [1]. Among high temperature glass forming compositions, Y2O3-

Al2O3-SiO2 (YAS) system presents the advantage of having a relatively low eutectic point (1350-1400ºC) [2] which

make feasible the use of the cost effective oxyacetylene Flame Spray technique (FS) for producing YAS coatings

in just one processing step. In this work, a YAS composition is designed and tested as compatible coating for SiC.

The coatings produced by the oxyacetylene FS technique are characterized at different levels; i.e. crystalline

phases, mechanical and thermal properties are studied. The effect of thermal treatments performed at specific

temperatures on the coating properties is also evaluated.

Figure 1. SEM micrograph of a cross section of an as-sprayed YAS coating on SiC substrate previously coated with a Si bond coat.

References

1. F.J. Buchanan, J.A. Little, Particulate-containing glass sealants for carbon–carbon composites. Carbon 33 (1995) 491

2. H. Maoa, M. Selleby, O. Fabrichnaya, Thermodynamic reassessment of the Y2O3–Al2O3–SiO2 system and its subsystems CALPAHD 32

(2008) 399.

92

NOTES

93

Raman spectroscopy of ZrCN/ZrN multilayer coatings

F. Agulló-Rueda1 and J. Barriga2

1 Instituto de Ciencia de Materiales de Madrid, ICMM-CSIC, 28049 Madrid, Spain 2 IK4-Tekniker, Polo Tecnológico de Eibar, Calle Iñaki Goenaga, 5, 20600 Eibar, Spain

E-mail: far@icmm.csic.es

Abstract

Tribological ZrCN/ZrN multilayer coatings deposited on steel substrates by cathodic arc evaporation have been

studied by Raman spectroscopy at room temperature for 633 and 514 nm excitation wavelengths. The influence

of growth temperature and bias voltage has been discussed. The Raman spectra (Fig. 1) show disorder induced

bands below 1100 cm-1 due to ZrN lattice phonons [1-3] and the typical D and G bands of carbon compounds at

1350 and 1580 cm-1, respectively, due to graphitic carbon nanoclusters. A band at 600 cm-1 has been assigned

to the carbon atoms incorporated into the ZrN lattice. For increasing deposition temperature the carbon

concentration increases. For low bias voltages carbon deposits mostly as graphitic precipitates. As the bias

voltage increases part of the carbon atoms dissolve into the ZrN lattice. The N/Zr ratio increases with bias voltage

and decreases with layer depth. (Project Consolider FUNCOAT CSD2008-00023)

Figure 1. Raman spectra of ZrCN/ZrN multilayer coatings deposited at different temperatures and bias voltages (632.8 nm excitation laser

wavelength).

References

1. W. Spengler and R. Kaiser, First and Second Order Raman Scattering in Transition Metal Compounds, Solid State Commun. 18 (1976) 881. 2. C.P. Constable, J. Yarwood, and W.-D. Münz, Raman Microscopic Studies of PVD Hard Coatings, Surf. Coat. Technol. 116–119 (1995) 155. 3. E. Silva, M. Rebelo de Figueiredo, R. Franz, R. Escobar Galindo, C. Palacio, A. Espinosa, S. Calderon V., C. Mitterer, and S. Carvalho, Structure-

property relations in ZrCN coatings for tribological applications, Surf. Coat. Technol. 205 (2010) 2134.

94

NOTES

95

Active Screen Plasma Nitriding to improve tribology performance of Austenitic Stainless Steels with good corrosion resistance

J. A. Sánchez-Garcia1, M. Brizuela1, P. Corengia1, A. Larrañaga2, I. Braceras1,3

1Tecnalia, San Sebastián (Spain) 2Tratamientos Térmicos TTT S.A. Bergara (Spain)

3Ciber-BBN, San Sebastian (Spain)

Jangel.sanchez@tecnalia.com

Abstract

Active Screen (AS) is an advanced technology for plasma surface engineering that offers advantages

over conventional direct current (DC) plasma treatments: ability to treat complex geometries, high reproducibility,

uniform heating and the minimization of the bias voltage applied to the components and consequent minimal risk

of damage on the treated parts due to arcing.

The main objective of this work is to explore the potential of ASPN (Active Screening Plasma Nitriding),

particularly the role of the different experimental parameters on the nitriding response of 316L stainless steel.

Stainless steel typically shows good corrosion resistance but poor tribology, Conventional nitriding can improve the

tribological properties of the steel, but typically decreases significantly its corrosion resistance.

316L was plasma nitrided under different parameters and characterized by various techniques.

