HAL Id: jpa-00223822
https://hal.archives-ouvertes.fr/jpa-00223822
Submitted on 1 Jan 1984
HAL is a multi-disciplinary open access archive for the deposit and dissemination of sci- entific research documents, whether they are pub- lished or not. The documents may come from teaching and research institutions in France or abroad, or from public or private research centers.
L’archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d’enseignement et de recherche français ou étrangers, des laboratoires publics ou privés.
X-RAY AND AUGER ELECTRON MICROANALYSIS IN STUDY OF THE CONTACT ZONE OF STEELS
UNDER FRICTION
V. Nemoshkalenko, V. Gorsky, E. Ivanova, A. Goncharenko
To cite this version:
V. Nemoshkalenko, V. Gorsky, E. Ivanova, A. Goncharenko. X-RAY AND AUGER ELECTRON MI- CROANALYSIS IN STUDY OF THE CONTACT ZONE OF STEELS UNDER FRICTION. Journal de Physique Colloques, 1984, 45 (C2), pp.C2-643-C2-646. �10.1051/jphyscol:19842150�. �jpa-00223822�
Colloque C2, supplément au n°2, Tome k5, février 198* pageC2-6W
X-RAY AND AUGER ELECTRON MICROANALYSIS IN STUDY OF THE CONTACT ZONE OF STEELS UNDER FRICTION
V.V. Nemoshkalenko, V.V. Gorsky, E.K. Ivanova and A.B. Goncharenko Institute of Metal Physics, Academy of Sciences Ukr SSR, Kiev, U.S.S.R.
Résumé - L'étude de la structure fine des spectres d'émission X du fer et de l'oxygène ainsi que les données de la spectromé- trie Auger permettent de réfuter les hypothèses anciennes sur la formation de solutions solides sursaturées ou de composés définis métal-oxygène aux interfaces de frottement des aciers dans l'eau. On suppose que les atomes d'oxygène sont piégés par les défauts de la surface de contact.
Abatraot - The study of fine structure of emission X - ray spectra of iron and oxygen in combination with Auger electron spectra data refute the earlier suppositions about forming the oversaturated solid solutions or chemical compounds of oxygen with metal in the contact zone of steels under sliding friction in water. Oxygen atoms are supposed to disposed in defects of desorganized boundary material.
The oxygen role in friction and wear of materials is marked by many investigators. But up to the present time there are contradictory opinions about mechanism of interaction between oxygen and metal atoms in the contact zone of metals under friction. Some investiga- tors suppose forming of the usual oxides, in particular for steels - PeO, Pe^O^ or Fe2°3. T h e °'tiiers consider that in this case oxygen forms with metal oversaturated solid solutions or chemical nonstoi- chiometric compounds. The study of the nature of a material in the contact zone of metals under friction is of great interest because it forms the protect films, which decrease a wear of metals under friction.
In the present work we studied the contact zone of high carbon high chrom steels (1.3 wt.% C and 15 wt.% Cr) with additional alloying elements V, Hb, Mo or W after these steels had undergone sliding friction in water. I n order to study its chemical and phase compo- sition, electron structure, the character of interatomic cohesion the X-ray and Auger spectroscopy, electron microscopy and the method of X-ray difraotion were used.
I - PROCEDURE
Local X-ray investigation was carried out with X-ray microprobe MS-46. The Duncumb and Reed / l / atomic number correction, Philibert and Duncumb /2,3/ absorption correction and Castaing and Reed / 4 /
characteristic fluorescence correction procedures were utilized in used computer program / 5 / . This program was applied for calculation of chemical composition of standard samples of steels, carbides and oxides. The total error of the calculation of the metal component concentrations did not exeed 0,5 wt.$. This fact allows to suppose that with such error the light element concentration was determined because it was calculated as difference between 100$! and the sum of the concentrations of remaining elements (Tabl.1).
?he great attention was paid to the procedure of registration of emission X-ray spectra with X-ray microprobe MS-46 and their mathe- matical treatment. 0Krf,-band was registrated in the second order of reflecting from O.D.Pb crystal. PeKoC^^2-lines _ in the third order Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:19842150
C2-644 JOURNAL DE PHYSIQUE
from BT c stal. FeKB -band - in the first order from the quartz
f a
(toil CrYs al. FeLd -. z d - , Lj3 ,-bands - in the fi~st order from
a~ crystal. Quantitative information about fine structure of X-ray spectra was obtained after computer treatment of experimental curves by the least s uares method. FeKd~,~-lines in the 9th order of re- flection from f l ~ crystal were used as inner standard lines for measuring of integral intensities and energy positions of FeLd- and FeLp I-bands (Fig. I 1.
