Reactivity between aluminum and (Ti,Al)N coatings for casting dies

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Thin Solid Films 516 (2

Reactivity between aluminum and (Ti,Al)N coatings for casting dies

E.K. Tentardini a, C. Aguzzoli a, M. Castro b, A.O. Kunrath c, J.J. Moore c,C. Kwietniewski d,⁎, I.J.R. Baumvol a,d

a Universidade de Caxias do Sul, CCET. Av. Francisco G. Vargas 1130, 95070-560 Caxias do Sul RS, Brazilb Universidade Federal de Minas Gerais, 31270-901 Belo Horizonte MG, Brazil

c Advanced Coatings and Surface Engineering Laboratory (ACSEL), Colorado School of Mines. 1500 Illinois St., Golden CO, 80401-1887, USAd Universidade Federal do Rio Grande do Sul, 91501-970 Porto Alegre RS, Brazil

Received 12 September 2006; received in revised form 17 October 2007; accepted 18 October 2007Available online 26 October 2007

Abstract

The susceptibility to reaction with solid and liquid aluminum of TiN and (Ti,Al)N coatings was investigated using complementary differentialscanning calorimetry and X-ray diffraction. Special freestanding, multilayered thin film structures of aluminum and the testing coating materialwere prepared for the calorimetric analyses. The results indicate that increasing concentrations of Al in the (Ti,Al)N compound coatings shift thereactions between coating and aluminum towards higher temperatures, reducing significantly the heat of reaction and inhibiting Al–Ti intemetalliccompound formation. Different effects determining the protective action of this kind of coating are discussed on the basis of the present findings,together with others from the literature. Aluminum-rich Ti1− xAlxN compound coatings, with x ranging from 0.6 to 0.7, are apparently inert (non-wettable) in the presence of aluminum up to 1000 °C, a temperature high enough to resist any known aluminum casting situation.© 2007 Elsevier B.V. All rights reserved.

Keywords: Intermetallic; XPS; X-ray diffraction; Nanohardness

1. Introduction

Chemical reaction involving the molten metal and the surfaceof the die is one of the importantmechanisms that lead to failure inaluminum die casting. Soldering is among the resultingphenomena that arise as a consequence of these reactions and itsoccurrence leads to damage to the die and poor surface quality ofthe casting [1–3]. An approach frequently used to lessen thisproblem is the deposition of a protective coating on the surface ofthe conventional die material, normally AISI H13 tool steel. Diesrepresent a significant part of processing cost and the coatingapproach is preferred to a complete change of the die material. Anideal coating would be chemically inert (non-wettable with alum-inum), adherent to the casting die, effective as a diffusion barrier,resistant to erosion and capable of enduring the mechanical andthermal cycling during die casting operation. The design method-

⁎ Corresponding author.E-mail address: [email protected] (C. Kwietniewski).

0040-6090/$ - see front matter © 2007 Elsevier B.V. All rights reserved.doi:10.1016/j.tsf.2007.10.088

ology for optimized die materials and coatings, discussing thepotentialities of diematerials and compound, graded, multilayeredand duplex coatings has been recently reviewed [4]. Preliminaryresults on differential scanning calorimetry (DSC) were used asillustrations, since this technique can be a powerful research tool indetermining the onset temperature and the nature of chemicalreactions taking place between a candidate die material or coatingand the aluminum melt.

(Ti,Al)N films have been used in several tribological applica-tions including cutting tools and forging dies [5–7]. The ability of(Ti,Al)N coatings to form a passive alumina (Al2O3) layer on itssurface greatly improves the coating resistance to oxidation andcorrosion at high temperatures. The structure of Ti1−xAlxN com-pounds can be either cubic (B1) or hexagonal (B4) depending onthe actual value of x. For x varying from zero to 0.6 the structure ofthe film is the same as that of TiN [8], i.e. rock salt or B1. For xvarying from 0.6 to 0.7 both phases may occur, whereas for xvalues exceeding 0.7 the film normally presents the wurtzite,hexagonal, or B4 structure which is characteristic of AlN. Thealuminum content and film structure are determining factors on the

http://dx.doi.org/10.1016/j.tsf.2007.10.088

Fig. 1. Rutherford backscattering yields of 2 MeV incident He+ ions from thethree different Ti1− xAlxN film coatings on polished AISI 304 stainless steelsubstrates.

