Sculptura Art Deco din otel

inoxidabil austenitic la cladirea

Niagara-Mohawk Power in
Syracuse, New York

OTELURI
INOXIDABILE
Austenitice
Prof.Dr.Ing. Ionelia VOICULESCU

Scurt istoric
Aparitia otelurilor inoxidabile poate fi considerat un moment
important al revolutiei industriale. Cu toate ca efectele
dezastruoase ale coroziunii asupra fierului si aliajelor sale au
fost cunoscute din cele mai vechi timpuri, numai la nceputul
acestui secol s-au facut evaluarile cantitative ale acesteia.
Speranta de a gasi o metoda de protectie a fierului care sa-i
redea ntr-o maniera eficace si durabila rezistenta la coroziune,
parea, pna n 1800, de nerealizat.
Istoria otelurilor inoxidabile este marcata de perioada foarte
mare care s-a scurs ntre momentul descoperirii proprietatilor
remarcabile ale fierului aliat cu crom (metal descoperit
n1797 de VAUGUELIN si izolat n 1854 de BUNSEN) si
momentul n care s-au nceput primele studii stiintifice asupra
acestui aliaj si exploatarea lui industriala.
Putem compara aceasta situatie cu cea a penicilinei pe care
FLEMING a descoperit-o n 1928, iar aplicatiile ei terapeutice
au nceput dupa 13 ani adica n 1941. Pentru otelurile
inoxidabile aceasta perioada a fost de aproape 90 de ani.

Scurt istoric

Primele observatii aupra proprietatilor chimice conferite fierului prin

introducerea de crom au fost facute de BERTHIER n 1821. Primele
compozitii de oteluri inoxidabile, datnd de la nceputul secolului, au
fost semnalate simultan de GUILLET,CHEVANARD si PORTEVIN, n
Franta, GOLDSCHMIDT, GIESEN si MONARTZ n Germania.
Rezultatele lor au fost strans legate de descoperirea proprietatilor
conferite fierului prin adaugarea unei cantitati suficiente de crom, care
face ca aliajul sa reziste foarte bine n numeroase medii agresive, ceea
ce n mod normal se numeste pasivitate.
Dupa norma europeana EN10020, otelul inoxidabil este un aliaj de
fier, crom si carbon, cu mai mult de 10,5%Cr si mai putin de
1,2%C. Alte elemente cum sunt nichelul, molibdenul, titanul s.a., pot fi
adaugate pentru a conferi aliajului proprietati particulare.
Denumirea de OTELURI INOXIDABILE este foarte restrictiva, ca si
cele folosite n engleza (stainless: otel inatacabil) sau cea n germana
(nicht rostende Stahl: otel care nu rugineste), denumiri care s-au impus
la nceputul descoperirii lor datorita rezistentei evidente a acestor
oteluri la coroziunea atmosferica.
n prezent cnd spunem despre un otel ca este inoxidabil trebuie sa
specificam: n raport cu care medii, lichide sau gazoase, n ce limita de
temperatura si rezistenta la coroziune n comparatie cu otelurile
ordinare sau cele slab aliate.

Domenii de utilizare

Domenii de utilizare

Domenii de utilizare

Domenii de utilizare

Domenii de utilizare

FAMILII DE OELURI INOXIDABILE

n funcie de constituentul structural

preponderent la temperatura camerei,
exist urmtoarea clasificare a oelurilor
inoxidabile:
- oeluri martensitice;
- oeluri feritice;
- oeluri ferito austenitice (duplex);
- oeluri austenito feritice;
- oeluri integral austenitice.

Inoxidabile

Steels are said to be stainless when they resist corrosion; the is achieved by
dissolving sufficient chromium in the iron to produce a coherent, adherent, insulating
and regenerating chromium oxide protective film on the surface. It is not surprising
therefore that they are used in the harsh environments of the chemical, oil production
and power generation industries, and in utility goods such as furniture, automotive
trims and cutlery, where both aesthetic appearance and corrosion resistance are
important design criteria.
The stainless character occurs when the concentration of chromium exceeds about
12 wt%. However, even this is not adequate to resist corrosion in acids such as HCl
or H2SO4; higher chromium concentrations and the judicious use of other solutes
such as molybdenum, nickel and nitrogen is then needed to ensure a robust material.
There are requirements other than corrosion which have to be considered in
engineering design. For this reason, there is a huge variety of alloys available, but
they can be classified into four main categories:

hardenable stainless steels;

ferritic stainless steels;
austenitic stainless steels;
duplex stainless steels.
Specialist grades include the precipitation hardened or oxide dispersion strengthened alloys.

