Effect of Nb on oxidation behavior of high Nb containing TiAl alloys

The isothermal oxidation behavior of Ti-45Al-8Nb and Ti-52Al-8Nb alloys at 900 °C in air was investigated. The early oxidation behaviors were studied by using XPS and AES. And the microstructure and the composition of the oxidation scale were studied by using XRD and SEM. The results show that the oxidation behavior of TiAl alloy is significantly improved by Nb addition. Nb substitutes for Ti in TiO₂ as a cation with valence 5, and thus to suppress TiO₂ growth. The (Ti,Nb)O₂-rich layer is a dense and chemically uniform which is more protective than the TiO₂ layer. Nb addition also lowers the critical Al content to form an external alumina. Nb₂Al phase is formed in the metallic matrix at the oxide–metal interface on the high Nb containing TiAl alloys.     

Hot-Corrosion Behavior of TiAl-Base Intermetallics in Molten Salts

The hot-corrosion behavior of Ti-50Al,Ti-48Al-2Cr-2Nb, and Ti-50Al10Cr alloys was investigatedin (Na, K)₂SO₄ andNa₂SO₄ + NaCl melts. TiAlintermetallics showed much better hot-corrosionresistance in (Na, K)₂SO₄ at900°C than the Ni-base superalloy K38G. Two types ofcorrosion products formed on Ti-50Al: some areas werecovered with a continuous Al2O3 scale, whereas otherareas formed a mixed Al₂O₃ +TiO₂ scale; TiS existed at the scale-alloyinterface. A mixed Al₂O₃ +TiO₂ scale formed on Ti-48Al-2Cr 2Nb, and nosulfide was found beneath the scale. An adherentAl₂O₃ scale, however, formed onTi-50Al-10Cr, which provided excellent hot-corrosionresistance. All three alloys suffered severe hotcorrosion in Na₂SO₄ + NaCl meltsat 850°C. A mixed Al₂O₃ +TiO₂ scale formed on all three alloys andmany voids and pits existed in the scale-alloy interface. Thehot-corrosion mechanisms are discussed.     

Studies concerning the effect of nitrogen on the oxidation behavior of TiAl-based intermetallics at 900°C

The oxidation behavior of the titanium aluminides Ti-50Al and Ti-48Al-5Nb has been investigated in Ar+20%O₂ and in air at 900°C. Thermogravimetric studies in combination with structural analyses using optical metallography, SEM/EDX and X-ray diffraction show a marked influence of nitrogen on the composition and growth rate of the oxide scales. For a more detailed study concerning the effect of nitrogen on the scale-growth kinetics, thermogravimetrical analyses were carried out during which the gas atmosphere was changed from air to Ar–O₂, and vice versa, without intermediate cooling of the specimen. The results show, that nitrogen adversely affects the formation of the initially formed alumina scale and that it enhances the growth rate of the rapidly growing Ti-rich oxide. This effect was observed in both alloys investigated, although the thermogravimetric results at first sight indicated an opposite effect for the Nb-containing alloy. This apparent contradiction is caused by internal oxidation which occurs in this alloy during exposure in Ar–O₂.     

Environmental Effects on Orthorhombic Alloy Ti-22Al-25Nb in Air Between 650 and 1000°C

The environmental behavior of an orthorhombictitanium-aluminide alloy, Ti-22Al-25Nb, was studied indry and humid air between 650 and 1000^°Cby scanning electron microscopy, energy dispersive spectroscopy, and X-ray diffraction.Microhardness measurements were performed after exposureto gage hardening due to nitrogen and oxygen ingress.The parabolic rate constant of Ti-22Al-25Nb was of the same order as conventional titanium alloys andTi₃ Al-base titanium aluminides at and below750^°C. Between 800 and1000^°C, the oxidation resistance ofTi-22Al-25Nb was as good as -TiAl base aluminides;however, the growth rate changed from parabolic tolinear after several tens of hours at 900 and1000^°C. The mixed oxide scale consistedof TiO₂, AlNbO₄, andAl₂O₃ with TiO₂ beingthe dominant oxide phase. Underneath the oxide scale, anitride layer formed in the temperature rangeinvestigated and, at 1000^°C, internal oxidation was observed below thislayer. In all cases, oxygen diffused deeply into thesubsurface zone and caused severe embrittlement.Microhardness measurements revealed that Ti-22Al-25Nbwas hardened in a zone as far as 300 m belowthe oxide scale when exposed to air at900^°C for 500 hr. The peak hardnessdepended on exposure time and reached five times theaverage hardness of the bulk material under the aboveconditions.     