Microhardness test was used to measure hardness and nitruration depth, pin-on disk under controlled atmosphere

to study friction and wear, X-ray diffraction to determine the different phases at the surface, glow discharge

optical emission spectroscopy (GD-OES) to evaluate the concentrations of N, O and various alloying elements

present in the surface of the nitrided samples. Finally, corrosion resistance of the steel was assessed.

The results have shown the dependency of the surface composition and microstructure with ASPN

parameters. Additionally, it has been shown that good corrosion resistance can be retained in ASPN treated 316L,

while improving the tribology performance, thus achieving a good compromise between these properties.

References 1. Paul Hubbard, Thesis: Characterization of a commercial Active Screen Plasma Nitriding System (2007)

2. E. de las Heras, P. Corengia, D. Gonzalez-Santamaria, A. Garcia-Luis, M. Brizuela, G.A. Lopez and M. Flores-Martinez, Duplex Surface

treatment of 316L stainless Steel, microstructure and tribological behaviour. Surface & Coat. Techn. 202 (2008) p. 2945

3. Design and development of a system of plasma assisted nitriding with active grid (ASPN): First results. J.A. Sanchez-Garcia, I.

Braceras, J.C. Antolin, A. Larrañaga, and P. Corengia. Proceedings TRATERMAT 2012

96

NOTES

97

Enhancement of corrosion behaviour in pressure vessels weldments through silica nanoparticles addition

E. Carneiro1,2 and S. Carvalho1,3

1 GRF-CFUM, University of Minho, Campus of Azurém, 4800-058 Guimarães, Portugal

2 PROHS – Equipamento Hospitalar e Serviços Associados, S.A., 4476-908 Maia

Portugal 3 SEG-CEMUC Mechanical Engineering Department, University of Coimbra, 3030-788 Coimbra, Portugal

E-mail: edgar.carneiro@fisica.uminho.pt

Abstract

Hospital sterilizers and autoclaves usually fail due to corrosion phenomena, inside the pressure chamber,

near the welding zones. Despite the good corrosion resistance of 316L stainless steel, after TIG welding the

characteristics of the heat affected zone (HAZ) are adversely affected. These occurrences oblige to costly repair

operations, severely limiting the service life of these devices.

In this work, two distinct size silica nanoparticle solutions were obtained by Stöber method [1] and then

manually applied onto the metal surface before welding. Cyclic potentiodynamic polarization (CPP)

measurements were performed in 5mm thick 316L SS welded by an A-TIG process in a 3.56% NaCl solution. The

results were correlated with microstructural features of the material in three separated zones as well as chemical

surface composition.

The presence of the active flux during the joining process substantially alters the CPP curve for both weld

metal and HAZ. The typical rapid rise in current, which occurs when the “pitting potential” is reached, is eliminated

suggesting an enhancement in corrosion resistance in those critical zones.

References

1. W. Stöber, A. Fink, E. Bohn, Controlled growth of monodisperse silica spheres in the micron size range, J. Colloid Interface Sci. 26

(1968) 62–69.

