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journal homepage: www.elsevier.com/locate/commatsci

steel Part 1: Prediction of microstructure evolution and

coupling with mechanical properties

A. Eser a, C. Broeckmann a, C. Simsir b,

a

b

Institute for Materials Applications in Mechanical Engineering (IWM), RWTH Aachen University, Augustinerbach 4, 52062 Aachen, Germany

_

Metal Forming Center of Excellence (MFGE), Atlm University, Kzlcasar Mah., 06836 Incek-Glbas

, Ankara, Turkey

a r t i c l e

i n f o

Article history:

Received 6 September 2015

Received in revised form 10 November 2015

Accepted 14 November 2015

Available online 2 December 2015

Keywords:

Tempering

Multiscale modeling

Precipitation simulation

Microstructureproperty relationships

AISI H13

a b s t r a c t

In the first part of this two part study, the mechanical properties necessary for the simulation of tempering of an AISI H13 (DIN 1.2344, X40CrMoV5-1) tool steel was derived using physically based precipitation

simulations and microstructureproperty relationships. For this purpose, the precipitation of fine

carbides were simulated using a thermo-kinetic software which allows prediction of the evolution of precipitation/dissolution reactions and the particle sizes. Then, those microstructural findings were coupled

with physically based microstructureproperty models to predict the yield stress, flow curve and creep

properties. The predicted mechanical properties were verified with corresponding experiments and a

good agreement was found. In the second part of this study, those properties were coupled with a

Finite Element (FE) model in order to predict the relaxation of internal stresses and the evolution of deformations at the macroscopic scale.

2015 Elsevier B.V. All rights reserved.

1. Introduction

Hot-work tool steel AISI H13 (DIN 1.2344, X40CrMoV5-1) is

mainly used as tools for extrusion, forging dies and especially as

die-casting dies for the processing of light metals. AISI H13 has distinguished mechanical properties like high hardness, good wear

resistance, thermo-cyclic stability and high strength at elevated

temperatures which are essential for high temperature tool applications. These properties can be generated only by a controlled

heat treatment process which consists of an austenitization treatment with a subsequent hardening and a multiple tempering procedure. The superior mechanical properties are due to the

nanometer size alloy carbides which precipitate during the tempering. In order to predict the mechanical properties of AISI H13

during and after tempering, the development of those carbides

should be well known. The chemical composition of the investigated steel is given in Table 1.

There are several attempts in the literature which concentrate

on predicting the macroscopic material properties from the

microstructural parameters. Most of the previous work in the liter-

Corresponding author.

E-mail address: caner.simsir@atilim.edu.tr (C. Simsir).

http://dx.doi.org/10.1016/j.commatsci.2015.11.020

0927-0256/ 2015 Elsevier B.V. All rights reserved.

other side there exist several studies about predicting the high

temperature creep behavior of 912% CrMoV-Steels [6,7]. All of

those models require microstructural parameters which should

be determined from highly costly experiments. Furthermore, most

of the previous attempts concentrated on one particular heat treatment state and did not simulate the evolution of the mechanical

properties during the heat treatment. Therefore the prediction

capability of those models for different microstructures is limited.

Moreover there is the commercial software JMatPro which simulates the material properties for different heat treatment conditions [8,9]. However, at best of authors knowledge, prediction of

the yield stress, flow and creep properties with this software during the tempering of steels is not possible.

In the present work, the previously mentioned singular efforts

were coupled together to determine the mechanical behavior of

an industrial steel during a heat treatment process. The precipitation kinetics were determined using the software MatCalc (Version

5.51.1011) [1012]. The results of the simulations namely size, volume fraction of carbides and the concentration of alloying elements in the matrix are used as input parameters for the

physically based material models to predict the mechanical

properties.

281

rss = solid solution hardening of matrix, rP = precipitation hardening, rdis = dislocation strengthening rsgb = subgrain strengthening.

Table 1

Chemical composition of steel AISI H13 (wt%).

C

Cr

Ni

Mo

Mn

Si

0.40

5.37

1.34

1.22

0.3

0.97

The temperature dependent

lowing expression [22]:

2. Modeling

rfe 78 0:023 T

worth summarizing the stress relaxation mechanisms before starting to calculate the required material properties to simulate this

effect.

During quenching of tool steels, residual stresses are induced

due to non-homogeneous inelastic deformation due to thermal

gradients in the part. Those stresses relax during tempering either

by time-independent (yielding/time-independent elasto-plastic

deformation) or by time-dependent (creep/visco-elasto-plastic

deformation) deformation. The deformation occurs so that the geometric mismatch between the neighboring regions in the parts

decrease resulting in a decrease (relaxation) in residual stress level.

Relaxation (deformation) by yielding occurs instantaneously

when the local yield strength of the material is below the yield

strength of the material due to the increasing temperature. This

usually occurs during heating up to the tempering temperature.

However, the bigger extent of the relaxation (deformation) usually

occurs during holding at the tempering temperature by creep

mechanism since creep occurs as time goes on at any non-zero

stress level without the need of exceeding a yield strength. Moroever, the regions having larger stresses creep (relax) faster than the

regions with low stresses; which also enhance the relaxation

process.

In order to simulate the stress relaxation and deformations during the tempering, both elasto-plastic properties (yield strength,

flow curve) and creep properties must be determined either experimentally or computationally.

According to Lacy rss , the strength contribution due to the

alloying elements can calculated as [23]:

The thermo-kinetic software package MatCalc is based on the

numerical KampmannWagner model [13,14] describing the precipitates in terms of size classes. The nucleation approach is based

on the classical nucleation theory [15,16]. The thermo-dynamic

calculations are considered by CALPHAD methods and CALPHAD

databases [17,18]. The program calculates chemical potential and

driving forces of all phases as well as the diffusion coefficient by

using chemical composition and temperature dependent mobility

database for all the elements. Based on these data, the development of the precipitate size and the composition of the precipitates

can be calculated. There are several studies in the literature for the

simulation of carbide development during the heat treatment of

hot-work tool steels and good agreement between the experimental findings and simulation results were reported [1921].