FAMILII DE OELURI INOXIDABILE

Diagrama de echilibru Fe-Cr

Diagrama de echilibru Fe-Cr-C

Sectiune Verticala prin

diagrama Fe-Cr-C
pentru 0.1% C

Diagrama Schaeffler

Without carbon, the limit beyond which austenite no longer forms is about
13.5 wt% chromium. However, additions of carbon help stabilise the
austenite and therefore increase this limit (Fig. 6).
Chromium and nickel equivalents are also used in the welding industry to
plot the microstructures obtained when a weld solidifies and cools to
ambient temperature (Fig. 7). Although these diagrams are popular, it
should be understood that they are not phase diagrams but rather represent
the microstructures obtained under specific cooling conditions.

Schaeffler diagram for weld metals.

Diagrama Schaeffler
The limits, for the chemical composition
are:
C < 0,2 % N = 0,05 % for % Cr 0 - 18 %
S < 1 % 0,07 18 - 25 %
Mn < 4 % 0,10 > 25 %
Mo < 3 %
Nb < 1,5 %

Diagrama Schaeffler

This diagram is interesting because, by quantifying the amount of types of

structures (ferrite, martensite, austenite), it does give an indication that the
material will comply with the standard. This is possible at a time that the metal
is still in the melting furnace because it does use the chemical composition that
is taken before pouring.
In this way corrections of the chemical composition are still possible.
It is very useful for austenitic stainless steels because the amount of ferrite
must be restricted (material becomes magnetic) and for martensitic stainless
steels because the amount of delta-ferrite must be controlled.

Diagrama Schaeffler
Austenite : above the lines (0-25) till (16-12) till
(36-36)
Ferrite : under the line (11-0) till (36-9)
Duplex : within the lines (36-36) till (16-12) till
(22-4) till (36-9)
Martensite : within the lines (0-7) till (3-0) till (70) till (12-8) till (0-19)
Precipitation hardening types are mostly
located in the zone with the presence of
austenite + martensiet or austenite +
martensite + ferrite.

Structuri comerciale
Austenite : austenite + 0 5 - 10 % ferrite
Ferrite : ferrite + carbides (chromium-carbides, TiC,
NbC...)
Duplex : 40 - 60 % austenite, 60 - 40 % ferrite
Martensite : martensite + (0 - 5 %) carbides + (0 - 15 %)
delta-ferrite
Precipitation-hardened : martensite + austenite + (ferrite)
+ intermetallic components
A stainless steel needs a minimum of 12 % of chromium
in the matrix. Due to this condition, the part of the graph
below a chromium-equivalent of 12 % is not applicable.

Reguli de calcul

EXEMPLE
During the calculation, the following rules will be applied:
1. if the real chemical composition is not known, two calculations will be
made: one with the minimum and one with the maximum values. Doing
this, we obtain an area (zone), in which the real composition
will be present.
2. silicon: mostly the maximum is given. We will calculate with:
minimum 0,3 % if the maximum is 1,0 % and minimum 0,6 % if the
maximum is 1,5 or 2,0 %.
3. manganese: we take a minimum of 0,6 % if only a maximum value is
given.
4. nickel and molybdenum: the minimum is 0 % if only a maximum is
given.
5. carbon: if only a maximum is given:
minimum 0,01 % if the maximum is 0,04 % or lower and
minimum 0,04 % if the maximum is higher as 0,04 %.

Exemplu

1. GX 20 Cr 14
C
Si
Mn
Cr
Ni
0,16-0,23 1,0 max 1,0 max 12,5-14,5 1,0 max
Creq min = 12,5 + 0,3x1,5 = 12,95
Creq max = 14,5 + 1,0x1,5 = 16,00
Nieq min = 0,0 + 0,16x30 + 0,6x0,5 = 5,10
Nieq max = 1,0 + 0,23x30 + 1,0x0,5 = 8,40
This steel can be located in three area:
martensite,
ferrite + martensite and
ferrite + martensite + austenite.

Due to the presence of mostly 5 to 15 % of chromium-carbides

(carbides remove and chromium and carbon from the matrix), the
commercially delivered steels will be located in the ferrite +
martensite zone.