98

NOTES

99

Author Index

Abad M. D. 69

Agüero A. 25,51,59,61,63

Agulló-Rueda F. 93

Albella J.M. 17

Alcalá G. 23,

Alegre D. 31,33

Almandoz E. 65,81

Alonso R. 71

Alvarez R. 73

Álvarez-Fraga L. 17

Amigó V. 65

Angurel L. A. 87

Arenas M. A. 39,69

Balmain J. 29

Baraibar I. 25,51,63

Baraka T. El 61

Barranco A. 75

Barriga J. 93

Bonnet G. 29

Borrasa A. 75

Bouchaud B. 29

Braceras I. 95

Brizuela M. 19,23,49,83,95

Brossard M. 29

Cano D. 45

Carneiro E. 97

Carretero E. 71

Carvalho S 41,43,97

Castañeda S.I. 55

Cavaleiro A. 21,41,89

Céspede E. 17

Conde A. 39,69

Corengia P. 19,95

Cotrino J. 73

Couto M. 79

Davydenko L. A. 57

Davydenko L. 57

de Castro A. 31,33

de Damborenea J. 39,69

de Francisco I. 87

de la Fuente G. F. 87

Díaz C. 37,45

Domínguez J. A. 63

Domínguez -Meister S. 67.83

Dörfel I. 57

Dosta S. 79

Esbrit P. 39

Escobar Galindo R. 17,23

Essa Y. 91

Esteban J. 39

Estepa L. C. 87

Esteve J. 45

Fernandes F. 89

Fernández-Carretero F. 19

Ferreira F. 21,89

Ferrer F.J. 73

Fietzek H. 53

Fuentes G. G. 45,65,81

García E. 27,91

García F. 75

García I. 69

Garcia-Cano I. 79

García-Esc osa E. 69

Garcia-Luis A. 19

Garcia-Martin J.M. 73

Gómez- Barrena E. 39

González V. 25,51

González-Elipe A. R. 73,75,87

Gonzalez-Santamaria D. 19

Guilemany J.M. 79

Gutiérrez M. 25,51

Hernandez-Lopez J. M. 39

Hernández-Pinilla D. 17

Illana A. 49

Juez-Lorenzo M. 53

Khalifa A. 91

Kolarik v. 53

Kranzmann A. 57

Kuchenreuther V. 53

Kulkarni S. 65

Lanceros-Mendez S. 41

Larrañaga A. 95

Lennikov V. V. 87

Lopez-Santos M.C. 73,75

Lousa A. 45

Lozano D. 39

Mändl S. 37

Manninen N. K. 41

Mariscal A. 69

Marques S. M. 41

Martín de la Escalera F. 91

Martínez de Olcoz L. 45

100

Martínez-Pérez M. 39

Martin-Rojo A.B. 31

Mato S. 23,49.81

Miranzo P. 27,91

Mora J. 59

Mosquera-Feijoo M. 57

Muelas R. 25

Nasiedkin D. 57

Nassiedkin D. 57

Nazarchuk M. 57

Nazarchuk M. 57

Nistal A. 27,31

Nofz M. 75

Oliveira J.C. 35,37

Osendi M. I. 27,91

Otazu D. 81

Oyarzabal E. 73

Palacio J. F. 65

Palmero A. 73

Parra-Barrancxo J. 75

Pedraza F. 29

Pereira J. C. 85

Pereiro R. 37

Pérez F.J. 23,49,55,57,81

Pérez-Jorge C. 39

Plana D. 25

Plyuto Yu 57

Plyuto Yu. 57

Portal-Núñez S. 39

Prieto C. 17

Rico V. 73,87

Rodriguez R. J. 65

Rojas T. C. 67,83

Sainz M.A. 91

Sainz M. A. 91

Saliwan-Neumann R. 57

Sánchez –García J.A. 95

Sánchez O. 17

Sánchez-Garcia A. 17

Sánchez-López J.C. 49,67,69,83

Sánchez-Mancilla M. A. 49

Sansom G. 15

Sojref R. 57

Tabarés F. L. 31,33

Tafalla D. 31

Tobar M. J. 85

Tonnillier X. 15

Yañez A. 85

Zambrano J. C. 85

2

PARTICIPANT´S LIST – XTREMECOAT 2014

Agüero Bruna A. INTA

Dept. Materiales y Estructuras

Ctra. Ajalvir KM.4

Torrejón de Ardoz

28850 Madrid

Spain agueroba@inta.es

Agulló-Rueda F. Instituto de Ciencia de Materiales de

Madrid - CSIC

Cantoblanco

28049 Madrid

Spain

Albella Martín Instituto de Ciencia de Materiales de

Madrid - CSIC

Cantoblanco

28049 Madrid

Spain jmalbella@icmm.csic.es

Alcalá G. Universidad Complutense de Madrid

Dept. Ciencia de los Materiales e Ingeniería

Metalurgica

Avda. Complutense s/n

28040 Madrid

Spain galcalap@ucm.es

Almandoz Sánchez E. AIN

AIN-TECH

Carretera de Pamplona 1

Cordovilla

31191 Pamplona

Spain ealmandoz@ain.es

Alonso R. Universidad de Zaragoza

Dept. de Física Aplica

Pedro Cerbuna 12

50009 Zaragoza

Spain ralonso@unizar.es

Arenas Vara M. A. CENIM

Dept. Surface Engineering, Corrosion and

Durability

Av. Gregorio del Amo 8

28040 Madrid

Spain geles@cenim.csic.es

Baráibar I. INTA

Dept. Metallic Materials

Ctra. Ajalvir km. 4

Torrejón de Ardoz

28850 Madrid

Spain baraibargmi@inta.es 34915202111 34915201592

Barriga J. IK4-TEKNIKER

Dept. Surface and Technology

Iñaki Goenaga 5

Eibar 20600

Spain Jbarriga@tekniker.es

Brizuela M. Tecnalia Research & Innovation

Dept. Materials for Energy Area

Mikeletegi Pasealekua 2

20009 San Sebastián

Spain marta.brizuela@tecnalia.com

Carneiro E. University of Minho & PROHS

Equipamento Hospitalar e Serviços

Physics Dept.