2.3. Prediction of yield stress

Several strengthening mechanisms contribute to the overall

strength of the steel AISI H13. The overall yield strength of a complex tempered martensite (ryield ) can be assumed to be a linear

superposition of each individual strengthening mechanism [13]:

rss

f

X

n

K iXi i

i1

matrix, K i and ni are alloying element dependent constants

(Table 2). The temperature dependency of the solid solution hardening is assumed to be similar to the temperature dependency of

the shear modulus (Eq. (7)).

2.3.3. Precipitation hardening

In order to calculate the strengthening of the steel due to the

precipitations, the MatCalc internal model was used. The model

is based on the work of Holzer et al. [4,5]. and based on the

assumption that the coherent precipitates are shearable on the

contrary incoherent ones are not shearable by dislocations. Then

the strengthening due to precipitation hardening can be expressed

as:

rP

Ncoh

Ntotal

1=2 q

1=2

N

r2chem r2coh r2mod incoh

ro

Ntotal

where Ncoh ; N incoh ; N total are the number densities of the coherent,

the incoherent and the sum of the number densities of precipitates,

respectively. The terms in the second square root are the strength

contributions due to chemical hardening effect (rchem ), the coherency strain effect (Misfit strengthening) (rcoh and the modulus

hardening effect (rmod ). The final term (ro ) in Eq. (4) is the strength

contribution of the impenetrable precipitates.

The chemical hardening term (rchem ) is described by the general

FriedelBrownHam equation [26]:

rchem

2M

bkC1=2

cb

3=2

b is the magnitude of the Burgers vector and k is the mean particle

spacing in the slip plane of the dislocation.

The so called misfit strengthening (rcoh ) due to the lattice

coherency of precipitates with the ferritic matrix is described

according to Brown and Ham [26]:

1=2

N

r2

b

where r represents the mean precipitate radius, G is the shear modulus, e is the linear misfit strain, and N is the corresponding number

density.

The modulus strengthening effect is due to the intersection of

dislocations with a spherical precipitate having a shear modulus

lower than the shear modulus of the matrix. The formulation based

on the work of Russell et al. [27]:

282

Table 2

Parameters K and n from Eq. (3) (for carbon from [3,24,4,25] and other alloying elements from [23]).

K i (MPa/wt%)

ni ()

rmod M

Al

Cr

Mn

Mo

Nb

Ni

Si

1171:3

1=3

4000

0:75

1400

0:75

7000

0:75

9600

0:75

4000

0:75

6100

0:75

11000

0:75

4000

0:75

11000

0:75

"

2 #3=4

Gb

Up

1

k

Um

where U p and U m are the line energies of the dislocation in the precipitate (U p ) and in the iron matrix (U m ), respectively.

Finally the strengthening effect of impenetrable particles (ro ) is

described by the Orowan Mechanism [28]:

ro CM

Gb

ro

ln

k

ri

radius of the dislocation stress field.

2.3.4. Dislocation strengthening

The contribution of the dislocations for the strengthening of the

steel can be defined by the well-known equation of Taylor [29,30]:

rdis a G b qdis

of the strengthening due to dislocations is taken into account with

Eq. (10) [1]:

10

can be calculated for the martensitic steel by Eq. (14) [33,34,37]:

rsgb

115

2w

14

carbon content of the steel. For a carbon content of 0.4% for the steel

of interest, the lath width is calculated as 0.1 lm [38]. This value

agrees well with the microstructural measurements from previous

studies for similar steels [31,39]. The temperature dependency of

the subgrain strengthening is correlated with the temperature

dependency of the shear modulus [40]. In this work, the lath width

was assumed to be constant for the tempering temperatures of

520 C and 600 C which are rather lower than the temperatures

at which static recovery of the martensitic lath structure can take

place. For the tempering temperature of 650 C, the static recovery

of the martensitic laths (coarsening of the martensite laths) is

known from the literature [41]. The evolution of the martensitic

lath width is predicted with an Arrhenius type equation similar to

Eq. (13).

dw

Q

C w wexp m

dt

RT

15

work of Straub within the temperature range of 298973 K [6]:

where C w is a constant with a value of 1.4 103. After double tempering at 650 C for two hours the martensite lath width was calculated to be around 0.17 lm from Eq. 15.

G 0:039431 T 98:46456

11

where G is in GPa.

Bhadeshia et al. [3] proposed a general equation to determine

qdis of martensite at room temperature (RT) after quenching

depending on the martensite start temperature (M s in Kelvin)

logqdis 9:2840

6880:73 1780360

Ms

M 2s

12

previous work of the authors [35]. Finally the dislocation density of

the martensitic structure of AISI H13 is calculated as 7.41 1015

[1/m2] at RT from Eq. (12). The evolution of dislocation density

qdis during tempering can be estimated with an Arrhenius type

equation [21,32]:

dqdis

Q

C dis qdis exp v

dt

RT

13

of vacancies (134 kJ/mol, [1]) and R is the gas constant. The

dislocation density of a double tempered tool steel (at 600 C for

two hours) of X38CrMoV5-1 which has a very similar chemical

composition to the steel of interest in this work was measured to

be 6 1014 [1/m2] [31]. Using the initial and final dislocation

density for a tempering process of two hours at 600 C, constant

C can be calculated from Eq. (13) as 3.002 104.

2.3.5. Subgrain strengthening

The contribution of the subgrains on the strength of the martensitic steel rsgb depends inversely on the mean value of the larger

diameter of slip planes [4,33,34,36]. The mean slip plane diameter

depends mainly on the thickness of the martensite lath w

evolution of the yield stress during the tempering but also a complete temperature dependent flow curve is necessary to describe

this phenomenon quantitatively.