Exemplu
2. GX 6 CrNiMo 18 10
C
Si
Mn
Cr
Ni
0,07 max 1,5 max 1,5 max 18,0-20,0 10,0-12,0

Creq min = 18,0 + 2,0x1 + 0,6x1,5 = 20,90

Creq max = 20,0 + 3,0x1 + 1,5x1,5 = 25,25
Nieq min = 10,0 + 0,04x30 + 0,6x0,5 = 11,50
Nieq max = 12,0 + 0,07x30 + 1,5x0,5 = 14,85
Localizare
Austenitic sau austenito-feritic.

Mo
2,0-3,0

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

WRC 1992 Constitution Diagram

Determinarea cantitatii de ferita

delta

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, 600C.
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;

oteluri stabilizate la coroziunea intergranulara prin adaugarea de titan sau niobiu;

oteluri cu continut scazut de nichel pentru a favoriza durificarea prin ecruisare;

oteluri cu continut ridicat de nichel pentru a favoriza ambutisarea adnca si pentru

aplicatii criogenice;

oteluri cu rezistenta mecanica crescuta prin adaugarea de azot;

oteluri in care manganul este substituit n parte de nichel;

oteluri cu rezistenta la coroziune ameliorata prin adaugare de molibden si cupru;

oteluri rezistente la oxidarea la cald prin adaugarea de siliciu;

oteluri la care comportarea la fluaj este ameliorata datorita adaugarii de N, Mo, W, V,

Ti, Nb si B;
oteluri pentru electrozi de sudare;

oteluri cu prelucrabilitate imbunatatita prin adaugarea de sulf, seleniu, cupru, etc.

Structura
La temperatura ambianta otelurile inoxidabile
austenitice au o structura formata din austenita, ferita
alfa si carburi de tipul M23C6.
Aceasta structura se obtine n cazul racirii lente.
Dupa tratamentul de hipercalire, cu racire rapida,
structura este formata numai din austenita.
Structura austenitica asigura o rezistenta foarte mare
la coroziune, plasticitate ridicata ceea ce permite
aplicarea cu rezultate bune a deformarii plastice la
rece, sudabilitate buna, duritate si limita de curgere
scazuta, proprietati paramagnetice.

Evolutia austenitei la diferite tipuri de

transformari

Structura austenitei

Imagine fractografica, austenita in otel 304.

Structura austenitei

Atac electrochimic, 500x.

Austenita placata prin pulverizare

cu alumina

Structura austenitei

Otel inoxidabil de tip 316, continand faza

sigma.

Austenita, cunoscuta si sub

denumirea de fier Gama, este
o faza ne-magnetica alotropa
a fierului sau solutie solida de
carbon in fier .
In otelul nealiat, austenita se
gaseste in domeniul
temperaturii critice eutectoide
de peste AC3 (921 oC); alte
tipuri de otel prezinta diferite
domenii de existenta care
depind de alierea cu diferite
elemente.
Denumirea sa provine de la
Sir William Chandler RobertsAusten (18431902).

Structura austenitei
Austenite is a metallic, non-magnetic solid solution of carbon and iron
that exists in steel above the critical temperature of 1333F
( 723C). Its face-centred cubic (FCC) structure allows it to hold a
high proportion of carbon in solution. In many magnetic alloys, the
Curie point, the temperature at which magnetic materials cease to
behave magnetically, occurs at nearly the same temperature as the
austenite transformation. This behavior is attributed to the
paramagnetic nature of austenite, while both martensite and ferrite
are strongly ferromagnetic.

Structura austenitei

As it cools, this structure either breaks down into a mixture of ferrite

and cementite (usually in the structural forms pearlite or bainite), or
undergoes a slight lattice distortion known as martensitic
transformation. The rate of cooling determines the relative proportions
of these materials and therefore the mechanical properties (e.g.
hardness, tensile strength) of the steel.
Austenite can contain far more carbon than ferrite, between 0.8% at
1333F (723C) and 2.08% at 2098F (1148C). Thus, above the
critical temparture, all of the carbon contained in ferrite and cementite
(for a steel of 0.8% C) is dissolved in the austenite. From 912 to 1,394
C (1,674 to 2,541 F) alpha iron undergoes a phase transition from
body-centred cubic (BCC) to the face-centred cubic (FCC)
configuration of gamma iron, also called austenite. This is similarly soft
and ductile but can dissolve considerably more carbon (as much as
2.04% by mass at 1,146 C (2,095 F)). This gamma form of iron is
exhibited by the most commonly used type of stainless steel for
making hospital and food-service equipment.