3063E.K. Tentardini et al. / Thin Solid Films 516 (2008) 3062–3069

properties of the film and several publications have proved theserelationships [9–11].

We report here on the reactivity of Ti1− xAlxN coatings in thepresence of aluminum. Ti1− xAlxN coatings with different valuesof x were used, namely x equal to zero, 0.3, 0.5, and 0.7.Compositional, structural, and mechanical analyses were per-formed to characterize the films evaluated in the chemicalreaction tests.

2. Experimental details

Films of Ti1− xAlxN, x=0, 0.3, 0.5, 0.7 were prepared forthis study using reactive unbalanced magnetron sputtering. TheTi1− xAlxN coatings were produced by co-deposition fromtitanium and aluminum targets positioned at 45° with respect toeach other. Polished AISI 304 stainless steel substrates wereemployed for X-ray diffraction (XRD) analysis and nanohard-ness measurements of the films. For calorimetric chemicalreactivity studies, freestanding films containing the test materialand aluminum were deposited on flexible AISI 316L stainlesssteel coupons and peeled off by bending the substrate. This lastgroup of film samples consisted of a multilayered structure withalternate layers of aluminum and test material with a totalthickness between 4 and 5 μm. Aluminum films were typically0.9 to 1 μm thick and TiN and (Ti,Al)N films were 1.2 to 1.3 μmthick. The films were then reduced to small flakes and placed inalumina crucibles for DSC.

Prior to deposition, all substrates were submitted to ultra-sonic cleaning in acetone and ethanol, respectively and insidethe deposition chamber they were sputter etched at 400 V in8.7 Pa of argon.

A nanoindenter Fisherscope HV 100 was used for hardnessand Young's modulus measurements. Indentations were con-ducted with a Berkovich geometry indenter, to amaximum depthof 100 nm. Even considering that the steel of interest for castingdies applications would be of the H13 kind, AISI 304 substratescould be confidently used for nanohardness measurements of theTi1− xAlxN films. Indeed, at the indentation depths used here thehardness of the films will not be influenced by the steelsubstrates. A differential scanning calorimeter (Netzsch model404) was used in the thermal analysis. DSC analyses were runwith 5mg samples at 4 different heating rates (5, 10, 15 and 20 Kmin−1) from room temperature to 1000 °C. A Philips X'PertPRO X-ray diffraction equipment was used to characterize the

Table 1Reactive sputtering deposition parameters of Ti1− xAlxN films

Nominal composition x=0 x=0.3 x=0.5 x=0.7

Power to Ti target (W) 1000 1000 1000 1000Power to Al target (W) 0 200 500 800Base pressure (Pa) b5×10−4

Working pressure (Pa) 2.4×10−4

Ar:N2 ratio 7:3Substrate bias 50 V pulsed at 50 kHz with 1 μs of

reverse timeTarget to substrate distance (mm) 150Deposition time (min) 90

freestanding film samples before and after thermal analysis. Thediffractograms were taken in a θ−2θ geometry, with entranceand exit slits of 1.1mm, and 0.02° angular steps. Copper K-alpharadiation was used (λ=0.15405 nm).

Preliminary work was performed to establish the parametersneeded to achieve a range of film compositions that would yielddifferent structures and consequently mechanical properties.The deposition parameters selected for this work are presentedin Table 1.