Cyclic oxidation behaviour of Ti3Al-based alloy with Ni-Cr protective layer

The influence of a thin 80Ni-20Cr (at.%) protective coating on the cyclic oxidation of a Ti-24Al-11Nb (at.%) alloy based on Ti₃Al at 600 and 900 °C in air was investigated using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction analysis (XRD). The results of the oxidation tests showed that deposited Ni-Cr layer provides an improved oxidation resistance due to the formation of protective oxide scale which barriers the outward Ti diffusion into the scale. In some extent surface formation of the nitride layer also prevents diffusion of alloying elements from the matrix. Although oxidation at 900 °C is faster than that at 600 °C, a remarkable reduction in mass gain of the alloy with protective coating was observed. The thickness of oxide scale on the coated samples is approximately two times less than that formed on the uncoated samples treated under the same exposure conditions (120 h).     

Oxidation of orthorhombic titanium aluminide Tl-22AL-25NB in air between 650 and 1000 °C

The oxidation behavior of orthorhombic titanium aluminide alloy Ti-22Al-25Nb was studied in air between 650 and 1000 °C by isothermal thermogravimetry and postoxidation scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and x-ray diffraction. Microhardness measurements were performed after exposure to gage hardening due to nitrogen and oxygen ingress. The parabolic rate constant of Ti-22Al-25Nb was of the same order as conventional titanium alloys and Ti₃Al-based titanium aluminides at and below 750 °C. Between 800 and 1000 °C, the oxidation resistance of Ti-22Al-25Nb was as good as that of γ-TiAl based aluminides; however, the growth rate changed from parabolic to linear after several tens of hours at 900 and 1000 °C. The mixed oxide scale consisted of TiO₂, AlNbO₄, and Al₂O₃, with TiO₂ being the dominant oxide phase. Underneath the oxide scale, a nitride-containing layer formed in the temperature range investigated, and at 1000 °C, internal oxidation was observed below this layer. In all cases, oxygen diffused deeply into the subsurface zone and caused severe embrittlement. Microhardness measurements revealed that Ti-22Al-25Nb was hardened in a zone as far as 300 μm below the oxide scale when exposed to air at 900 °C for 500 h. The peak hardness depended on exposure time and reached five times the average hardness of the bulk material under the above conditions.     

(S)TEM study of different stages of Ti-45Al-8Nb-0.2W-0.2B-0.02Y alloy oxidation at 900 °C

The oxidation process of Ti-45Al-8Nb-0.2W-0.2B-0.02Y (at%) can be divided into three stages during 100 h at 900 °C. The change of ion diffusion path leads to the discontinuity of the oxidation curve between the second and third stage. Different stages of oxidation morphology have been investigated combined with TEM and STEM. AlNb₂ phase forms at the interface of oxide scale/base alloy. Contrary to a continuous formation of ‘x’ phase in γ-TiAl with Nb free at the interface of oxide scale/base alloy. AlNb₂ phase hinder continuous ‘x’ phase formation, which can promote TiAl oxidation protection.     