Structura austenitei

The austenitic structure has good creep resistance and good oxidation resistance

Otel AISI 304L sinterizat

Structura austenitei

Quenching (to induce martensitic transformation), followed by tempering (to

break down some martensite and retained austenite), is the most common
heat treatment for high-performance steels. The addition of certain other
metals, such as manganese and nickel, can stabilize the austenitic
structure, facilitating heat-treatment of low-alloy steels. In the extreme case
of austenitic stainless steel, much higher alloy content makes this structure
stable even at room temperature.
The ferritic stainless steel
on the left has a body
centered cubic (bcc)
crystal structure. By
adding nickel to this
stainless steel the
structure changes from
bcc to face centered cubic
(fcc), which is called
austenitic

Structura austenitei
On the other hand, such elements as
silicon, molybdenum, and chromium tend
to de-stabilize austenite, raising the
eutectoid temperature (the temperature
where two phases, ferrite and cementite,
become a single phase, austenite). The
addition of certain alloying elements, such
as manganese and nickel, can stabilize the
austenitic structure, facilitating heattreatment of low-alloy steels.

Structura austenitei
Adding 8% nickel
to a ferritic
chromium
stainless steel
makes an
austenitic
chromiumnickel stainless
steel, for
example Type
304 stainless
steel.

Faze si constituenti in oteluri

inoxidabile austenitice
Matricea de baza este alcatuita din solutii
solide si continnd 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 avnd 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 () cu retea cristalina complexa n
care compozitia poate merge de la tipul B4A la
tipul BA4;
faza de tipul AB2 si faza Laves (n), n prezenta
molibdenului (Fe2Mo), titanului,
niobiului,volframului, etc.
faza intermetalica cu caracter electronic, de tip
Hume-Rothery, cum sunt faza cu retea
cristalografica izomorfa.

Efectul elementelor de aliere

Curbele de nceput de precipitare a carburilor n functie de

timpul de mentinere dupa ncalzirea de punere n solutie la
temperatura ridicata pentru diferite concentratii ale carbonului.

Fenomene de precipitare
Dup punerea n soluie este indispensabila o
rcire rapida pentru a evita precipitarea n
cursul rcirii.
Cu ct coninutul de carbon este mai mic, cu
att durata de meninere pn la apariia
precipitatelor este mai mare.

Imperfectiuni structurale
Structura de baza a acestor oteluri este austenita- (CFC)
cu un parametru al retelei de a =0,3595 nm.
Structura CFC prezinta particularitatea de a fi una din cele
doua structuri compacte,alaturi de reteaua cristalina
hexagonala (HC).
Atomii sunt dispusi n mod dens ca niste bile, identice si
nedeformbile.
Planurile dense [111] au o structura compacta (centrul
atomilor n vrfurile unor triunghiuri echilaterale)

Impachetarea c.f.c.

Directii dense (110), planuri dense {111}

Dislocatii si defecte de impachetare

Deplasarea dislocatiilor prin cristal produce o alunecare, de marime

si directie anumita, definita prin vectorul BURGERS al dislocatiei.
Acest vector nu poate lua valori arbitrare ci numai valori
corespunzatoare distantelor dintre punctele de retea, ceea ce
nseamna ca alunecarea reciproca a doua parti din cristal se face pe
distanta care leaga o pozitie atomica de echilibru de alta pozitie de
echilibru.
n cazul otelurilor inoxidabile austenitice, cu retea CFC, cristalul se
obtine prin asezarea de structuri atomice compacte (111) n
succesiunea ABC ABC ...

Aparitia unui defect de impachetare la deformarea

plastica a unui cristal cu retea c.f.c.

Defecte de deformare - MACLE

n timpul deformarii plastice a otelurilor inoxidabile apar ca si la
celelalte metale si aliaje, macle de deformare.
Macla reprezinta o portiune dintr-un cristal cu o alta orientare
cristalina dect restul cristalelor. La microscop ele apar nuantate
diferit fata de restul grauntelui, ca urmare a diferentei de orientare
cristalina pusa in evidenta de atacul cu reactivi metalografici.
Maclele de deformare apar ca urmare a unor forfecari n cristal n
cursul procesului de deformare. Se remarca faptul ca vectorul
forfecarii este vectorul BURGERS al unei dislocatii SHOCKLEY.
Un defect de mpachetare poate fi considerat ca un generator de
macla. O suprapunere de defecte de mpachetare va duce la
formarea unei macle mecanice. O dislocatie SHOCKLEY C face sa
treaca atomii dintr-un plan (111) din pozitia A n B ; B n pozitia C siC
n pozitia A.
Astfel se poate spune ca macla mecanica se poate forma fie prin
forfecarea directa a austenitei, fie prin suprapunerea defectelor de
mpachetare.