Complementary Rutherford backscattering (RBS) and cali-brated energy dispersive X-ray spectrometries, as well as X-rayphotoelectron spectroscopy (XPS) calibrated by RBS andnuclear reaction analysis [12,13] were used to determine filmelementary and chemical compositions. The same samples usedfor nanohardness measurements were used for film compositiondeterminations.

3. Results and discussion

Fig. 1 shows the He+ RBS spectra for the different Ti1− xAlxN,x=0.3, 0.5, 0.7 samples on polished AISI 304 stainless steelsubstrates. The incidence energy of the He+ ions was 2 MeVandthe detection angle was 160° with the direction of incidence. TheAl/Ti ratios determined from Fig. 1 confirmed the aimedcompositions within the accuracy of the method, namely 5%.XPS analysis was undertaken to complement the elementarycomposition analysis by cross-checking the RBS results and toinspect the chemical composition of the films. N 1s and Al 2p X-ray photoelectron intensity groups in Fig. 2 were calibrated by thenuclear reactions 14N(d,α)12C at 1.45 MeV [12] and 27Al(p,γ)28Si at 992 keV [14]. On the other hand, the (Ti 2p)/(Al 2p)photoelectron intensity ratios were calibrated using the RBSresults of Fig. 1. The average Ti1− xAlxN film compositions agreewith the aimed ones declared above, within the accuracy of theused methods which is again about 5%. Furthermore, comparingthe XPS results obtained here with previous results in theliterature [15–17], one can see that in near surface regions of ourfilms the composition is a mixture of Ti1− xAlxN and Ti–Aloxynitrides, whereas in the bulk it is essentially Ti1− xAlxN.Contributions to the photoelectron spectra in Fig. 2 due to

Fig. 2. Ti 2p, Al 2p, and N 1s X-ray photoelectron groups at a 30° take-off anglefrom the Ti1− xAlxN film coatings on polished AISI 304 stainless steelsubstrates. The components in the photoelectron spectra originated fromtitanium-aluminum oxynitrides – (Ti,Al)ON – are indicated by arrows.

Fig. 3. X-ray diffraction patterns of substrate and as-deposited coatings ofTi1 − xAlxN coatings, produced by co-deposition from titanium and alu-minum targets positioned at 45° with respect to each other, using polishedAISI 304 stainless steel substrates.

3064 E.K. Tentardini et al. / Thin Solid Films 516 (2008) 3062–3069

titanium–aluminum oxynitrides are indicated by arrows andlabeled (Ti,Al)ON. The XRD patterns shown in Fig. 3 for theTi1− xAlxN films confirm the results from the literature [8, 10],namely that the films retain the B1 cubic structure for x=0, 0.3,and 0.5, whereas for x=0.7 they assume mainly the B4 hexa-gonal structure.

In the same lines, Fig. 4 shows the results of nanohardnessmeasurements for Ti1− xAlxN films on polished AISI 304stainless steel substrates, confirming previous observations [8]that indicate an increase in hardness and Young modulus forx=0.3 and 0.5 with respect to x=0. A pronounced decrease isobserved at x=0.7, consistent with the presence of the B4

hexagonal structure of the latter. Although the hardness valuesfor the present Ti1− xAlxN are consistent with those of theliterature, the values of the Young modulus here determined aresubstantially smaller, which may be due to differences in de-position conditions.

Reactions that proceed at a rate that varies with temperaturepossess activation energies and present a peak shift in the DSCscan with varying heating rates. For those reactions that couldbe isolated, the peak (maximum) temperatures in the DSC plotwere recorded for each heating rate and the Kissinger model forfirst order reaction can be applied to extract activation energyvalues [18, 19]. The peak temperature, Tm, and the heating rate,Φ, are related to the activation energy, Q, by the followingequation:

d ln UT2m

� �

d 1Tm

� � ¼ �Qk

where k is the Boltzmann constant. Thus, the activation energycan be extracted from a logarithmic plot of α /Tm

2 versus Tm−1.