In this work, the development of the work hardening was modeled by KocksMecking type equation [42]. Assuming that the

mobile dislocations move a mean free path L before they are

immobilized or annihilated, the evolution of the dislocation density qdis can be described by [43]:

dqdis M e_ pl

dt

bL

16

where e_ pl is the plastic strain rate, M is the Taylor factor. The mean

free path L is limited by the average spacing between dislocations:

A

L p

17

qdis

During the softening due to spontaneous annihilation, the

reduction of the dislocation density can be defined by Eq. (18) [44]:

dqdis

dann

q Me_ pl

B2

dt

b dis

18

in which B is a constant depending on the different number of activated slip systems. The critical distance dann is described by [45]:

4

dann

Gb

2p1 mQ mf

19

283

m is the

The modeling of recovery by dislocation climb is based on the

model of Lindgren et al. [43], with the assumption that the thermally activated climb is controlled by the self-diffusion coefficient

along dislocations Dd (pipe-diffusion) [46]:

dqd

Gb

C2Dd

q2 q2deq

dt

kB T dis

3

20

the equilibrium dislocation density and C is a constant, which takes

solute trapping into account.

Finally the dislocation core diffusivity Dd is coupled to the

bulk diffusivity Db by Eq. (21) in MatCalc via a temperature

dependent factor ad :

Dd ad Db

21

parameter should be defined. First of all the parameter A which

depends on the average distance between dislocations and dislocation density should be known. In the work of Polcik [7] for a

martensitic chromium steel, the distance between the free dislocations was reported as 0.117 lm and for the dislocations in subgrains as 0.01 lm respectively. Hence the material parameter A

can be calculated from Eq. (17) between 0.17 and 4.59. This parameter was determined as 0.4 from iterative fitting of the calculated

and experimentally determined flow curve and is between the possible value of 0.17 and 4.59 [7]. The other two parameters namely B

from Eq. (18) and C from Eq. (20) were taken from the work of

Sherstnev et al. [47] and have values 5 and 0.001.

Especially for tool steels which are normally tempered for long

soaking times at elevated temperatures above 0:4T m , where T m is

the melting temperature of the steel, creep plays a major role on

the amount of stress relaxation.

The physically based creep model used in this work is based on

the composite model of Mughrabi et al. [48,49]. Blum et al. implemented this model to predict the high temperature creep behavior

of the martensitic steels [6,7,50,51]. The basic idea of the model is

that the heterogeneous dislocation distribution causes a heterogeneous stress distribution. Correspondingly the material is treated

as a composite of a hard (subscript h) phase with high dislocation

density and a soft (subscript s) phase with low dislocation density. It is assumed that the total strain etot is identical in both

regions:

rs

E

es

rh

E

eh

22

where etot is the sum of elastic and the plastic strain, E is the elastic

modulus, rs and rh are the local stress acting in soft and hard

region. The elastic strain is calculated by the terms rs =E; rh =E for

the soft and hard region respectively. es and eh are representing

the plastic strains in the corresponding regions. Due to the heterogeneous distribution of the dislocations, internal forward stresses

rf are formed at the (hard) subgrain boundaries corresponding to

internal back stresses rb in the subgrain interior. The local stresses

rs and rh can be defined as:

rs rA rb ;

23

rh rA rf ;

24

where

r

etot 1 f h es f h eh

rA f s rs f h rh :

25

26

where the first term rE is the elastic strain and the plastic strain

epl is defined by Eq. (27) as follows:

epl 1 f h es f h eh :

27

Differentiating Eq. (27) for the case of creep (r = constant) gives the

plastic deformation rate:

e_ pl 1 f h e_ s f h e_ h f_ h eh es

28

where e_ s and e_ h are the deformation rates in the soft and hard

region of subgrains respectively. The local deformation rates are

formulated as:

e_ s

b

q ms ;

M dis

29

e_ h

b

q mh ;

M dis

30

with ms and mh the velocity of the dislocations in soft and hard region

and defined by Eqs. (31) and (32) respectively.

s

b s rh

M kb T

2

mh v h;0 sinh

2.5. Creep

etot

In Eq. (25), the terms f h and f s is the volume fraction of the hard

and soft regions. The volume fraction of hard region is defined as

f h a 2=w (a = width of hard region, 2=w: subgrain boundary area

per volume) and for the soft region as f s 1 f h , so that the total

strain can be calculated from Eqs. (22) and (25) as:

31

!

32

the subgrain boundaries. b and n are parameters and Bs and v h;0

describes the temperature dependency with Arrhenius type

equations.

Q

B As exp s

RT

v h;0 Ah exp

33

Q

h

RT

34

regions and As ; Ah are constants. The effective stresses rs ; rh

defined in Eqs. (29) and (30) in soft and hard regions are defined

as follows:

35

rh rh rp;h :

36

The effective stress in a soft region r is described as the difference between the local stress in soft regions rs and the stress components resulting from the interaction with other free dislocations

rdis and precipitates rp;s . On the other side, the effective stress in

hard regions rh is defined as the difference between the local stress

in the hard region rh and the stress component resulting from the

interaction with other free precipitates rp;h . The athermal stress

component rdis which results from the interaction of the free dislocations, is calculated using Eq. (9). The stress component rp;s

resulting from particle hardening in soft regions can be formulated

with particle size dp and the average volume fraction f p of the

precipitates.

s

37

284

rOrowan:s 3:32 G b

q

Np

f p;s;k

X

k1

38

dp;k

where N p is the number of precipitates. The phenomenological relationship between the parameter C p;s and the local stress rs is

described by Eq. (35).

rs

1 exp

C1

C p;s

C 2 !!1=C2

39

The volume fraction of different particles in the soft region f p;s;k

can be calculated as:

f p;s;k

1 Up;SGB

f p;k

1 f p;SGB

40

and f p;SGB is the volume fraction of the subgrain boundary region

where particles attached to subgrain boundaries are lying. The

value of f p;SGB is related to subgrain sizew and particle size dp;k :

p dp;k 3

f p;SGB 1 1 p

2 6 w

41

free precipitates rp;h in the hard region is calculated from

rp;h

2

f p;h;k

Eo X

b 1 dp;k

42

dp are expressed in meters.