Campus de Azurém

4804-533 Azurém Guimaraes

Portugal edgar.carneiro@fisica.uminho.pt

Carretero E. Universidad de Zaragoza

Dept. De Fisica Aplicada

Pedro Cerbuna 12

50009 Zaragoza

Spain ecarre@unizar.es

3

Carvalho S. SEG-CEMUC

Dept. of Mechanical Engineering

University of Coimbra

Rua Luis Reis Santos

3030-788 Coimbra

Portugal sandra.carvalho@fisica.uminho.pt

Castañeda Quintana S. Universidad Complutense de Madrid

Dept. Ciencia de los Materiales e Ingeniería

Metalurgica

Avda. Complutense s/n

28040 Madrid

Spain sicastan@quim.ucm.es

Conde del Campo A. CENIM

Dept. Surface Engineering, Corrosion and

Durability

Av. Gregorio del Amo 8

28040 Madrid

Spain a.conde@cenim.csic.es

Damborenea J.J. CENIM

Dept. Surface Engineering, Corrosion and

Durability

Av. Gregorio del Amo 8

28040 Madrid

Spain jdambo@denim.csic.es

Davydenko L. Cuiko Institute of Surface Chemistry

Lab. Of Nanochemistry of Functional

Coatings

General Naumov Str. 17

03164 Kiev

Ukraine nasedkin@isc.gov.ua

de Castro A. Asociación EURATOM-CIEMAT para Fusión

Lab. Nacional de Fusión

Av. Complutense 22

28040 Madrid

Spain alfonso.decastro@ciemat.es

de la Fuente G.F.

FICMA (CSIC-Universidad de Zaragoza)

Dept. Materials for Energy and Laser

Processing

Maria de Luna 3

50018 Zaragoza

Spain xerman@unizar.es

de Segovia J.L. Instituto de Ciencia de Materiales de

Madrid

Sor Juana Inés de la Cruz 3

Cantoblanco

28040 Madrid

Spain jldesegovia@icmm.csic.es

Domínguez Aguililla J.A. INTA

Lab. De Procesos y Tecnologías. Área de

Materiales

Ctra. Ajalvir Km. 4

Torrejón de Ardoz

28850 Madrid

Spain baraibargmi@inta.es

Dominguez Meister Instituto de Ciencia de Materiales de

Sevilla, ICMS-CSIC

Av. Americo Vespucio 49

41092 Sevilla

Spain s.dominguez@csic.es

Esteban J. IIS-Fundación Jiménez Díaz

Dept. Clinical Microbilogy

Av. Reyes Católicos

28040 Madrid

Spain jestebanmoreno@gmail.com

Esteve J. Univeristat de Barcelona

Dept. Física Aplicada i óptica

Marti i Franques 1 - planta 5

08028 Barcelona

Spain Joan.Esteve@gmial.com

Fernandes F. SEG-CEMUC

Dept. of Mechanical Engineering

4

University of Coimbra

Rua Luís Reis Santos

3030-788 Coimbra

Portugal filipe.fernandez@dem.uc.pt

Ferreira F. SEG-CEMUC

Dept. of Mechanical Engineering

University of Coimbra

Rua Luís Reis Santos

3030-788 Coimbra

Portugal fabio.ferreia@demuc.pt

García Diego I.M. CENIM

Dept. Surface Engineering, Corrosion and

Durability

Av. Gregorio del Amo 8

28040 Madrid

Spain igarcia@cenim.csic.es

García Fuentes G. AIN

AIN_TECH

Carretera de Pamplona

Cordovilla

31191 Pamplona

Spain gfuentes@ain.es

García Granados E. Instituto de Cerámica y Vidrio (ICV-CSIC)

Dept. Cerámica

28049 Madrid

Spain garcia@icv.csic.es

González Martín V. INTA

Dept, Metallic Materials

Ctra. De Ajalvir km. 4

Torrejón de Ardoz

28850 Madrid

Spain gonzalezmv@inta.es

González-Elipe A. Univesidad de Sevilla-CSIC

Instituto e Ciencia de Materiales de Sevilla

Av. Americo Vespucio 49

41092 Sevilla

Spain arge@icmse.csic.es 34954489528 A.

