INTERNAL FRICTION INVESTIGATIONS OF ELECTROLYTICALLY DEPOSITED THIN LAYERS

(1)

HAL Id: jpa-00223421

https://hal.archives-ouvertes.fr/jpa-00223421

Submitted on 1 Jan 1983

HAL

is a multi-disciplinary open access archive for the deposit and dissemination of sci- entific research documents, whether they are published 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.

INTERNAL FRICTION INVESTIGATIONS OF ELECTROLYTICALLY DEPOSITED THIN LAYERS

G. Haneczok, R. Kuśka, R. Kwiatkowski, J. Moro_

To cite this version:

G. Haneczok, R. Kuśka, R. Kwiatkowski, J. Moro_. INTERNAL FRICTION INVESTIGATIONS

OF ELECTROLYTICALLY DEPOSITED THIN LAYERS. Journal de Physique Colloques, 1983, 44

(C9), pp.C9-487-C9-492. �10.1051/jphyscol:1983971�. �jpa-00223421�

(2)

JOURNAL DE PHYSIQUE

Colloque C9, supplkment au n012, Tome 44, d6cembre 1983 page C9-487

INTERNAL FRICTION INVESTIGATIONS OF ELECTROLYTICALLY DEPOSITED THIN LAYERS*

G . Haneczok, R . Kugka, R . Kwiatkowski and J.W. Moroii

I n s t i t u t e o f t h e Physics and Chemistry o f Metals, S i l e s i a n U n i v e r s i t y , Bankowa 1 2 , 40-007 Katowice, Poland

~ d s u m g

-

A 1' aide de pendule inverse K$ on a ktudi6 le frotte- ment interne et le module de torsion des couches Ni et Cu-2% en pds Cd d6posdes 6lectrolytiquement sur les fils de molybdsne, dans l'intervalle de temp6ratures de 300

-

⁸⁰⁰^K.Sur les cour- bes Q-'/T/ on a observ6 de larges maximums existant dans les temp&atures de 564 K /Ni/ et de 550 K /Cu-Cd/. I1 semble que les r6sultats obtenus pour la couche de nickel d6montrent 1' existance de la transformation de phase de 1' &at amorphe-fin cristallin 2 l'dtat cristallin dans la tem&rature de 564 K.

Abstract

-

Using a type K & inverted pendulum investigations were made of internal friction /IF/ and shear modulus for Cu-2wt.% Cd and Ni layers electrolytically deposited on molybdenum wire,in the temperature range 300

-

800 K . On the Q-~/T/ curves a wide maximum was found to occur at temperature 564 K /Ni/ and 550 K /Cu-Cd/. Results obtained for the nickel layers appear to indicate that at 564 K a phase change takes place from an amorphous- fine crystalline state to a crystalline phase.

I

-

INTRODUCTION

During recent years several authorscl

-

7]have reported that in tests conducted using the IF method an important role is played by samples surface. In [l

-

3J it was ascertained that covering the sample with mineral oil causes several maxima to appear on the Q-~/T/ curves at peak temperatures /T / which are independent of vibrations frequency.

P

These maxima occur in the temperature range 200

-

250 K, in which range lies the melting temuerature of the oil. IF peaks were observed in [2] associated with a layer of FeO and Fe304 oxides on the surface of d

-

iron samples /thickness 1 pm/. The authors postulate that this effect is due to phase changes taking place in the oxide laver /e.g. FeO cubic

-

FeO rhombohedra1 at temperature 198 K/. Samples of Copt alloy covered with saturated hydrocarbons /e.g. C10H22, C12H16/

were tested in [4]and similarlv as in [l-31 the temperatures of the peaks observed corresponded to the meltinq temperatures of the hydrocarbons.

However, in [5, 6)a maximum was observed to occur at T = 340 K, associated with the melting of trace quantities of Wood's alloy caught in P

*This research was supported by the Polish Academy of Sciences.

Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:1983971

(3)

C9-488 JOURNAL DE PHYSIQUE

the surface micropores of the molybdenum sample. The IF method was used in [7]to study the electrical resistance of a silver layer deposited on mica by vacuum evaporation, and two peaks were observed at temperatures 373 and 503 K. After heating the sample for two hours at temperature 723 K the maximum at 373 K disappeared. This unstable peak was thought by the authors to be associated with structural defects occurring in the newly deposited Ag layer.