Since the scans took the system to temperatures far above thealuminum melting point, one notices that the present thin filmreactions take place in the solid or, eventually solid–liquidphases [20,21].

The DSC plots for the TiN/Al thin film multilayers shown inFig. 5(a) exhibit two exothermic peaks. Onset temperatures for

Fig. 4. Hardness and Young's modulus as a function of aluminum concentrationin the Ti1− xAlxN polished AISI 304 stainless steel substrates.


5 K min−1 heating rate were around 860 and 933 K, for the firstand second reactions, respectively. For higher heating rates,slightly higher onset temperatures for the two reactions wereobserved. No evident endothermic peak for the melting ofaluminum was observed, indicating that most of the aluminumfilm layers undergone a solid phase reaction with TiN filmlayers. XRD analysis of final products, Fig. 5(b), indicates theformation of the TiAl3 intermetallic compound. From the XRD

Fig. 5. (a) Differential scanning calorimetry plot of TiN film at four differentheating rates; (b) X-ray diffraction patterns of TiN+Al films before and after thedifferential scanning calorimetry analysis.

results, one cannot disregard the possibility that some of thealuminum could be in solid solution within the TiN rock saltstructure [8]. The calculation of the activation energy via theKissinger equation yielded questionable values probably due tothe proximity between the two reactions as well as to theirproximity to the melting point of aluminum. Thus, the use ofTiN as a coating for aluminum casting dies will lead to theformation of an intermetallic compound, namely TiAl3. Inter-metallic formation has been described [22–24] as the origin ofsoldering, a major die failure mode. It is noteworthy from thepresent DSC results that the TiAl3 intermetallic is apparentlyformed at or below the melting temperature of Al. This factpoints out to a solid state reaction, which may be diffusion-controlled, even if the activation energies could not be deter-mined satisfactorily.

The DSC results for the Al/Ti0.7Al0.3N multilayered structurein Fig. 6(a) showed a shift in the onset temperature for theexothermic reactions. In this case, reaction only starts after thealuminum layers melt at 933 K, probably triggering the reactionwith the Ti0.7Al0.3N film. TiAl3 is again noticed in the XRDresults of Fig. 6(b), among the products generated after the DSCexperiment. The formation of the TiAl3 intermetallic in the Al/Ti0.7Al0.3N multilayered films at a temperature slightly above themelting point of aluminum is an indication that, although dif-fusion-controlled solid state reaction cannot be disregarded, theprocess is now also assisted by the solid–liquid couple mecha-nism [25]. In any case, the non-wettability of the coating byaluminum is not assured. Therefore, although the hardness and

Fig. 6. (a) Differential scanning calorimetry plot of Ti0.7Al0.3N film at 4 differentheating rates; (b) X-ray diffraction patterns of Ti0.7Al0.3N+Al films before andafter the differential scanning calorimetry analysis.

Fig. 7. (a) Differential scanning calorimetry plot of Ti0.5Al0.5N film at 4 differentheating rates; (b) X-ray diffraction patterns of Ti0.5Al0.5N+Al films before andafter the differential scanning calorimetry analysis.

Fig. 8. (a) Determination of activation energy associated with reactions betweenTi0.5Al0.5N and aluminum indicated by peaks 1 and 2 in Fig. 7(a). (b) Square ofthe fractions of reaction, α2, versus time, t, for peak 1 in the 15 K/min DSCcurve and for peak 2 in the 20 K/min DSC curve of Fig. 7(a).


Young modulus of the Ti0.7Al0.3N compound are substantiallyhigher than those of TiN, this coating is not expected to lead tomajor improvement of casting die performance.