Influence of water vapor on the oxidation behavior of aluminized coatings under low oxygen partial pressure

FeCrNi alloy after aluminizing was oxidized at 1000 °C in dry and humid (2.23 vol.% water) H₂. Experimental results showed that H₂ promotes the formation of θ alumina and its transformation to α alumina. The morphology of surface alumina coating does not change significantly, but the oxidation rate of the aluminized layer accelerates by the addition of water vapor. As a result, more cracks are found beneath the alumina layer when water vapor is present. The addition of water vapor seems having a favorable effect on the selective oxidation of Al and concentration of oxygen vacancy in the aluminized alloys.     

High-Temperature Oxidation Behavior of Ti-22Al-27(Nb, Zr) Alloys

研究了Ti2Al Nb基合金Ti-22Al-(27-x)Nb-x Zr(x=0,1,6,at%)在650~800℃的氧化行为。采用XRD和SEM等测试技术对此温度区间形成的氧化层特征进行了分析。结果表明,相比Ti-22Al-27Nb,含锆合金具有较好的抗氧化性能。Ti-22Al-(27-x)Nb-x Zr合金在650℃氧化100 h,主要氧化产物为Ti O2,而在800℃氧化100 h,Ti O2,Al2O3和Al Nb O4为主要产物,但是在Ti-22Al-21Nb-6Zr合金中还有Zr O2生成。Ti-22Al-26Nb-1Zr合金具有优异抗氧化性能,归因于氧化产物细化形成了致密的氧化层,而Ti-22Al-21Nb-6Zr合金,虽然在800℃也形成了较多Al2O3,但是氧化层中的Zr O2为氧的快速扩散提供通道,进而导致该合金氧化增重明显。     

Structure of Al-modified silicide coatings on an Nb-based ultrahigh temperature alloy prepared by pack cementation techniques

In order to prepare Al-modified silicide coatings on an Nb-based ultrahigh temperature alloy, both a two-stage pack cementation technique and a co-deposition pack cementation technique were employed. The two-stage process included siliconizing a specimen at 1150 °C for 4 h followed by aluminizing it at 800-1000 °C for 4 h. The coating prepared by pack siliconization was composed of a thick (Nb,X)Si₂ (X represents Ti, Cr and Hf elements) outer layer and a thin (Nb,X)₅Si₃ transitional layer; after the siliconized specimens were aluminized at or above 860 °C, a (Nb,Ti)₃Si₅Al₂ phase developed at the surface of the coating, and furthermore, when aluminizing was carried out at 860 °C, a new (Nb,Ti)₂Al layer formed in the coating between the (Nb,X)₅Si₃ layer and the substrate, but when aluminizing was performed at 900-1000 °C, the new layer formed was (Nb,Ti)Al₃. The co-deposition process was carried out by co-depositing Si and Al on specimens at 1000-1150 °C for 8 h under different pack compositions, and it was found that the structure of co-deposition coatings was more evidently affected by co-deposition temperature than pack composition. An Al-modified silicide coating with an outer layer composed of (Nb,Ti)₃Si₅Al₂, (Nb,X)Si₂ and (Nb,Ti)Al₃ was obtained by co-depositing Si and Al at 1050 °C.     

The Oxidation Behavior of Several Ti-Al Alloys at 900°C in Air

Ti-23Al, Ti-50Al and Ti-50Al-2Nb (at.%) wereoxidized in air at 900°C for times up to 1130 hr.The resulting oxide scale structures were analyzed ingreat detail by metallographic and microprobe investigations and theAl₂O₃ structures in the complexoxide scales were correlated with the course of thethermogravimetric curves. It appears that in order toachieve long-term protective behavior of the scales, it is necessary to stimulate theformation of a thin Al₂O₃ barrierat the scale-metal interface and not at a position inthe outer part of the scale. The Nb effect seems to bemostly due to this stimulation of anAl₂O₃ layer at theinterface.     