The volume fraction of particles in the hard region is equal to

the average volume fraction f p;k of different particles times the

local relative particle density in the hard region:

f p;h;k f p;k

Up;SGB

43

f p;SGB

The evolution of the microstructure during creep can be formulated from the equations above. The parameters of the dislocation

structure are the mean subgrain size w, the spacing between free

dislocations in the subgrain interior q0:5

, the width of the hard

f

region a, and the spacing s between the dislocations in the subgrain

boundaries. Their steady state values (after creep) designated by

the subscript 1 are given by the equations:

w1 10

bG

jrj

q0:5

dis;1 3:9

bG

jrj

s1 1:5 b

a1

44

45

0:5

46

jrj

0:05 w1

2

47

dis ; a and s is

assumed to develop with strain e along a path relating the initial

value to the steady states values:

log f log f1 logfo =f1 exp

e

kf

48

dis ; a and s with appropriate values for kf .

Under constant loading (creep), the rate of the local stress in the

soft region can be calculated by differentiation of Eq. (23):

r_ s f h Ee_ h e_ s f_ h

rs r

fh

49

Eq. (49) was integrated over the plastic strain, so that the development of the plastic strain rate during creep can be achieved. The

necessary material and microstructure parameters for the modeling

of creep is summed up in Table 3.

3. Results and discussion

3.1. Precipitation

For realistic simulation of the precipitation evolution during

annealing, the initial precipitation state should be known. In this

work, the initial microstructure (carbide size, carbide content)

after austenitization and quenching was determined from the

scanning electron microscope (SEM) investigations [52]. The

undissolved carbides after austenitization and quenching found

to be MC carbides with a volume fraction of 0.65 vol% and average

radius of 57.01 nm. In order to define the initial state, a so called

Virtual Pre Treatment in MatCalc was conducted. The parameters

of the Virtual Pre-Treatment can be arbitrarily selected so that

the phase fraction and the size of the carbides in the initial structure are consistent with the experimentally determined values.

After several iterative Virtual Pre Treatment simulations, the calculated carbide phase fraction and the average radius of the MC

carbides matched with the experimental findings, which describes

the initial state before tempering.

The carbide types and the possible nucleation sites considered

in the simulation were selected to be the same as in the previous

work of Sonderegger [53] where a similar hot-work tool steel

was investigated (Table 4). Furthermore dislocation density and

subgrain size were given as input for the simulation of precipitation during tempering, whose values were discussed already in

the previous section.

The simulation of the precipitation development during tempering was conducted for three different tempering temperatures;

520, 600 and 650 C (Figs. 13). 520 C is the tempering temperature, where the maximum hardness can be achieved [56]. 600 C

is a common tempering temperature for this kind of steels and

650 C is towards the highest temperature, that the hot-work tool

steel can be tempered. The heating and cooling times were selected

as 0.5 h and the soaking time at the corresponding tempering temperature as 2 h. The diagrams show only the secondary hardening

carbides, which precipitate during tempering. Phase fraction and

size of MC carbides, which do not dissolve during austenitization,

change only slightly during tempering.

For all of the tempering temperatures, cementite was formed

during the heating to the tempering temperature in the first tempering step and dissolves rapidly at the tempering temperature.

The M7C3 carbides were formed rapidly upon reaching the tempering temperature and the phase fraction was higher than all the

other carbides except for the tempering temperature of 650. However, its fraction decreases with further soaking time. In contrast,

the fraction of the second Cr rich carbide namely M23C6 increases

gradually during the tempering. For the tempering temperature

of 650 C, M23C6 carbide has the highest volume fraction in comparison with the other carbides. The calculated phase fraction of

M6C carbide has its maximum value during tempering at 600 C.

The phase content of this carbide also rises gradually with the

increasing tempering time, except during tempering at 650 C, like

the M23C6 carbide. However, the calculated phase portion of this

carbide was lower than that of the other carbides except for the

285

Table 3

Material and microstructure parameters for the creep model.

Definition

Value

Source

kw

ka

kqdis;0

Initial dislocation density

Initial spacing between the dislocations in the subgrain

the fraction of particles located at subgrain boundaries

Eq. (48)

Eq. (48)

Eq. (48)

Eqs. (8) and (9)

0.01 (lm)

0.87

0.1243

0.003

0.0005

[38]

[2]

[7]

[7]

[7]

[7]

[7]

ks

C 1 rOrowan;s

C 2 rOrowan;s

Eq. (48)

Eq. (39)

Eq. (39)

0.0005

116:37 53:54 ln0:25 rOrowan;s 21:65

[7]

[7]

[7]

Eq. (10)

[1]

b

G

Qs

Qh

As

Ah

Bs

b

n

Burgers vector

Shear modulus

Activation energy (soft region) Eq. (33)

Activation energy (hard region) Eq. (34)

Eq. (33)

Eq. (34)

Eq. (31)

Eq. (31)

Eq. (31)

0.248 (nm)

Eq. (11)

562 (kJ/mol)

562 (kJ/mol)

3.59 1015 (m/s Pa)

4.39 1020 (m/s)

9.0 1019 (m/Pa s)

0.59

0.045

[7]

[6]

[7]

[7]

[7]

[7]

[7]

w0

qdis;0

s0

Up;SGB

Table 4

Carbide types and their possible nucleation sites which were considered in the

precipitation simulations.

Carbide type

MC

M23C6

M7C3

M6C

Cementite (M3C)

Grain boundary,

Grain boundary,

Grain boundary,

Grain boundary,

Dislocations

Subgrain

Subgrain

Subgrain

Subgrain

boundary, Dislocations

boundary

boundary

boundary

shows its maximum value after annealing at 650 C. In particular

the phase fraction of MC carbide increases significantly towards

the end of the second tempering step at 650 C (Fig. 3).