For x=0.5, the onset temperature for reactions in the Al/Ti0.5Al0.5N multilayered thin film structure shifts further towardshigher temperatures. Two exothermic peaks are observed and areindicated as 1 and 2 in Fig. 7(a). The XRD analysis of Fig. 7(b),before and after the DSC experiment, again shows the presence ofTiAl3 among the products. These higher onset temperatures forthe exothermic reactions are indicative that a higher concentrationof Al in the Ti1− xAlxN compound creates a diffusion barrier thatinhibits solid state reaction, even if it does not prevent it entirely.The easily distinguishable peak temperatures for each reactionallowed us to plot in Fig. 8(a) the ln(Φ /Tm

2 ) as a function of 1 /Tmand thus obtaining the activation energy values for both reactions,whose figures are 1.85 eV for peak 1 in Fig. 7(a) and 1.5 eV forpeak 2. Reaction enthalpies were obtained by integration of theexothermic peaks of Fig. 7(a), giving 1.60 and 1.44 eV, for peaks1 and 2, respectively. The reaction enthalpy determined frompeak2 compares well, within experimental accuracy, with thecorresponding activation energy, whereas there is an appreciabledisagreement in the case of peak 1. However, the Kissingerequation above only holds for a first order reaction, but not in caseof a diffusion-controlled rate, and therefore it might not beadequate to interpret the results.

Thermokinetic analyses of diffusion-controlled reactionshave been investigated under several different approaches [26].

In the present case we calculated from the DSC exothermicpeaks of Fig. 7(a) the fractions of reaction, α, completed atdifferent times t [27]. Two alternative equations recentlyreported in the literature were used to fit diffusion-controlledreaction kinetics data: a) the first equation [25] was employedfor the direct chemical reaction of Ti (solid) and Al (liquid) toform TiAl3

lndadt

� �¼ � E

kTþ ln Af að Þ½ �

where A, E, k, T, and f(α) are the apparent pre-exponentialfactor, apparent activation energy, Boltzmann constant, tem-perature, and kinetic model function and (b) the second one isessentially the Avrami model [28, 29]

ln � ln 1� að Þ½ � ¼ n ln t þ nlnk

where k is the kinetic rate constant and n the Avrami exponent.None of these equations gave a satisfactory (i.e. linear) fit to thedata and therefore activation energies and reaction orders couldnot be determined from them.

A final approach was made by considering that the physicalprocess in force in the planar structure formed by the Al/TiAlN


multilayer requires a limiting reactant diffusing across reactionproducts formed at the interface. Assuming a progressing, uni-directional reaction front, a simple parabolic reaction kineticsmodel was adopted [30]

a2 ¼ kpt

where kp is the parabolic rate constant including the diffusioncoefficient of the migrating species, Al in the present case. InFig. 8(b), α2 is plotted as a function of time for peak 1 in the15 K min−1 and for peak 2 in the 20 K min−1 DSC curves ofFig. 7(a). The obtained linear fits of Fig. 8(b) are representativeof the good fits obtained for all exothermic peaks of Fig. 7(a).This allowed to determine kp and assuming Arrhenius behaviorfor its dependence on the peak maximum temperature

kp ¼ A exp �E=kTmð Þ

the activation energies could be determined, although with apoor accuracy of about 20%. The figures were 1.77 and 1.40 eVfor peaks 1 and 2, respectively, which are consistent with thereaction enthalpies mentioned above.

The DSC results for the Al/Ti0.3Al0.7N multilayered filmstructures in Fig. 9(a) do not show any exothermic peak. At this

Fig. 9. (a) Differential scanning calorimetry analysis of Ti0.3Al0.7N film at fourdifferent heating rates; (b) XRD patterns of Ti0.3Al0.7N+Al films before andafter the differential scanning calorimetry analysis.