I . . . .
700 710 720 eV
Fig. f - Emiss~on X-ray spectrum o f Fe in FeO in L d - L j 3 ~ region.
Dotted line corresponds to the experimental ourve, dashed line is result of the decomposition of the experimental curve into Lorentz form peaks, solid line is the superposition of mentioned peaks.
The differences of mass absorption coefficients for FeLoC, L p I -
and K ~ 2-lines were taken into account on comparing their integral I intensities, Springer /6/ modification of the Heinrich /?/expres- sion was used to estimate mass absorption coefficients for PeLoC- and L p I-bands :
/u-- (C/R)J~ .
Coefficients R were taken from the Springer work. The values c and n were obtained from Yakowita /8/ expression:
c = exp(AO+ AIlnZ + ~ ~ ( l n ~ ) ~ ) . (n>
Authors of the work /5/ said that the values of coefficients 80, A1 and Ag obtained by the least squares method give the better results than in work /8/.
Antieontaminator provided the sample surface purity in the, course of analysis and spectrum registration.
Auger spectra were obtained under electron beam energy 5 KeV. Cle- aning of the studyed surface was provided by ion et hing in Auger spectrometer chamber in ar on a mosphere (p = 5.70-9 torr) under tension 600 V and current 8*1O-6 A.
I1 - RESULTS AND DISCUSSION
The results of the investigation have shown that with all the steels the contaot zone consists of a ~ystem of four layers. The overall thickness of these layers does not exeed 1 5 mkm. The layers have sharp boundaries between each other and with the base metal. The
ro 0 tione of metal components in the layers do not varify in com-
!arls?on with the base metal. Inner layer I, adjacent to the de- formed base metal, contains 5-8 at.% 0. Layers 2, 3 and 4 contain about I6 at.% 0, 28 at.% 0 and 38 at.% 0 correspondingly(/g/,Tabl.g).
The oxygen content in four friction surface layers does not conform with its content both in Fe oxides and in solid solutions of oxygen in steels. The presence of the dispersive oxide particles as second phase in the studyed layers would be displayed in fine structure of X-ray and Auger spectra which give an information about electron structure and interatomic cohesion in objects under investigation.
The study of electron structure and interatomic cohesion in friction
The compositions (wt.%) of the standard steel sample, M C carbide, Be 0 and Fe203 oxides
7 3 3 4
.
element I/I, MS-46 chemical element I/Ie MS-46 chemical
compos . compos.
Steel 933 M7C3 carbide
Si 0,0017 0.40 0.33 C - 8.4 8.7
v 0.0020 0.19 0.19 Cr 0,551 53.6 53.5 Cr 0,141 12,O 71-92 Fe 0.266 33.65 33.8 Nn 0.0091 0.89 0.82 lo 0,031 4.3 490
0,825 85,6 85964 Fe304 oxide
Fe 0.0023 0.29 0 - 27.6 27.64
Oa2' Fe 0.0006 0.10 0.21
Nb 0.690 72:4 72-36
Mo 0.0038 0.58 0.60 Fe 0 oxlde
0 - 29.9 30.06
Fe 0.664 70.1 69.94
-
Table 2
The averaged proportions of 0, Cr and Fe in the friction layers
base metal - 1.01 1 .OO 1.02
layer 1 1.05 1.04 1.04 1 .OO
layer 2 I .OO 1.02 0.9 6 0.95
layer 3 I .OO 1 .OO 1.01 0.99
FeO 1.19 0.69 1.84 0.50
Fe304 7.22 0.71 1.72 0.49
Fe203 1.17 0.82 1.60 0.48
Teble 4
The distributio? of 3d-electrons in the upper energy band near Fe atoms
object studied
I layer layer 2 layer 3 layer Table 3 4 1 14.9 9.9 2.3 5.2 27.5 37.7 15.9 7.5 84.1 77.5 72.3 81.8 78.8 71 52.3 61.6 .8 13.6 13.0 12.7 12.8 13.7 12.2 10.8 10.0
The integrated intensities of the X-ray spectra lines from the friction layers and FeO, Fe304 and Fe203 in cornperision with Fe
object studied
3d3/2 3d5/2 3d3/2 ' 3d5/2
Fe, base metal
and friction layers 1.9 4.6 6.5
FeO 3.6 3.1 6.7
Fe304 3.4 3.3 6.7
Fe203 3.1 3.7 6.8
0 Fe Cr
wt .% at .% wt .% at .% w t .% at .%
object studied Integrated intensities of the following bands OKoc FeL& FeLB 1 "eKB 5
C2-646 JOURNAL DE PHYSIQUE
swfaoe layers was carried out in comparision with the electron structure and interatomic cohesion in FeO, Fe304 and Fez0 oxides.