Another important parameter with regards to the precipitation

strengthening is the carbide size. The simulation results show that

the M23C6 carbides were larger than all other carbides at each tempering temperature. The coarsening rate of this carbide, especially

at 650 C was observed to be very high compared to the other

carbides (Fig. 3). Although the M7C3 carbide shows coarsening with

increasing tempering temperatures, the coarsening rate, when

compared with the M23C6 carbide was very low. However, the

coarsening of the M7C3 carbide is faster than the MC and M6C carbides. The M6C carbide has a higher resistance to coarsening, especially at elevated temperatures. The size of the carbide was higher

at the tempering temperatures of 520 C and 600 C than that of

MC carbide, however, the size of the carbide after tempering at

650 C was almost equal to be the size of the MC carbide. Finally,

the mean radius of the MC carbide after each tempering temperature was calculated as the smallest compared to the other carbides.

Fig. 4 shows the results of the calculated phase fraction and the

carbide size of the secondary hardening carbides after two times

tempering at the corresponding tempering temperatures. The total

fraction of the secondary carbides corresponds to about 5.6 vol.% at

520 C, 5.8 vol.% at 600 C and 5.3 vol.% at 650 C. In the work of

Ebner et al. [54] the phase fraction of secondary carbides was

determined for the steel X38CrMoV5-3 as 4.5 vol.% for the austenitization temperature of 1050 C. Although the exact tempering

temperature was not mentioned in the work, the tempering

Fig. 1. Kinetic simulation of the precipitate evolution of steel AISI H13 during tempering at 520 C: (a) tempering temperaturetime profile; (b) phase fraction; (c) mean

precipitate radius; and (d) number density.

286

Fig. 2. Kinetic simulation of the precipitate evolution of steel AISI H13 during tempering at 600 C: (a) tempering temperaturetime profile; (b) phase fraction; (c) mean

precipitate radius; and (d) number density.

Fig. 3. Kinetic simulation of the precipitate evolution of steel AISI H13 during tempering at 650 C: (a) tempering temperaturetime profile; (b) phase fraction; (c) mean

precipitate radius; and (d) number density.

Fig. 4. Simulated phase fraction and mean radius after two times tempering at the tempering temperatures of 520 C, 600 C, and 650 C.

HRC were achieved, which corresponds to a tempering temperature of 600 C. In a further study [53], the carbides of the steel

X38CrMoV5-3 were examined with SANS (small-angle neutron

scattering). The samples were austenitized at 1060 C for 50 min

and tempered twice at 550 C for one hour and at 610 C for two

hours. The phase fraction of Cr-rich secondary hardening carbides

corresponded to 2.3 0.2 vol.% and the fraction of MC and Mo-rich

secondary hardening carbides 1.9 0.2 vol.%. The sum of the phase

fraction of the MC and M6C carbides secondary hardness in this

work was calculated as 0.97 vol.%, 1.58 vol.% and 1.60 vol.% for

the tempering temperatures of 520, 600 and 650 C correspondingly. On the other side, total phase fraction of M7C3 and M23C6

Cr-rich corresponds to 4.6 vol.%, 4.2 vol.% and 3.7 vol.% for tempering temperatures each for 520, 600 and 650 C. In this work, the

calculated phase fraction of the Cr-rich carbides was higher than

that of the experimentally measured values from the literature.

However, the phase fractions of the MC and M6C carbides were

more consistent with the literature data.

The above-mentioned discrepancy between the simulated and

experimentally observed phase fractions can be explained with

two aspects. First of all, the steel X38CrMoV5-3 contains less carbon (0.38 wt% instead of 0.40 wt%), chromium (4.8 wt% instead of

5.37 wt%) and vanadium (0.62 wt% instead of 1.22 wt%) and more

molybdenum (2.8 wt% instead of 1.34 wt%) than the steel AISI

H13. The higher estimated proportion of Cr-rich carbides in this

study can be explained by the higher percentage of chromium.

The lower phase fraction of M6C carbides MC and in this work compared to the literature [53] should be connected to the lower content of molybdenum. The higher phase fraction of the total

simulated secondary carbides in this work compared with the literature can be explained due to the higher carbon content of the

investigated steel. The second important aspect that can lead to

above mentioned deviations can be due to different heat treatment

processes. In Ref. [53], tempering time and tempering temperatures varies from the present work. (1st tempering step = 550 C

(1 h) and 2nd tempering stage = 610 C (2 h)). This can affect not

only the carbide size, but also the phase fraction. The coarsening

of Cr-rich carbides for the steel X38CrMoV5-1 was also

investigated in the work of Hu et al. with transmission electron

microscopy (TEM) measurements [55]. For the relative fraction of

Cr-rich carbides to the total carbides was reported to be 65.4%

which was very close to the calculated value of 66% in this work

(tempering temperature of 600 C). In contrast, the relative fractions of the M6C and MC carbides were identified in the work

[55] to be 23% and 11% respectively, in the present study they

are calculated to 16% and 18% (without considering the MC carbides, which do not dissolve during austenitization). At this point

it should be mentioned that the vanadium content of the steel in

the work of Hu et al. [55] was 1.02 wt% (instead of 1.22 wt% in

the present study) and the molybdenum content was 1.5 wt%

(instead of 1.34 wt% in the present work). The calculated higher

fraction of MC carbides and lower fraction of M6C carbides in this

work compared to reference [55] is due to the higher vanadium

and lower molybdenum content of the investigated steel in this

work.

The secondary carbides show a gradual coarsening with the

elevated tempering temperatures (Fig. 4). The mean radius of the

Cr-rich carbide after tempering was measured to be around

44 nm for a similar steel [55] for the tempering temperature of

610 C. This value lies between the calculated mean radius of

M7C3 and M23C6 at 600 (about 25 nm for M7C3 and M23C6) and

650 C (about 50 nm for M7C3 and M23C6). Furthermore in the same

study, the rod-shaped carbides of M6C reported to have the dimension of 20 55 nm (approximately 17.5 nm average radius if it was

assumed to be spherical carbides). This was between the calculated

287

size of MC carbides values was reported between 20 and 40 nm

in Ref. [55]. These values were slightly higher than the calculated

values of approximately 8 nm at 600 C and 16 nm at 650 C.

Despite the existing deviations of the measured phase fractions

and carbide sizes in the literature and simulated values in this

work, the discrepancy is within the deviation range of the experiments and simulations.