Modificari structurale

Otelurile inoxidabile pot suferi modificari

de structura prin aplicarea unor prelucrari
termice sau mecanice:
tratament termic (impus de procesul de
fabricatie);
deformare plastica la rece (oteluri
austenitice);
recoacere dupa deformare la rece;
tratament termomecanic la temperatura nalta
(impus de exemplu otelurilor laminate la cald
sau supuse solicitarilor mecanice la
temperatura nalta).

Modificari structurale
Exemple tipice de structuri ale unor oteluri inoxidabile:
a) otel cu structur feritic;
b) otel cu structur martensitic;
c) otel cu structur austenitic;
d) otel cu structur austenito-feritic (duplex).

Transformarea martensitica n otelurile

inoxidabile

Transformarea martensitica duce la aparitia a doua faze: faza , hexagonal

compact, neferomagnetica si faza ', cubica cu volum centrat tetragonal,
feromagnetica.
Faza' corespunde martensitei ' specifica otelurilor cu continut redus de carbon
(oteluri inoxidabile) si nu permite aparitia unei deformari a retelei tetragonale.
Aceste faze pot aparea prin transformarea spontana a austenitei la o temperatura
mai mica dect MS, temperatura care depinde de compozitia aliajului. Nu s-a reusit
sa se puna n evidenta punctele MS pentru cele doua faze ' si .
La temperaturi mai mari de MS, transformarile pot sa apara si n timpul deformarii
plastice a materialului, pna la o temperatura limita Md, peste care transformarea
martensitica nu mai este posibila. Daca se executa deformarea la rece la
temperatura MdMs+150...200C atunci nu are loc transformarea austenitei n
martensita, indiferent de gradul de deformare aplicat.
Se poate astfel defini fie o temperatura de nceput de transformare martensitica Ms,
de origine termica, fie o temperatura Md de transformare martensitica produsa prin
deformare plastica. Aceste temperaturi pot fi calculate plecnd de la compozitia
chimica a otelului:
Ms = 1302 -42(Cr%)-61(Ni%)-33(Mn%)-28(Si%)-1667(%C+Ni) [[C]

Aceasta formula empirica este valabila pentru urmatoarele compozitii chimice:

10-18%Cr; 6-12%Ni;0,6-5,0%Mn; 0,3-2,69%Si; 0,004-0,12%C; 0,01-0,06%N.

Formarea martensitei intr-un otel austenitic de tip

18-8 la diferite temperaturi in functie de alungire
Pentru o tempertura Ms foarte scazuta (de exemplu -188 oC), un otel
poate suferi o transformare martensitica prin deformare;
procentajul de martensita formata, depinde n acelasi timp de gradul
real de deformare plastica si de temperatura: pentru un grad de
deformare dat, procentajul de martensita creste cu tempertura de
deformare.
Astfel, rezulta ca se poate defini o temperatura Md corespunzatoare
unei deformari date.

Efectul elementelor principale de aliere

Cr, Ni asupra Ms
Evolutia temperaturii Ms ntr-un
otel cu 10-14% Ni n functie de
continutul de Cr pentru 0,06% si
0,008% C.

Evolutia temperaturii Ms ntr-un

otel 18%Cr si 0,04%C n
functie de continutul de nichel .

Efectul deformarii plastice

Influenta deformarii plastice

asupra proportiei de si '
formata ntr-un otel 18/8 cu
putin carbon.

Influenta deformarii plastice si a

temperaturii de preracire la -196C
dupa hipercalire la 1050C, asupra
proportiei de si .

Efectul deformarii plastice

Deformarea otelurilor inoxidabile austenitice are loc dupa

mecanisme complexe care includ:
alunecarea normala a dislocatiilor la aliajele care au o mare energie
de mpachetare (EDI)
alunecare plana de dislocatii disociate n aliaje cu o slaba energie de
mpachetare. n urma acestor alunecari au loc:

formarea fazei hexagonale ;

formarea maclelor mecanice;
formarea martensitei ' prin unul din urmatoarele mecanisme:
' sau '.

Aceste doua mecanisme pot coexista, preponderenta unuia asupra

altuia fiind strns legata de parametrii reali si cei teoretici ai fazei .