X-ray emission K-bands of oxygen and iron and L-bands of ?ron are known to give the information about the distribution of valence p- and d-electrons correspondingly, It was determined that under tran- sition from base metal to oxides the integral intensity of PeK 5-
I t band deareased about by 2 time and the integral intensity of 0 oC.- band increased respectively. !&is fact points to the correspondent redistribution of upper p-electrons of iron and oxygen atoms. Be- sides, the computer analysis of the fine structure of X-ray FeLd- and L~I-bands has shown the mutual redistribution of 3d3/2- and 3d5/ -electrons of Fe atoms.3ut in this case the total amount of 3d-ef ectrons near Fe atoms remained invariable ( M I . 3,4 )
These data lead to conclusion that under oxide formation ;he ionic component of cohesion between iron and oxygen atoms is formed only by upper p-electrons of these atoms and the redistribution of 3d -
electrons of Fe atoms takes place inside the energy bands of iron atoms. The detailed discussion of this problem was given earlier/IO/.
The parameters of X-ray emission spectra of iron do not change under transition from base metal to the friction surface layers. This fact leads one to suppose that in these layers the chemical iron-oxygen compounds are absent, i.e. the metallic type of cohesion is con -
served here.
The changes in the nature of interatomic cohesion must be displayed in the low energy region of the Auger electron spectrum which cor- responds to the valence electrons, as the valance electrons do take part in the formation of chemical cohesion. Really, the transition from the base metal to oxides, i.e, from metallic to ionic-covalent type of cohesion, is accompanied by the splitting of the 47 eV iron peak of Auger spectrum into two peaks with energies 42 and 51 eV.
It is in agreement with the data of other investigators. There is no such splitting for the studyed friction surface layers. This fact confirms once more the conservation of the metallic type of inter- atomic cohesion.
Transmission electron rni~r0~~0gy investigations has shown the fric- tion surface layers to have ultrafine crystalline struc ure with b.a.0. iron lattice (the grain size does not exeed 500 1 1.
The dath, recieved by the method of X-ray difraction by a thin beam, show that the lattice parameter in friction layers c incides with the lattice parameter in base metal to within 0,005 4.
The sum total of the present work data about ultrafine crystalline structure, compolsition and interatomic cohesion between iron and oxygen atoms in the surface layers, formed on the steels upder sli- ding friction in water, all4ws to suppose that oxygen in these la- yers forms neither ovemsaturated solid solutions no chemical. compo- unds, but disposes in defects of desorganized grain boundary material.
Duncumb P., Reed S. J.B., Quantitative Electron Probe Microanaly- sis.-U . S . , Nat.Bur,Stand., Spec.Publ., 298( 1968) 133.
Duncub P. Shilds P.K., The Electron Microprobe.-New York:
wiley( 19665284.
Philibert J., X-ray Optics and X-ray hficroana1ysis.-New York:
Academic Press( 1963)379.
Reed S.J.B. ,Brit.J.Appl.Phys., 16(1965)913.
Cickunov N.C., Baturev V.A.. Gripachevsky A.N., Razumov O.N.,
~!ihonovich V.V. ,Preprint of Inst .Met .Phys. ,Kiev, 81.16(1981).
Springer G., Nolan B., Canad.J.Speptr. ,=,8( 1976)134.
Heinrich K.F.J., The Blectron Microprobe.-New York: wiley( 1966) Yakowits H., Myklebust R.L., Heinrich K.F.J.,U.S.,Eat,Bur.Stand
~ech,~ote,796(1973)9.
Gorsky V.V., Ivanova E.K., Ivashchenko Ju.N. ,~ear,81(?382)109.
Ivanova E.K., Dissertation, Kiev (1982)