Results reported in [l

-

7Iprovide evidence that the IF method can be a source of information on the deposited layer and probably also on the layer/substrate interface. For this reason it was decided to use IF measurements to test metallic Ni and Cu-Cd layers deposited electrolytically on~molybdenum substrate.

I1

-

MATERIALS AND METHOD

The substrate taken for deposition of metallic layers was pure molybdenum wire of diameter 1 mrn, previously recrystallised in a vacuum furnace Tr/ at temperature 2400 K for 1 hour. For molybdenum prepared in this way the IF spectrum exhibits only a background of the order of 2

-

³

.

/Fig. 2 curve 3/, hence this material is suitable for application in studies of this kind.

Two types of layers were deposited on the molybdenum wire, i.e. nickel and Cu-2 wt.% Cd alloy. The Cu-Cd alloy layer was deposited using a copper anode in a bath of composition:

CuS04

.

^5H20

-

60 g/dm 3 Na2S04 10H20

-

50 g/dm 3 /NH4/2SO4

-

^{50 g/dm}³

3CdS04 8H20

-

23 g/dm ³

ethylenediamine in a quantity of 70 cm3 per litre. Current density was

-

1.5 ~ / d m ~ . The nickel layer was deposited using a nickel anode in a Watts bath /plus brightener/ of composition:

NiS04. 7H20

-

^{300 g/dm3}

NiC12 6H20

-

60 g/dm3 H3B04

-

25 g/dm3

The brightener contained: 1.4-butanediol, saccharine, phthalimide.

,.

Current density was 4 ~ / d m ~ . Thickness of the deposited layers was about 10 pm.

IF measurements were perfomed on an inverted K$ pendulum type RIM

-

^3,

as described in

[a] ,

in the temperature range from 300 to 800 K with a frequency f = 1

+

¹¹Hz. The mean deformation amplitude was 2

(4)

Temperature of the tested samples was varied linearly at a rate

v = 2 . 5 K/min. Measurement of vibration frequency permitted the dyna-

mic shear modulus of the sample to be determined at the same time.

I11

-

MEASUREMENT RESULTS

On Fig. 1 and 2 are given the Q-~/T/ curves obtained for Cu-Cd and Ni layers at a measurement frequency of f = 6 . 5 Hz. On both figures number 1 denotes curves obtained immediately after deposition of the layer while number 2 denotes curves obtained after heating the same sample /linear heating rate of v = 2 . 5 K/min./ in the temperature range from 3 0 0 to 8 0 0 K. Followinqelectrolyticdeposition of the metallic layers on the Mo wire wide maxima appear on the Q-~/T/ curves and these disappear when the sample is heated to a high temperature;

repeated heatinq of the sample does not alter the IF soectrum. For the Cu-Cd layer a maximum was observed at about 5 7 0 K / ~ i g . 1/ and for Ni a maximum at about 5 6 4 K /Fig. 2 / .

For further investigations to elucidate the mechanism by which the observed phenomenon takes place only the nickel layers were studied as these exhibited a sharper IF peak. It was ascertained that peak height increases with increase in thickness of deposited layer.

Fig. 3 shows three IF curves obtained for samples with deposited Ni layer at different pendulum vibration frequencies. It may be seen that the temperature at which IF maximum occurs is independent of vibrations frequency /T = 5 6 4

f

²K/, giving evidence that the tested

P

effect is not related to a migrational relaxation process [9]

.

Fig. 4 shows the curve of dynamic shear modulus G versus temperature / G/T/-f /T/ 2 / and the IF curve for the Ni layer. At the temperature of occurrence of the IF peak a marked rise in f2 /of the order 3 % /

was observed. This effect, as also the form of the q - l / ~ / curves, appears to indicate that the phenomenon studied is associated with structural changes taking place in the layer at the sample surface.