Cea mai buna plasticitate este obtinuta atunci cnd diferitele

mecanisme pot sa se succeada n loc sa se confrunte. Aceasta
apare n timpul unei deformari la o temperatura apropiata de cea
a punctului Md sau cnd deformarea este facuta, n parte, peste
Md, n parte sub Md (efect TRIP).

Tratamente termice

Otelurile inoxidabile austenitice contin n general mai putin de

0,15%C, aceasta cantitate fiind n ntregime solubila n austenita cnd
temperatura este mai mare de 1000oC. Daca sunt racite lent sau
mentinute ntre 500-900oC, carburile pot precipita si prin aceasta pot
compromite anumite proprietati de utilizare.
Pentru a evita acest neajuns se aplica tratamentul de hipercalire.
Hipercalirea este un tratament termic aplicat otelurilor austenitice
care se efectueaza printr-o ncalzire de punere n solutie a carburilor
la o temperatura ridicata, cuprinsa ntre 1000oC si 1150oC,urmata de
o racire rapida n apa sau n aer (pentru piesele mici), pentru a evita
precipitarea carburilor la limita de graunte.
Carburile prezente n otelurile inoxidabile austenitice sunt de tipul
(CrFeMo)23C6 cu continut ridicat n crom, iar precipitarea lor pe limita
grauntilor duce la o saracire n crom a matricei adiacente, care
provoaca o sensibilitate a metalului la coroziunea intergranulara. O
mentinere ntre 600-1000oC duce la precipitarea fazei sigma, ceea ce
predispune la fragilizare si pierderea caracteristicilor de utilizare.

Fisuri

The microstructure consists

of a ferrite matrix containing
a volume fraction of around
20% of austenite. Ferrite
grains, formed as a result of
dynamic recrystallization, are
small and equiaxial, while
austenite particles are
elongated and aligned in the
direction of deformation. This
micrography also shows the
formation of some cracks at
interphase boundaries,
although most of them are
located at the ferrite/ferrite
boundaries.

Fisurarea la cald
Austenitic structures have a tendency to hot cracking
Hot cracking occurs slightly
above the melting
temperature of the lowest
melting constituent.
At this moment in the
welding solidification
process, dendrites are
surrounded by regions
containing interdendritic
low-melting liquid.
Strain causes fracture of
the solid bridges.
Schaeffler diagram, area of hot cracking

Fisurarea la cald

Keep away from oil and grease, clean

painstakingly after welding, use stainless
steel brushes.

Rezistenta la coroziune a oelurilor

inoxidabile
Teorii privind coroziunea intergranular
1. Teoria srcirii n Cr reducerea continutului de Cr sub
12% in stratul intergranular datorita precipitrii carburilor
de Cr micoreaz local rezistena la coroziune.
2. Teoria electrochimic - consider zona cu precipitate
ca o pil cu 3 electrozi, dintre care unul este matricea cu
coninut normal de Cr, al doilea matricea srcit in Cr
iar al treilea carbura de Cr, ansamblul fiind scldat n
electrolitul reprezentat de mediul de lucru. Curenii de
micropil determin corodarea matricei mai srace in Cr.
3. Teoria tensional - are n vedere promovarea
intercristalin a coroziunii pe seama tensiunilor mecanice
determinate de precipitarea carburilor.

Mechanism of sensitisation

As explained earlier, sensitisation is caused by the formation of chromium carbides on

grain boundaries. The precipitates absorb chromium from the adjacent austenite causing
a localised breakdown in passivity.

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
(cM23C6) 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 800C, 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 heattreatment. 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
750C. 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.

Time and temperature dependency of sensitisation (Mayo, 1997).

Evitarea sensibilizarii
A variety of solutions exist to avoid sensitisation:

The first one is to reduce the carbon content of the steel, making it more difficult to precipitate
carbides. Stainless steels with an 'L' associated with their numerical designation (e.g., 304L and
316L) have been manufactured with carbon cocentrations less than about 0.03 wt%, which
compares against the normal grades which typically have some 0.08 wt% of carbon. Figure 4
shows how carbon accelerates sensitisation.

Figure shows that an excessive amount of chromium can eliminate austenite

at all temperatures, making it impossible to achive a to transition. This is
the domain of the ferritic stainless steels discussed below.