3.2. Yield stress

The calculated precipitation strengthening during tempering

from Eq. (4) is represented in Fig. 5. The overall precipitation

strengthening decreases with increasing tempering temperatures,

due to the coarsening of the secondary carbides as expected. However the drop of the precipitation strengthening of the Cr-rich carbides (M7C3 and M23C6) compared to the V-rich MC carbides and

Mo-rich M6C carbides was much larger due to the higher coarsening rate of the Cr-rich carbides at elevated temperatures

(Figs. 2 and 3). Nevertheless, M7C3carbides has the highest precipitation strengthening for the tempering temperature of 520 C. In

contrast, the second Cr-rich carbide M23C6, despite higher phase

fraction has lower precipitation strengthening due to its large size.

For tempering temperatures of 600 C and 650 C provide the secondary MC carbides the largest contribution to the overall yield

strength. MC carbides show higher precipitation strengthening

due to their high resistance to coarsening, especially at higher

tempering temperatures and longer soaking times (2nd tempering

step). On the other hand the coarser MC carbides which were not

dissolved during the austenitization have minor effect on the

overall precipitation strengthening.

The The simulated total yield stress, each strengthening component and the experimental yield stresses for three different tempering temperatures are summarized in Fig. 6. The experimental

yield stresses were measured by compression tests in the previous

work [52]. Experiments were conducted with the same temperature profile applied in the simulations (0.5 heating/cooling time, 2

h soaking time at tempering temperature). By comparing the calculated and experimental values, very good agreement can be

observed in the error range of experiments. It should be noted that

during the tempering, the microstructure was not stable and the

experiments had larger error bars especially for the first tempering

step.

Subgrain boundaries of the martensitic steel are the major

obstacle against gliding of mobile dislocations [41]. The simulation

results capture this phenomena quite well and the subgrain

strengthening was the highest strength component for all tempering temperatures. For the tempering temperatures of 520 and

600 C, it was assumed that there is no change of the lath width

during tempering. For the tempering temperature of 650 C, coarsening of the martensitic lath was calculated from Eq. (15). The precipitation strengthening has its maximum contribution to the

overall strength for the tempering temperature of 520 C, where

the maximum hardness of the steel AISI H13 is also expected

[56]. The effect of the precipitation strengthening gradually

decreases with increasing temperature due to the coarsening of

the carbides.

3.3. Flow curve

One of the major stress mechanisms during tempering is due to

the yielding under the influence of quenching induced residual

stresses due to decreasing yield strength. After determining the

yield stress during tempering, the presence of the stress relaxation

due to this mechanism can now be estimated. However, the magnitude of this relaxation can only be calculated if the complete flow

288

Fig. 5. Simulated precipitation strengthening rp during tempering compared with the experimental findings: (a) Tempering temperature 520 C. (b) Tempering

temperature 600 C. (c) Tempering temperature 650 C.

Fig. 6. Simulated yield stresses and the corresponding strengthening terms during tempering compared with the experimental findings: (a) Tempering temperature 520 C.

(b) Tempering temperature 600 C. (c) Tempering temperature 650 C.

curve is known aside the yield strength. For this reason, simulations of the flow curves during tempering are required. The critical

point during tempering where the stress relaxation (time independent) due to the drop of yield stress can occur should be where the

tempering temperature is just reached. After reaching the tempering temperature, the time dependent relaxation due to creep

of the flow curve was carried out immediately after the tempering

temperature reached.

The calculated and measured flow curves at 520 C, 600 C and

650 C for the first and second tempering step are shown in Fig. 7.

The measured and simulated flow curves match quite well with

289

Fig. 7. Simulated flow curves at the corresponding tempering temperatures (immediately after reaching the tempering temperature) compared with the experimental

findings: (a) Tempering temperature 520 C. (b) Tempering temperature 600 C. (c) Tempering temperature 650 C.

each other. At this point it should be once more pointed out, that

especially for the first tempering due to the higher instability of

the microstructure at elevated temperatures, the measured values

has higher uncertainty [52]. Considering this, a better agreement of

the measured and calculated flow curves for the second tempering

cycle can be observed from Fig. 7 as expected.

3.4. Creep

Especially for steels with higher tempering temperatures, creep

(time-dependent/viscous deformation) is the major stress relaxation mechanism during tempering. The experimental observation

showed that short term creep effect for the steel AISI H13 becomes

significant for the tempering temperatures of 600 C and 650 C

[52]. In contrary to the instant compression tests conducted during

the tempering to determine yield stress and the corresponding

flow curves, the creep experiments were conducted on three times

tempered specimen, so that a stable microstructure before the

experiments is assured. During tempering, the microstructure is

instable. The compression tests to determine flow curves were relatively short, the effect of microstructure evolution during the test

can be neglected. However during a short term creep test (10 h) of

a not tempered martensite, the tempering process takes place during the test itself which will affect the measurements remarkably.

Consequently creep experiments were simulated only for the tempering temperatures of 600 C and 650 C for three times tempered

martensite under the loads of 400, 500 and 600 MPa.

The mathematical model of creep was programmed in Matlab

and solves the differential equation (Eq. (49)) with the Matlab

Solver ode45. In Table 1, the required microstructure and material parameters for the simulation of creep are summarized. In

addition to those parameters, the model requires for the description of the Orowan stress (rOrowan:s , Eq. (38)) the volume fraction

and the size of the carbides. These two parameters were calculated

by MatCalc and the creep model is taking those parameters from

the precipitation simulations. Two other parameters b and n (Eq.

(31)) used for the description of the dislocation velocity in the soft

region (Subgrain interior) were required to be estimated as in the

reference work [7]. In this work, these parameters were determined in Matlab by the optimization function fmincon. The

calculated parameters b and n are given in Table 1.