Cracking and Healing of Oxide Scales on Ti-Al Alloys at 900°C

The behavior of oxide scales on Ti-50Al andTi-50Al-2Nb (at.%) was investigated in constantstrain-rate tensile tests at 900°C in air. Thestrain rates ranged between 1 × 10^-9sec^-1 and 3 × 10^-4sec^-1. The tests were accompanied byacoustic-emission measurements in order to detectscale-cracking processes during deformation. Thecritical strains to scale cracking amounted to 0.12-0.5%for the scales on TiAl and 0.17-0.58% for Ti-50Al-2Nb. Thesevalues were found to depend strongly on the size of thepores in the scales and, by using a fracturemechanics-based model, the results for the criticalstrains could be condensed into a narrow scatterband,which is independent of the applied strain rate. Healingof scale cracks was found for strain rates below 1.5× 10^-6 sec^-1 (Ti-Al) and 1.9× 10^-4 sec^-1 (Ti-Al-Nb), respectively. It turned out that the healingprocess is dominated by TiO₂ growth. In alater healing stage, the originalAl₂O₃ barrier is, however,restored in the scale on Ti-50Al. For Ti-50Al-2Nb, an Al₂O₃ layer is found onthe former scale-crack contours. The healing process isalso described by a quantitative model. As a generalconclusion from the investigations, it turned out thatcritical strains to oxide-scale cracking can be estimated fromjust simple oxidation experiments without sophisticatedmechanical testing if the microstructural parameters ofthe scale are determined quantitatively as a function of oxidation time by metallographicmeans.     

High-Temperature Oxidation of Ti-48Al-2Nb-2Cr and Ti-25Al-10Nb-3V-1Mo

The short-term oxidation behavior of a-TiAl alloy (Ti-48Al-2Nb-2Cr) was compared andcontrasted to that of an₂-Ti₃Al base(Ti-25Al-19Nb-3V 1Mo) alloy. Oxidation ofTi-25Al-10Nb-3V-1Mo was found to occur at a moderate rate at 800°C, in aN₂ + 20% O₂ environment. A largeincrease in the oxidation rate occurred above thistemperature. This large weight increase was attributedto a breakdown in the protective oxide scale on the surface of the₂ intermetallic alloy, therebypermitting rapid diffusion of oxygen and nitrogen to thesurface of the intermetallic. The oxidation rate of thisalloy at 1200°C was not significantly higher thanthe oxidation rate at 1000°C. In contrast, theoxidation rate of Ti-48Al-2Nb-2Cr remained low up to1200°C. At this temperature, a significant increasein oxidation was observed and was attributed to acceleratedoxygen diffusion through the ₂ phaseand increased solubility of oxygen in the gamma phase ofthe intermetallic microstructure. This weight increaseoccurred despite the fact that at 1200°C, theintegrity of the oxide layer formed on the surface ofthis alloy was maintained. The results of this studyillustrate the need for developing protectiveenvironmental coatings tailored to the individualintermetallic alloy.     

Oxidation resistance of aluminized coatings on a directionally solidified Ni-Al-Cr3C2 eutectic alloy

Although a directionally solidified Ni-Al-Cr₃C₂ eutectic alloy has good high-temperature mechanical properties, it does not have adequate oxidation resistance for prolonged exposure to high surface temperatures. Thus the oxidation behavior of several aluminized coating systems on this alloy in flowing air at temperatures of 900 to 1100°C under isothermal and thermal cycling conditions has been investigated. Attempts to produce an oxidation-resistant system by direct aluminizing have not been successful since removal of carbide fibers results in a porous coating which gives little protection to the alloy. The deposition of a layer of nickel or a Ni-20%Co-10%Cr-4%Al alloy on the eutectic prior to aluminizing gives improved isothermal oxidation resistance for prolonged exposure to high surface temperatures. Thus the eutectic alloy substrate occur during thermal cycling. A more successful system has been produced by depositing a thin layer of platinum on the eutectic alloy prior to aluminizing. Protective -Al₂O₃ scales are formed and maintained during isothermal and thermal cycling oxidation at 900 and 1000°C. Similar scales are developed at 1100° C although these do break down during thermal cycling. However, surface -Al₂O₃ scales are able to re-form rapidly, thereby preventing excessive oxidation of the coating.     