Microaliere

An alternative is use solutes (such as Nb, Ti, V or Ta) which have a greater affinity for
carbon than chromium. These are called stabilised stainless steels, for example,
types 321 (Ti stabilised) and 347 (Nb stabilised) austenitic stainless steels. Titanium
cannot in general be used to make alloys deposited by arc welding because it readily
oxidises; type 347 is used instead as a filler metal. In welding applications, grade 321
is not used as a filler metal because titanium does not transfer well across a high
temperature arc. Niobium stabilised 347 is used instead as a filler metal.
Stabilisation involves more than just an addition of Nb or Ti. A heat-treatment must be
performed to stimulate the formation of TiC or NbC, for example by hoding at 900C
for one hour. This is because during lower temperature heat treatments, M23C6 may
form faster than TiC or NbC.
In some cases, a solution-treatment can be given after fabrication to dissolve
carbides which may have formed on grain boundaries.
A variety of other factors impact on the problem, such as the austenite grain size and
the crystallographic character of the grain boundaries. Sensitisation can be avoided
by grain boundary engineering (Shimada et al., 2002), by creating a crystallographic
textures which favours low-energy boundaries which are less effective as
heterogeneous nucleation sites. A reduction in the austenite grain size can also help
by increasing the number density of any carbides and hence reducing the extent of
associated Cr diffusion fields.

Environmentally assisted
cracking

Environmentally assisted cracking (EAC) is a generic term used to describe the

consequences of a three--fold interaction between stress, environment and
microstructure, an interaction which leads to unexpected failure with no ductility,
usually involving a period of slow crack growth prior to final failure.
Failure occurs at applied stresses well below the macroscopic yield strength. The
stress can be due to factors other than the intended design stress, for example,
residual stress induced during fabrication.
An aqueous environment is required in the form of immersion or via a thin film on the
surface when the component is exposed to humid atmospheres. Dissolved oxygen
and anionic species such as chlorides and fluorides accelerate EAC.
Some forms of this kind of cracking can be particularly dangerous because it may
take thousands of hours for a crack to nucleate, but considerably less for it to
propagate. Dramatic examples of catastrophic failure include the collapse of
swimming pool ceilings becuase of the stress corrosion cracking o Type 304 or 316
austenitic stainless steels. For this reason, it has been suggested that 6 wt% Mo
austenitic stainless steels should be used in these environments.
Recent work has shown that it is also possible to sensitise titanium--containing
stainless steels by the grain boundary precipitation of Ti(C,N) at 1100C, by a
microgalvanic mechanism (Joe and Kim, 1999).
A sensitised steel becomes more sensitive to EAC when impurities such as sulphur
and phosphorus segregate to the austenite grain boundaries (McIntyre et al., 1996).

Coroziune intercristalina

Efectele coroziunii

Fisurare datorata coroziunii intr-un otel inoxidabil austenitic 304L expus in mediu
cu methanol si acid oxalic.

Efectele coroziunii

Goluri de fluaj in otelul inoxidabil tip RA 330, prezentat prin iluminare

in contrast de faza (interferenta Nomarski) (200X).

Efectele coroziunii

Coroziune tenso-fisuranta in otel inoxidabil 310, expus in gaz natural cu

continut ridicat de sulf (100X).

Efectele coroziunii

Fisuri si crpturi intr-un tub din

otel inoxidabil turnat 304 expus in
etilena la temperaturi ridicate
(100X).

Multiple corrosion fatigue cracks at the I.D.

of a AISI 1020 carbon steel downhole tool.
The tool was rotating with the I.D. exposed
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 oelurilor inoxidabile

n cazul oelurilor inoxidabile, Cr nu influeneaz dect
tenacitatea. Aceasta este controlat mai ales de coninutul
de C i N2, a cror solubilitate n ferit scade foarte mult
odat cu creterea coninutului de Cr.
Ca urmare, la coninuturi mari de Cr, C i N 2, vor apare
precipitate din ce n ce mai abundente, sub form de
carburi, nitruri sau carbo-nitruri, avnd ca rezultat
micorarea tenacitii matricei de ferit fa de cea
corespunztoare oelurilor feritice comune, oelurile
devenind din ce n ce mai dificil de utilizat.
Pornind de la aceste constatri au aprut oelurile ELY
(Extra Low Interstitial) la care coninutul de carbon este C <
0,01% iar cel de azot N2< 0,005%, impunndu-se condiia
ca suma C+N2 s nu depaeasc 0,001%.
De exemplu la 28-35% Cr, C < 0,002% pn la 0,006% i N 2

Rupere fragila

Cleavage facets on a 410 stainless steel component

fracture surface resulting from brittle fracture.