Al concentration, Ti1− xAlxN coatings seem to be inert (non-wettable) in the presence of aluminum up to 1273 K (1000 °C), atemperature high enough to resist any known aluminum castingsituation. Consistently, the diffraction peaks of Fig. 9(b) can beall assigned either to Al or to (Ti,Al)N, without any evidence forthe formation of TiAl3 or other intermetallics. At this Alconcentration the (Ti,Al)N compound consists [8] of a mixtureof the B4 and B1 crystallographic phases. In the B1 phase, Alatoms substitute Ti atoms in cubic TiN, the lattice parametersdecreasing with the increase of x. This more compact, cubic B1+hexagonal B4 structure together with a higher Al concentrationare responsible for the formation of an effective diffusion barrierthat slows down solid state reactions as well as solid–liquidreactions. Indeed, superior oxidation resistance, as well as otherproperties that rely on diffusion barriers has been demonstrated[8] for Ti1− xAlxN, with x in the 0.6 to 0.7 range. The action ofAl, alumina (Al2O3), as well as aluminum nitride and oxynitridesas effective diffusion barriers at high temperatures has beendescribed in the literature, either in the specific field of castingdies [4] or in several others [31,32].

Although Ti0.3Al0.7N seems to be the ideal composition for diesurface coating applications, one must recall that both hardnessand Young modulus decrease substantially at this Al concentra-tion. This can affect negatively the resistance of the die to abrasiveand erosive wear, as well as the adhesion of the coating to the dieand the enduring of mechanical and thermal cycling during diecasting operation. On the other hand, Ti1− xAlxN coatings with xbetween 0.6 and 0.7 or, alternatively graded or multilayered thinfilm coatings have substantially higher hardness and Youngmodulus, thus probably constituting optimum solutions.

Furthermore, the onset temperatures for the different react-ions may not be strictly representative of the process in actualcasting operation, but they can be used as means for comparisonbetween candidate coatings. In the only case of the present workwhere activation energies could be determined, namely the Al/Ti0.5Al0.5N multilayered structures, the activation energy for thefirst reaction is consistent with Al diffusing into (Ti,Al)N,occupying Ti sites with consequent formation of nitrogenvacancies. In other words, a substitutional diffusion mechanismgoverning the solid state reaction. On the other hand, theactivation energy for the second reaction would be consistentwith an interstitial diffusion mechanism, with Al diffusing intolattice sites of suitable sizes of the rather non-compact B1 cubicstructure. Further heating in presence of aluminum leads to theformation of TiAl3.

The DSC and XRD results discussed above have shown thatprotective Ti0.3Al0.7N coatings are inert in liquid aluminum upto 1000 °C, inhibiting chemical reaction that lead to the for-mation of intermetallic compounds. In order to assure hardnessand Young modulus to the coating, and therefore adhesion anderosion resistance to liquid aluminum, compatible with therequirements for a casting die, lower Al concentrations (x in the0.6 to 0.7 range) should be used. Further lowering of the Alconcentration in the Ti1− xAlxN coating, namely x inferior to0.6, could render the coating even harder and with higherYoung modulus, but it will be wettable in aluminum, proneto intermetallic TiAl3 formation, and therefore inadequate.


Besides non-wettability, the barrier diffusion constituted byTi1− xAlxN coatings, here attributed to aluminum oxide andoxynitrides formed during work, will prevent physicochemicalinteractions between die steel and liquid aluminum. Conse-quently, the formation of intermetallics involving Al and thecomponents of the steel, such as Al–Fe, Al–Si and others willbe avoided. Therefore, damage to the die due to mass loss ofthe die steel by soldering, dissolution of the intermetallics,corrosion, abrasion, and erosion of the steel by hard inter-metallic particles will be prevented [33,34].

