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OTELURI
INOXIDABILE
Austenitice
Localizare
Austenitic sau austenito-feritic.
Diagrama de Long
This refines the Schaffler diagram by
taking account of the strong austenite
stabilising tendency of nitrogen. The
chromium equivalent is unaffected but
the nickel equivalent is modified to
Ni (eq) = Ni + (30 x C) + (0.5 x Mn) + (30
x N)
The diagram, identifying the phase
boundaries is shown below. This shows
the ferrite levels in bands, both as
percentages, based on metallographic
determinations and as a ferrite number
'FN', based on magnetic determination
methods.
Combined Schaeffler / WRC 1992
Constitution Diagram
Diagrama WRC
Magne Gage
Ferrite Number versus Ferrite Content
The Ferrite Number is not equal to the volumetric ferrite content (%). Although an absolute ferrite content can not be measured accurately,
a reasonable estimate of the ferrite content can be made by dividing the Ferrite Number by the factor f (% ferrite = FN / f) which
is dependant of the iron content in the weld metal as shown in figure 4.
Limitations
With the practice of measuring the Ferrite Number or ferrite content, welding conditions deviating from the standardized conditions
have always to be taken into account. Furthermore, comparison tests showed that the accuracy between measurements in various
laboratories may show differences up to +/- 10%.
Precipitate Phases
• These include carbides, nitrides or intermetallic compounds. Since most
stainless steels serve at ambient temperature, the intermetallic compounts
are of little relevance as they are extremely slow to precipitate because
even though they may be thermodynamically stable phases, they are
difficult to nucleate.
• It is evident from Figure 6 (Fe-Cr-C phase diagram) that typical martensitic
steels should exhibit ferrite and M23C6 in equilibrium at for example, 600°C.
In practice, this carbide is only found after relatively long ageing. because it
is preceded by Intermediate phases in the sequence cementite, M2X and
M7C3, leading finally to M23C6.
• These precipitation sequences become more complex in heavily alloyed
ferritic or austenitic stainless steels, such as those destined for the power
generation industry. Considerable effort is being devoted to understanding
and estimating the precipitation sequences in such alloys because the are
intended to serve safely for 30 or more years, i.e., for time periods far in
excess of what can be reasonably achieved in the alloy development
exercise (Robson and Bhadeshia, 1997; Fujita and Bhadeshia, 2002;
Sourmail, 2001; Sourmail and Bhadeshia, 2003).
Carburi
• The carbides formed at high temperatures (500 to 850
°C) will be of the type M23C6 .
• Those formed at lower temperatures, during tempering
or stress relieving, will be of the types M3C, M7C3 and
M23C.
• More alloying elements will initiate complex carbides:
– Tungsten W M2X X is alloying element
– Molybdenum Mo M2X and M23C M is (Fe, C, X)-combination
– Vanadium V MX and M23C
– Niobium Nb MX
– Titanium Ti MX
– Chromium Cr M23C6, M7C3 and in a lesser degree M3C, and
M23C
Carburi
• The carbides take carbon and chromium out of the matrix. The first
two types (M23C6 en M7C3) do contain about 40 to 60 % of
chromium. The amount of chromium compared to the amount of
carbon, taken out the matrix by the M23C6 carbides, can be
estimated (not correct value) as:
% Crcarbides = 14,54 * (% C).
• But not all the carbon will combine with chromium to form carbides,
even with a very slow (but realistic) cooling. In the special types of
austenitic stainless steel, the carbon is equal or lower than 0,03 %
and for these types nearly never carbides are formed. So we can
estimate that this amount of carbon, at least, remains in the matrix.
• So the “minimum” amount of chromium, still in the matrix (for the
maximum amount of carbides) is:
% Crmatrix = % Crchemical compositon - 14,54 * (% C – 0,03).
• So, the higher the carbon, the more carbides can be formed and the
faster the cooling must be to avoid their formation.
Tipuri de oteluri inoxidabile austenitice
• oteluri de tip 18Cr -10Ni, cu 0,02-0,15%C;
The austenitic structure has good creep resistance and good oxidation
resistance
Otel AISI 304L sinterizat
Structura austenitei
Adding 8% nickel
to a ferritic
chromium
stainless steel
makes an
austenitic
chromium-
nickel stainless
steel, for
example Type
304 stainless
steel.
Faze si constituenti in oteluri
inoxidabile austenitice
Matricea de baza este alcatuita din solutii
solide α si γ continând elemente de aliere
dizolvate interstitial (de exemplu C si N) sau
substituind atomul de fier (de exemplu Cr, Ni, Ti).
Constituentii minori sunt formati din fazele
interstitiale si intermetalice si din incluziuni.
Fazele interstitiale: tipurile de carburi cele mai
frecvente sunt M23C6. Mai pot exista Cr23(B,C)6 si
Cr23C6. Carbura Cr23C6 poate dizolva elemente
ca Mo, W, V si Ni. Se pot forma si alte carburi de
crom: Cr7C3, Cr6C, precum si nitruri de tip CrN si
Cr2N. Prezenta elementelor caTi, Nb sau Zr
conduc la formarea de carburi, nitruri sau
carbonitruri de tip MX având structura cubica cu
fete centrate [teza doctorat - Cercetari privind
comportarea la coroziune a otelurilor inoxidabile supuse
deformarii plastice si nitrurarii ionice – Cluj Napoca].