Formarea fazei
Faza este un compus alcatuit din atomi de Fe si Cr.
n oelurile feritice cu 18% Cr, fr alte elemente de
aliere, faza fragilizant , n anumite condiii,
micoreaz i rezistena fa de coroziunea ce apare
dup 103 104 ore de functionare prin meninere la
550C.
Creterea coninutului de Cr reduce timpul de
precipitare i mrete temperatura la care precipita
faza . Adugarea de Si i mai ales Mo, scurteaz
foarte mult acest timp.
De exemplu la un oel cu 17% Cr i 2% Mo la 600C,
faza apare dup 200 de ore de meninere. Similar cu
cazul oelurilor austenitice Cr-Ni, precipitarea fazei
ncepe numai dup o precipitare prealabil de carburi n
masa fertitic care astfel devine srcit n Cr.

Intermetallic phase embrittlement: Sigma phase

Intermetallic phases (Sigma phases) may form at

temperatures between 500 and 900C in ferritic stainless
steels containing more than 14% Cr.

Schaeffler diagram, area of intermetallic phase embrittlement

Faza sigma
Sigma

Sigma

Faza Sigma (particule de culoare roie) 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

For a carbon percentage > 0,10 %, even with the fastest
cooling, they cannot
be avoided.
To avoid the formation of carbides, a special type of
stainless steel is
produced, having C </= 0,03 %.
The austenitic types with this low carbon are designated
with the letter L in
the American) ASTM standards. The production of them
is very difficult and
an extra metallurgical treatment (vacuum, argon
flushing) will be necessary,
which increase the cost.

Masuri pentru evitarea aparitiei carburilor

2. Another solution, except low carbon, it to stabilise the stainless steel

with
titanium (Ti) and or niobium (Nb). These elements have a strong tendency
to
form carbides, which will be formed at high temperatures (normal cooling
around 1000 to 1100 C). The chromium carbides, depending on the cooling
rate do form in the temperature range of 650 - 900 C.
If the titanium or niobium content is sufficient to combine all available carbon
(perhaps except 0,03 %), than no carbon is anymore available for the
chromium.
The following ratios do comply with these conditions:
Theoretically : %Ti / %C = 4 and %Nb / %C = 8
EN-standard : %Ti / %C = 5 and %Nb / %C = 10
ASTM-standard : 0,20 % + 4(%C + %N) < (%Ti + %Nb) < 0,80 %

Fragilizarea la 475C

Aceasta este o form particular de fragilizare care apare cu prilejul

unei recoaceri n jurul temperaturii de 475C, la oelurile inoxidabile ce
conin ferit (feritice, austenito-feritice, ferito-austenitice).
La concentraii de peste 12% Cr este necesar un timp de meninere
foarte ndelungat pentru apariia acestui mod de fragilizare (105ore).
Prin creterea coninutului de Cr, Si, Al, Mo timpul de meninere se
reduce foarte mult. Carbonul reduce aceast tendin de fragilizare
datorit faptului c producerea carburilor determin srcirea n crom a
matricei metalice de baz.
Aceast fragilizare se produce sub aproximativ 500C ca urmare a
unor procese de segregare care au loc n ferit. Se separ mai nti o
faz feromagnetic bogat n Fe, numit faza apoi o faz bogat
n Cr i paramagnetic. Nici una dintre acestea nu este decelabil cu
ajutorul microscopiei optice datorit precipitrii foarte fine. Se obine
creterea duritii, a rezistenei la rupere, a limitei de curgere,
micorndu-se alungirea i gtuirea la rupere dar, mai ales reziliena
i tenacitatea la rupere.

Comportarea la sudare

Oelurile feritice cu Cr au aprut mai trziu dect cele austenitice,

datorit creterii preului Ni i a ncadrrii acestui metal ntre
materialele strategice.
Prin dezvoltarea oelurilor feritice cu Cr s-a urmrit nlocuirea
oelurilor austenitice Cr-Ni. Din pcate, oelurile feritice nu au reusit
s le nlocuiasc pe cele austenitice dect pentru anumite aplicaii,
dei sunt mult mai ieftine i au o rezisten superioar fa de
coroziunea fisurant sub sarcin. Acestea prezint totodat
urmtoarele dezavantaje:
sudabilitate slab;
sensibilitate, n anumite condiii, fa de fisurarea la rece;
caracteristici mecanice ale sudurilor nesatisfctoare n cazul unor
aplicaii pretenioase;
prelucrabilitate mecanic slab.