Gracia-Escosa E. CENIM

Dept. Surface Engineering, Corrosion and

Durability

Av. Gregorio del Amo 8

28040 Madrid

Spain elenagracia@cenim.csic.es

Guilemany J.M. Thermal Spray Centre (CPT)

Dept. Ciéncuia dels Materials i Enginyeria

Metal-Lúrgica

University of Barcelona

Marti Franqués 1

080228 Barcelona

Spain jmguilemany@cptub.eu

Gutiérrez del Olmo M. INTA

Dept, Metallic Materials

Ctra. De Ajalvir km. 4

Torrejón de Ardoz

28850 Madrid

Spain gutierrezdom@inta.es

Illana A. Universidad Complutense de Madrid

Dept. Ciencia de los Materiales e Ingeniería

Metalurgica

Avda. Complutense s/n

28040 Madrid

Spain ailla01@ucm.es

Juez Lorenzo M.M. Fraunhofer ICT

Dept. Energetic System

Joseph-von-Fraunhofer

76327 Pfinztal

Germany Maria.juez-lorenzo@ict.fraunhofer.de

Kranzmann A. BAM Federal Inst. for Materials Research

and Testing

5

Divison 5.1

Unter den Eichen 87

12205 Berlin

Germany Michaela.kay@bam.de

Lousa A. Univeristat de Barcelona

Dept. Física Aplicada i óptica

Marti i Franques 1 - planta 5

08028 Barcelona

Spain Alousa@ub.edu

Manuelas Gamo R. INTA

Dept. Materials and Structures

Crta. De Ajalvir

28850 Madrid

Spain Modsur3.pers_externo@inta.es

Marques S.M. University of Minho

Physics Dept.

Campus de Azurém

Guimaraes

4800-058

Portugal mariana.marques@fisica.uminho.pt

Mato Díaz Universidad Complutense de Madrid

Dept. Ciencia de los Materiales e Ingeniería

Metalurgica

Avda. Complutense s/n

28040 Madrid

Spain msmatodi@quim.ucm.es

Mora J. Isdefe

Materials (INTA)

Ctra. De Ajalvir Km.4

Torrejón de Ardoz

28850 Madrid

Spain jmora@isdefe.es

Mosquera Feijoo M. BAM Federal Inst. for Materials Research

and Testi

Divison 5.1

Unter den Eichen 87

12205 Berlin

Germany Michaela.kay@bam.de

Nasiedkin D. Cuiko Institute of Surface Chemistry

Lab. Of Nanochemistry of Functional

Coatings

General Naumov Str. 17

03164 Kiev

Ukraine nasedkin@isc.gov.ua

Nistal González A. Instituto de Cerámica y Vidrio (ICV- CSIC)

Dept. Cerámica

Kelsen 5

28049 Madrid

Spain andresnistal@icv.csic.es

Oyarzabal E. Foundation UNED (CIEMAT)

Dept. Plasma-wall-interaction

Av. Complutense 22

28040 Madrid

Spain Eider.oyarzabal@externos.ciemat.es

Palmero A. CSIC-Universidad de Sevilla

Instituto de Ciencia de Materiales de Sevilla

Av. Americo Vespucio

41092 Sevilla

Spain Alberto.palmero@csic.es

Pedraza F. Université de La Rochelle

LaSIE UMR-7356 CNRS

Pole Scienceas er Technologie

La Rochelle

17042 cedex 1

France fpedraza@univ-lr.fr

Pereira Falcon J.C. Universidad Politécnica de Valencia

Camino de la Vera s/n

46022 Valencia

Spain jpereira@uc.edu.ve

Pérez Trujillo F.J Universidad Complutense de Madrid

6

Dept. de Ingeniería de Superficies y

Mateiales Nanoestructurados

Facultad de Ciencais Químicas

28040 Madrid

Spain fjperez@ucm.es

Plana D. INTA

Dept. Matariales

Ctra. De Ajalvir Km. 4

Torrejón de Ardoz

28850 Madrid

Spain planad@inta.es

Prieto C. Instituto de Ciencia de Materiales de

Madrid

CSIC

Cantoblanco

28049 Madrid

Spain cprieto@icmm.csic.es

Rojas Ruiz T.C. Instituto de Ciencia de Materiales de Sevilla

(ICMS)

Av. Americo Vespucio 49

41092 Sevilla

Spain tcrojas@icmse.csic.es

Sanchez-Lopez J.C. Instituto de Ciencia de Materiales de Sevilla

(ICMS)

Av. Americo Vespucio 49

41092 Sevilla

Spain JCSLOPEZ@ICMSE.CSIC.ES

Sansom C. Global CSP Laboratory

Cranfield University

Beldfordshire MK43 0AL

Cranfield

3030-788

UK c.l.sansom@cranfield.ac.uk

Schulz W. BAM Federal Institute for Materials

Research and Testing

Dibvision 5.1

Berlin

12205

Germany Michaela.kay@bam.de