The simulation results and their comparison with the experimentally determined strain rate during loading is shown in

Fig. 8. Although the overall shape of the calculated curves particularly for smaller strains up to 0.004 at the tempering temperature

of 600 C, deviates from the experimental curves, the model predicts the minimum creep rate e_ min very well. It should be noted

that the initial microstructure for the creep tests at 600 C and

650 C are completely different, while the specimens were tempered for three times at the corresponding tempering temperatures. This effect was taken into account in the model with the

consideration of the dislocation density, subgrain size, volume

fraction and size of carbides.

One of the simplest material models to describe creep in the

macroscopic scale is Nortons creep law, where the stress dependency of the steady state creep rate e_ c is described in a power

law:

e_ c Ac rnc

50

Fig. 8. Simulated creep curves at the corresponding tempering temperatures compared with the experimental findings: (a) Tempering temperature 600 C. (b) Tempering

temperature 650 C.

290

Table 5

Parameter Ac and nc for the power law at temperatures 600 C and 650C.

Ac (s1 MPanc )

600 C

650 C

simulations.

nc ()

Exp.

Sim.

Exp.

Sim.

6.72393 1013

1.59987 1023

3.47308 1013

2.80594 1022

2.06132

6.57970

2.17178

6.12114

curves, the Ac and nc values can be calculated (Table 5). The effect

of the discrepancy between the values of Ac and nc for the experimental and simulated creep parameters on the stress relaxation

will be examined in the second part of this study.

4. Conclusion

In this work, the dominant mechanical material properties

(yield stress, work hardening, creep) which are necessary to model

the stress relaxation during tempering of a tool steel were calculated using physically based approaches. Suitable modeling

approaches for the simulation of yield stress, flow curve and creep

were selected from the literature. Coupling those models with precipitation simulations was the most important achievement of this

study. Utilizing this methodology, different tempering conditions

(soaking time, tempering temperature) can be considered in the

FEM-Model to predict the stress relaxation without going through

a tedious, time consuming and expensive experimental campaign.

The MatCalc program was chosen for the simulation of the precipitation. Especially for similar steels, the prediction power of the

program was already demonstrated in previous work [1921,53].

In this work the simulated phase fraction and carbide size was

compared with the previous experimental results taken from the

literature. Although simulation results were in good agreement

with the experiments from the literature, a detailed experimental

investigation should be conducted in the future, to verify the prediction of carbide size and volume fraction over the whole range of

relevant tempering temperatures.

Considering the calculated and experimentally measured yield

stresses during tempering a very good prediction of the simple

model used in this study can be observed. The evolution of the dislocation density and martensite lath width was calculated using

new equations compared to previous work [52], which results in

better estimation of the measured yield stress values. The work

hardening model which is integrated in MatCalc also gives very

good results, although for the first tempering step, the calculated

flow curves deviates more from the measured ones. Finally the

creep model delivers quite good results especially for the steady

state strain rate e_ c .

The material models in use still need a big number of

microstructure and material parameters. The parameters used in

this study were taken from similar steels from the literature. The

experimental investigation of those parameters will definitely help

to increase the precision of the models. Beside the precipitations,

the evolution of the dislocations and the martensite lath width

during tempering are the key factors describing the tempering process. In this work the evolution of those parameters was taken into

account with simple equations, although these phenomena are

highly complex. The precipitation simulations should be coupled

in the future with physical models to simulate the evolution of

the dislocations and the recovery process.

Acknowledgement

The authors gratefully acknowledge Prof. Dr. Ernst Kozeschnik

(Institute of Materials Science and Technology, Technical

References

[1] Y. Wang, B. Appolaire, S. Denis, J. Microstruct. Mater. Prop. 1 (2) (2006) 197

207.

[2] Q. Li, Mater. Sci. Eng. A. 361 (2003) 385391.

[3] C.H. Young, H.K.D.H. Bhadeshia, Mater. Sci. Technol. 10 (3) (1994) 209214.

[4] I. Holzer, Modelling and Simulation of Strengthening in Complex Martensitic

912%Cr Steel and a Binary FeCu Alloy, PhD thesis, Graz University of

Technology, Graz, 2010.

[5] I. Holzer, E. Kozeschnik, Mater. Sci. Eng. A. 527 (2010) 35463551.

[6] S.Straub: VDI-Fortschritt Berichte, Dissertation Universitt Erlangen- Nrnberg

1994, VDI-Verlag, Reihe 5, Nr. 405, Dsseldorf, 1995.

[7] P. Polcick, Modellierung des Verformungsverhaltens der warmfesten 9-12%Chromsthle im Temperaturbereich von 550650 C. Diss., Der Technische

Fakultt der Universitt Erlangen-Nrnberg, 1998.

[8] N. Saunders, X. Li, A.P. Miodownik, J.P. Schille, Computer modelling of

materials properties. In: Materials Design Approaches and Experiences,

Minerals Metals & Materials Society, 2001.

[9] Z. Guo, N. Saunders, J.P. Schill, A.P. Miodownik, Mater. Sci. Eng. A. 499 (2009)

713.

[10] J. Svoboda, F.D. Fischer, P. Fratzl, E. Kozeschnik, Mater. Sci. Eng. A. 385 (2004)

166174.

[11] E. Kozeschnik, J. Svoboda, P. Fratzl, F.D. Fischer, Mater. Sci. Eng. A 385 (2004)

157165.

[12] E. Kozeschnik, J. Svoboda, F.D. Fischer, CALPHAD 28 (2005) 379382.

[13] R. Kampmann, R. Wagner, Decomposition of Alloys: The Early Stages,

Pergamon, Oxford, 1984.

[14] R. Wagner, R. Kampmann, Mater. Sci. Technol. 5 (1991) 213303.

[15] R. Becker, W. Dring, Ann. Phys. 5 (1935) 719751.

[16] J.B. Zeldovich, Acta Physicochim. 18 (1943) 122.

[17] H.K. Lukas, S.G. Fries, B. Sundman, Computational Thermodynamics: The

CALPHAD Method, Cambridge University Press, Cambridge, 2007.

[18] N. Saunders, A.P. Miodownik, CALPHAD Calculation of Phase Diagrams: A

Comprehensive Guide, Elsevier Science Ltd., Oxford, 1998.