.
Faze si constituenti in oteluri inoxidabile
austenitice
• Fazele intermetalice sunt :
– faza sigma (ζ) cu retea cristalina complexa în
care compozitia poate merge de la tipul B4A la
tipul BA4;
– faza de tipul AB2 si faza Laves (n), în
prezenta molibdenului (Fe2Mo), titanului,
niobiului,volframului, etc.
– faza intermetalica cu caracter electronic, de
tip Hume-Rothery, cum sunt faza χ cu retea
cristalografica izomorfa.
Efectul elementelor de aliere
This short description of the problem hides most of its interesting complexity.
The minimum chromium concentration reached in the austenite ajacent to the
carbide is in principle determined by the appropriate part of the phase diagram,
which predicts that the chromium content of the austenite in equilibrium with
M23C6 (cγM23C6) is slightly lower than the bulk composition. However, the
minimum concentration reached in the austenite is smaller than indicated by the
phase diagram because of multicomponent diffusion effects, the dynamics of the
solute fluxes towards the precipitates.
• In normal conditions, austenitic stainless steels are given a high-temperature heat-treatment, often
called a solution-treatment, which gives a fully austenitic solid solution. However, at temperatures
below about 800°C, there is a tendency to precipitate chromium-rich carbides as the alloy enters
the carbide plus austenite phase field.
• The main carbide phase is M23C6, where the 'M' stands for a mixture of metal atoms including
iron, molybdenum, chromium and manganese, depending on the steel composition and heat-
treatment. These carbides require long-range diffusion in order to precipitate and hence can be
avoided by rapid cooling from the solution-treatment temperature.
• The precipitation of M23C6 and M7C3 occurs primarily at the austenite grain surfaces which are
heterogeneous nucleation sites; it can occur in a matter of minutes at temperatures around 750°C.
The chemical composition in the vicinity of the grain boundaries can be altered by the
precipitationof the chromium-rich particles. The resulting chromium-depleted zone at the grain
boundaries makes them susceptible to intergranular anodic-attack even under stress--free
conditions. Once again, the anodic regions present a much smaller area (grain boundaries)
compared with the rest of the exposed surface which is cathodic; the localised rate of corrosion at
the boundaries is therefore greatly exaggerated. This is the essence of sensitisation.
• Sensitisation in the context of welded samples leads to the phenomenon of weld decay. Regions
are created in the heat-affected zones of the welds which precipitate carbides, become sensitised
and fail by localised corrosion, almost as if the weld is unzipped in the sensitised region.
Remedies to Sensitisation
• Figure shows that the steel is safe from sensitisation at low times because precipitation has not
yet occurred with a vengence. Prolonged heat treatment makes the steel safe by permitting
diffusion to eliminate chromium concentration gradients in the austenite.
Fisuri si crăpături intr-un tub din Multiple corrosion fatigue cracks at the I.D.
otel inoxidabil turnat 304 expus in of a AISI 1020 carbon steel downhole tool.
etilena la temperaturi ridicate The tool was rotating with the I.D. exposed
(100X). to a water based drilling fluid. 2% Nital Etch,
50X
H2S SSC Cracks in a 17-4pH stainless steel
stud from an O&G Wireline Valve Manifold
Assembly
Grain boundary corrosion and intergranular cracking from excessive
solution annealing temperatures in a 316L stainless steel
microstructure. Oxalic acid etch. (50X)
304 Stainless Steel White Water
Filter Screen Corrosion
Tunneling corrosion of a 304 stainless steel screen wire in a papermill white stock
water service thought to be influenced by microbiologically induced corrosion (MIC).
Fragilizarea oţelurilor inoxidabile
• În cazul oţelurilor inoxidabile, Cr nu influenţează decât
tenacitatea. Aceasta este controlată mai ales de conţinutul
de C şi N2, a căror solubilitate în ferită scade foarte mult
odată cu creşterea conţinutului de Cr.
• Ca urmare, la conţinuturi mari de Cr, C şi N2, vor apare
precipitate din ce în ce mai abundente, sub formă de
carburi, nitruri sau carbo-nitruri, având ca rezultat
micşorarea tenacităţii matricei de ferită faţă de cea
corespunzătoare oţelurilor feritice comune, oţelurile
devenind din ce în ce mai dificil de utilizat.
• Pornind de la aceste constatări au apărut oţelurile ELY
(Extra Low Interstitial) la care conţinutul de carbon este C <
0,01% iar cel de azot N2< 0,005%, impunându-se condiţia
ca suma C+N2 să nu depaşească 0,001%.
• De exemplu la 28-35% Cr, C < 0,002% până la 0,006% şi
N2
Rupere fragila
Sigma
Faza Sigma (particule de culoare roşie) in otel refractar inoxidabil 310 expus la
temperaturi ridicate.
Masuri pentru evitarea aparitiei carburilor
• 1. Heat treatment
• Pay attention that during the heat treatment:
• 1. carbon dissolves very quickly in the matrix
• 2. chromium does not solve easily (relative large atom)
and the stay at high
• temperature must be sufficiently long
• 3. too long stay on high temperature does increase the
grain size of the matrix,
• which leads to a somewhat lower ductility.
• 2. An increasing amount of carbon will tend to form more
austenite (present times 30
• in the nickel-equivalent) but the tendency to form
carbides will also increase.
Masuri pentru evitarea aparitiei carburilor