Phase equilibria in Ti3Al-Nb alloys at 1000 °C

Titanium aluminides are considered to be the future high-temperature structural materials for turbine applications. Major focus is on α₂Ti₃Al based and γTiAl based alloys. Niobium additions to Ti₃Al alloys is found to improve the room-temperature ductility. Thus phase equilibria in Ti-Al-Nb system is of practical significance with regard to their processing and high-temperature phase stability characteristics. In the present research, four alloys with compositions Ti-22Al-12Nb, Ti-21A1-16Nb, Ti-20Al-20Nb, and Ti-25Al-25Nb (all in atom percent) were equilibrated at 1000 °C for 225 hours and then quenched in water. The quenched alloys were characterized for phase relations by optical microscopy, X-ray diffraction (XRD), and electron probe microanalysis (EPMA). Based on the phase analysis, the ternary isotherm of the Ti-Al-Nb system at 1000 °C was constructed on the Ti₃Al-rich side. The orthorhombic Ti₂AlNb phase was observed in the sample with Ti-25Al-25Nb composition signifying the presence of this phase at 1000 °C.     

Study of microstructure and mechanical properties of Ti-45Al-(Fe,Nb) (at. %) alloys

In the present work, the microstructure and compression properties of two novel γ(TiAl) based alloys, Ti-45Al-5Fe and Ti-45Al-5Fe-5Nb, have been investigated. Both alloys had a relatively fine as-cast structure generally consisting of the γ(TiAl) and τ₂(Al₂FeTi) phases with a minor amount of the α₂(Ti₃Al) and β(B2) phase. The compression properties of the novel alloys were measured at room and elevated temperatures. The Ti-45Al-5Fe-5Nb alloy showed higher room temperature ductility and similar strength at room and elevated temperatures as well as improved workability at elevated temperatures as compared to β-solidifying γ(TiAl) alloys of last generation (TNM alloys).     

B元素对Ti-46Al和Ti-46Al-5Nb合金柱状晶组织的影响

B元素对Ti-46Al和Ti-46A1-5Nb(原子分数,%)合金的柱状晶组织均有明显的细化作用,且对后者的细化效果更显著.这一现象可归结为:B元素在Ti-46Al-5Nb合金中的溶解度较低,硼化物析出量增加,柱状晶组织进一步细化.     

V/Nb对Ti-45Al-9(V, Nb, Y)合金抗氧化性能的影响

βγ-TiAl合金具有良好的高温变形能力,为TiAl合金的发展开辟了新的途径。成功制备了不同x=V/Nb(x=1,1.5,2,3.5)的βγ-TiAlTi-45Al-9(V,Nb,Y)合金,研究了上述合金在800℃静止空气中的氧化行为。结果表明:当x=1时,Ti-45Al-9(V,Nb,Y)合金中形成条带状、连续致密的Al2O3氧化层,显著提高了合金的抗氧化能力。随着x=V/Nb的增加,Al2O3氧化层厚度变薄,合金的抗氧化能力下降。     

Microstructure and mechanical properties of low- and heavy-alloyed intermetallic alloys based on γ-TiAl + α2-Ti3Al

The microstructure and mechanical properties of the Ti-43.7Al-3.2(Nb,Cr,Mo)-0.2B alloy in the as-cast state (after gasostatistic processing) and of the Ti-45Al-8Nb-0.2C alloy after hot extrusion at temperatures corresponding to the ?? + ?? phase field followed by heat treatment have been studied. The extruded heavy-alloyed alloy has demonstrated significantly higher plastic/mechanical properties at room temperature with close values of the plasticity/tensile strength and long-term strength at elevated temperatures. A comparison of the results with literature data has shown the properties of the as-cast Ti-43.7Al-3.2(Nb,Cr,Mo)-0.2B to be similar to or superior to those of the best-known casting ?? (TiAl) + ??₂ (Ti₃Al) alloys.