A full comparison between different routes for casting dieprotective coating is far beyond the purpose of this work.Nevertheless, previous work on surface engineering orprotective coatings can be compared with the present results.Plasma nitriding of the casting die steel near surface (50 to100 μm) region [23] led to harder, diffusion barrier, and erosionresistant zones which provided an overall improvement on dieperformance. However, oxidation resistance was in general notsufficient to prevent soldering as well as craters and crackformation, most probably assisted by intermetallic formation.One route of high success, having shown excellent casting dieperformance in the laboratory scale, is the duplex treatment,combining plasma nitriding and TiN thin film coating [1,2].Conceptually, this route provides a much harder overall diematerial and can incorporate all the benefits of plasma nitridingand of aluminum-inert thin film coatings. Although TiN isinferior concerning non-wettability in liquid aluminum whencompared with the present results, a large improvement isexpected to be brought by introducing compound coatings likeTi1− xAlxN instead of TiN in duplex treatments. Alternativesingle-coating compounds have been tried [4] and CrN coatingswere shown to be competitive, specially for being almost aschemical inert as Ti1− xAlxN. However, adhesion to the die steel(mostly H13) at the working temperatures, was superior in thelatter. Multilayered coatings of TiN/TiAlN, TiN/CrN and gradedcompound coatings of Ti1− xAlxN with variable x, with orwithout an intermediate Ti-film layer designed to improveadhesion to the die steel [4,11], constitute undoubtedly superiorcoating strategies concerning casting die performance.

Unfortunately, there are not enough thermochemical andstructural data in the literature yet to allow for a comparisonwith the present results.

4. Summary and conclusions

We investigated the reactivity of Al/Ti1− xAlxN thin filmmultilayered coatings by complementary DSC and XRD. In thecase of TiN (x=0), a solid state reaction leads to the formationof an intermetallic compound, TiAl3, below the melting tem-perature of Al.

For x=0.3 or 0.5, the onset temperatures for the reactions areshifted to temperatures slightly above the melting point ofaluminum. Higher onset temperatures for the exothermic react-ions are indicative of a diffusion barrier that inhibits reaction withmolten Al, even if it does not prevent it entirely. For x=0.5, twodifferent model equations recently applied in the literature to theanalysis of diffusion-controlled reactions failed to fit the ex-

perimental data, whereas a simple, uni-directional parabolicreaction kinetics model gave a good fit to the data, allowing todetermine the activation energies.

For x=0.7, the Ti1− xAlxN coatings seem to be inert (non-wettable) in the presence of aluminum up to 1273 K (1000 °C)and there is no evidence for the formation of TiAl3 or otherintermettalics. The action of Al, alumina (Al2O3), as well asaluminum nitride and oxynitrides as effective diffusion barrierscan justify this non-reactivity. Furthermore, when hardness andYoung modulus are taken into account, Ti1− xAlxN coatings withx between 0.6 and 0.7 or, alternatively, graded, multilayered orduplex thin film coatings probably will constitute optimumsolutions.

References

[1] K.S. Klimek, H. Ahn, I. Seebach, M.Wang, K.-T. Rie, Surf. Coat. Technol.174–175 (2003) 677.

[2] P. Panjan, I. Urankar, B. Navinsek, M. Tercelj, R. Turk, M. Cekada, V.Leskovsek, P. Panjan, Surf. Coat. Technol. 151–152 (2002) 505.

[3] A. Persson, S. Hogmark, J. Bergströn, Surf. Coat. Technol. 191 (2005)216.

[4] J. Lin, S. Carrera, A.O. Kunrath, D. Zhong, S. Myers, B. Mishra, P. Ried,J.J. Moore, Surf. Coat. Technol. 201 (2006) 2930.

[5] O. Salas, K. Kearns, S. Carrera, J.J. Moore, Surf. Coat. Technol. 172(2003) 117.

[6] E. Spaina, J.C. Avelar-Batista, M. Letch, J. Housden, B. Lerga, Surf. Coat.Technol. 200 (2005) 1507.

[7] Y. Yin, L. Hang, S. Zhang, X.L. Bui, Thin Solid Films 515 (2007)2829.