[19] H. Leitner, P. Staron, M. Bischof, H. Clemens, E. Kozeschnik, J. Svoboda, F.D.

Fischer, Coarsening of secondary hardening carbides in a hot-work tool steel:

experiments and simulation, in: Proceedings of MS&T 2004, 26.-29.9.New

Orleans, 2004, pp. 623632.

[20] B. Sonderegger, E. Kozeschnik, M. Bischof, H. Leitner, H. Clemens, J. Svoboda, F.

D. Fischer, in: Proc. 7th Tooling Conference, TOOL06, 2.-5. May 2006, Torino,

Italy, Characterization and Simulation of Precipitation Kinetics During Heat

Treatment of the Hot-Work Tool Steel X 38 CrMoV 5-3, 2006, pp. 533540.

[21] B. Sonderegger, E. Kozeschnik, H. Leitner, H. Clemens, J. Svoboda, F.D. Fischer,

P. Staron, Steel Res. Int. 81 (2010) 6473.

[22] C. Liebaut, Rheologie de la deformation plastique dun acier FE-C durant sa

transformation de phase, Diss, Nancy, INPL Nancy, 1988.

[23] C.E. Lacy, M. Gensamer, Trans. ASM 32 (88) (1944).

[24] P.G. Winchell, M. Cohen, Trans. ASM 55 (1962) 347361.

[25] J. Hald, Steel Res. 67 (1996) 369374.

[26] L.M. Brown, R.K. Ham, in: A. Kelly, R.B. Nicholson (Eds.), Strengthening

Methods in Crystals, Applied Science Publishers, London, 1965, pp. 9135.

[27] K.C. Russell, L.M. Brown, Acta Metall. Mater. 20 (1972) 969974.

[28] M. Ashby, in: G.S. Ansell, T.D. Cooper, F.V. Lenel (Eds.), Metallurgical Society

Conference, vol. 47, Gordon and Breach, New York, 1968, pp. 143205.

[29] G.I. Taylor, in: Proceedings of the Royal Society. vol. 145. 1934, pp. 362387.

[30] G.I. Taylor, J. Inst. Met. 62 (1938) 307324.

[31] H. Wurmbauer, H. Leitner, M. Panzenboeck, C. Scheu, H. Clemens, Mat.-wiss. U.

Werkstofftechn. 41 (2010) 1828.

[32] Zengshou Hou, Guangxi Lu, Physical Metallurgy, Presse des Sci. & Tech., de

Shanghai, 1989.

[33] J.P. Naylor, Metall. Trans. 10A (1979) 861.

[34] J. Daigne, M. Guttmann, J.P. Naylor, Mater. Sci. Eng. 56 (1982) 110.

[35] A. Eser, A. Bezold, C. Broeckmann, I. Schruff, T. Greeb, HTM J. Heat Treat. Mater.

69 (2014) 127137.

[36] D.W. Smith, R.F. Hehemann, J. Iron Steel Inst. 209 (1971) 467481.

[37] H.K.D.H. Bhadeshia, Bainite in Steels, second ed., The Institute of Materials,

London, 2001, ISBN 1-86125-112-2.

[38] S. Cobo, O. Bouaziz, in: New Developments on Metallurgy and Applications of

High Strength Steels, Argentina, Buenos Aires, Materials Science and

Technology, 2008.

[39] N. Mebarki, D. Delagnes, P. Lamesle, F. Delmas, C. Levaillant, Mater. Sci. Eng. A

Struct. Mater. Prop. Microstruct. Process. 387 (2004) 171175.

[40] K. Maruyama, K. Sawada, J. Koike, ISIJ Int. 41 (2001) 641653.

[41] H. Ghassemi-Armaki, R.P. Chen, K. Maruyama, M. Yoshizawa, M. Igarashi,

Mater. Lett. 63 (2009) 24232425.

[42] U.F. Kocks, ASME J. Eng. Mater. Technol. 98 (1976) 7683.

[43] L.E. Lindgren, K. Domkin, S. Hansson, Mech. Mater. 40 (2008) 907919.

[44] F. Roters, D. Raabe, G. Gotstein, Acta Mater. 48 (2000) 41814189.

[45] S. Brinckmann, R. Sivanesapillai, A. Hartmaier, Int. J. Fatigue 33 (2011)

13691375.

[46] M.S. Soliman, E.A. El-Danaf, A.A. Almajid, Adv. Mater. Res. 83 (2009) 407414.

[47] P. Sherstnev, P. Lang, E.P. Kozeschnik, in: Tagungsband zur European Congress

on Computational Methods in Applied Sciences and Engineering. Vienna,

Austria, 1014 September 2012.

[48] H. Mughrabi, in: P. Haasen, V. Gerold, G. Kostorz (Eds.), Proc. of 5th Conf. on

the Strength of Metals and Alloys (IGSMA 5), Pergamon Press, 1980, pp. 1615

1635.

[49] H. Mughrabi, Acta Metall. (1983) 13671379.

[50] W. Blum, S. Vogler, M. Biberger, A.K. Mukherjee, Mater. Sci. Eng. A Struct.

Mater. Prop. Microstruct. Process. 112 (1989) 93106.

[51] W. Blum, A. Rosen, A. Cegielska, J.l. Martin, Acta Metall. 37 (9) (1989) 2439

2453.

291

Diss., RWTH Aachen, 2014.

[53] B. Sonderegger, E. Kozeschnik, H. Leitner, H. Clemens, J. Svoboda, F.D. Fischer,

P. Staron, Steel Res. Int. 81 (2010) 6473.

[54] R. Ebner, H. Leitner, D. Caliskanoglu, S. Marsoner, F. Jeglitisch, Z. Metallkd. 92

(2001) 820829.

[55] X. Hu, M. Zhang, X. Wu, L. Li, J. Mater. Sci. Technol. 22 (2006) 153158.

[56] Bhler Edelstahl GmbH: Werkstoffdatenblatt Warmarbeitsstahl W302,

November 2006.

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