[8] M. Zhou, Y. Makino, M. Nose, K. Nogi, Thin Solid Films 339 (1999) 203.[9] J. Bujak, J. Walkowicz, J. Kusinski, Surf. Coat. Technol. 180–181 (2004)

156.[10] K. Chakrabarti, J.J. Jeong, S.K. Hwang, Y.C. Yoo, C.M. Lee, Thin Solid

Films 406 (2002) 159.[11] J.H. Hsieh, C. Liang, C.H. Yu, W. Wu, Surf. Coat. Technol. 108–109

(1998) 132.[12] G. Amsel, J.P. Nadai, E. D'Artemare, D. David, E. Girard, J. Moulin, Nucl.

Instrum. Methods Phys. Res. 92 (1971) 481.[13] I.J.R. Baumvol, Surf. Sci. Rep. 36 (1999) 1.[14] M.M. Frank, Y.J. Chabal, M.L. Green, A. Delabie, B. Brijs, G.D. Wilk,

M.-Y. Ho, E.B.O. da Rosa, I.J.R. Baumvol, F.C. Stedile, Appl. Phys. Lett.83 (2003) 740.

[15] C.-L. Chang, J.-Y. Jao, T.-C. Chang, W.-Y. Ho, D.-Y. Wang, DiamondRelat. Mater. 14 (2005) 2127.

[16] V. Maurice, G. Despert, S. Zanna, P. Josso, P. Bacus, P. Marcus, Surf. Sci.996 (2005) 61.

[17] M. Schmiedgen, C.J. Graat, P. Baretzky, E.J. Mittemeijer, Thin Solid Films415 (2002) 114.

[18] M.E. Kissinger, Anal. Chem. 29 (1957) 1702.[19] R.B. Bird, W.E. Stewart, E.N. Lightfoot, Transport Phenomena, John

Wiley & Sons, New York NY, 1960.[20] D. Ovono, I. Guillot, D. Massinon, J. Alloys Compd. 432 (2007) 241.[21] I.G. Polyakova, T. Hubert, Surf. Coat. Technol. 141 (2001) 5.[22] Z.W. Chen, Mater. Sci. Eng., A Struct. Mater.: Prop. Microstruct. Process.

Mater. 397 (2005) 356.[23] V. Joshi, A. Srivastava, R. Shivpuri, Wear 256 (2004) 1232.[24] V. Joshi, K. Kilkarni, R. Shivpuri, R.S. Bhattacharya, S.J. Dikshit, D. Bhat,

Surf. Coat. Technol. 146 (2001) 338.[25] T. Wang, J. Zhang, Mater. Chem. Phys. 99 (2006) 20.[26] J. Sestak, Thermophysical Properties of Solids, Elsevier, Amsterdam,

1994.[27] T.J. Ozawa, Thermal Anal. 2 (1970) 301.[28] A. Brummer, V. Honkimaki, P. Berwian, V. Probst, J. Palm, R. Hock, Thin

Solid Films 437 (2003) 297.


[29] W.K. Kim, S. Kim, E.A. Payzant, S.A. Speakman, S. Yoon, R.M.Kaczyinsky, R.D. Acher, T.J. Anderson, O.D. Crisalle, S.S. Li, V. Craciun,J. Phys. Chem. Sol. 66 (2005) 1915.

[30] F. Hulbert, J. Br. Ceram. Soc. 6 (1969) 11.[31] G.V. Soares, K.P. Bastos, R. Pezzi, L. Miotti, C. Driemeier, I.J.R.

Baumvol, C. Hinkle, G. Lucovsky, Appl. Phys. Lett. 84 (2004) 4992.

[32] L. Miotti, R.P. Pezzi, M. Copel, C. Krug, I.J.R. Baumvol, Appl. Phys. Lett.90 (2007) 052913.

[33] M. Soković, P. Panjan, R. Kirn, J. Mater. Proces. Technol. 157 (2004) 613.[34] W.Y. Ho, D.-H. Huang, L.-T. Huang, C.-H. Hsu, D.-Y. Wang, Surf. Coat.

Technol. 177 (2004) 172.

Reactivity between aluminum and (Ti,Al)N coatings for casting dies

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