Fig. 5 shows three IF curves determined for: 1

-

sample immediately after depositing an Ni layer, 2

-

the same sample but heated to 5 5 5 K, i.e. only a little lower than the temperature of occurrence of the maximum T = 5 6 4 K, 3

-

for this sample heated to temperature 6 2 0 K

P

-

¹

/ T > T

/.

Heating to 5 5 5 K causes only a certain drop in value of Q , P

while after heating to T = 6 2 0 K the observed peak disappears comple- tely.

(5)

JOURNAL DE PHYSIQUE

500 GOO 700 800 Fig. 1

-

IF curves for Cu-2wt.%Cd Fig. 2

-

IF curves for an Ni layer on an Mo substrate. layer on an &To substrate.

500 GOO

-

³⁰

-f

CKI

I I I

400 500 GOO 700 800 Fig. 3

-

IF curves for an Ni layer Pig. 4

-

Curve of shear modulus on an Mo substrate determined for G-f/T/ /1/ and of IF /2/ deter- various pendulum frequencies: mined for an Mo sample with an 1

-

^{11 Hz,}²

-

^1.2H z , 3

-

^6.5^Hz. Ni layer.

4

^a-'.104

₄

30

-

0

20

-

I L

400 500 GOO

Fig. 5

-

IF curves obtained for an Fig. 6

-

Curves of shear modulus Ni layer on an Mo substrate: /1/ and IF /2/,obtained for an

1

-

immediately after deposition Ni layer deposited on an Mo sub- of layer, 2

-

after heating to strate, after linear heating

555 K, 3

-

after heating to 620 K. to 800 K.

(6)

The IF measurements perfomed for the nickel layer were supplemented by X-ray tests. For the sample immediately after depositing the Ni layer only the characteristic Ni ( 1 1 1 ) reflex was observed while the nature of the whole diffraction pattern was similar to that for metallic glasses. After heating this sample to temperature 620 K at a rate of 2.5 K/min. this reflex clearly increased in intensity. Simultaneously the diffraction pattern became rather normal and new reflexes Ni (200) and Ni (220) appeared which are also characteristic reflexes of this element.

IV

-

DISCUSSION

From these investigations it was found that on the IF spectrum for Ni and Cu-Cd electrolytically deposited layers on molybdenum a wide maximum is observed which disappears following linear heating of the sample at a rate of v = 2.5 K/min. to temperature 800 K /Fig. 1, 2 / . For the Ni layer, further tests provided the basis for postulating an interpretation of the effects observed. From Fig. 2 and 3 it may be seen that the peak at 564 K is not of migrational relaxation origin and is most probably associated with structural change. The form of the G/T/ curves corroborate this conclusion. The curve of f2 plotted immediately after deposition of the layer shows an increaseoftheorder of 3 % in the peak temperature /Fig. 4/, while for the sample heated to T > T only a monotonic decrease is found /Fig. 6/. X-ray tests sho-

P

wed that the Ni on Mo layers are in an amorphous-fine crystalline state, and after heating the sample to tem~erature T

>

T a marked

P growth in the crystalline phase is observed.

The results achieved appear to indicate that for an Ni layer on an Mo substrate a phase change from an amorphous-fine crystalline state to a crystal state takes place at about 564 K.

Considering the results of these investigations it may be postulated that the interpretation of the unstable peak associated with a silver layer, as reported in [7] , is open to discussion.

Acknowledgements

-

The authors express their thanks to Mr. J. Gala, M. Eng., from the Institute of the Physics and Chemistry of Metals

-

Silesian University, Katowice, for electrodeposition of metallic layers.

(7)

JOURNAL DE PHYSIQUE

References.

1. CHOMKA W., DENGA E., J. Physique

42

/19R1/ C5-1165

2. CHOMKA W., DENGA E., MOSER P., Phys. Stat. Sol. /a/

62

/1980/ K53 3. AUGUSTYNIAK B., Proceedings of the RENIOM-82 Conference, Katowice

1982, Silesian University Press, in press /in Polish/

4. CHOMKA W. DENGA E., Proceedings of the RENION-82 Conference, Kato- wice 1982, Silesian University Press, in press /in Polish/

5. HANECZOK G., POLOCZEK T., M O R O ~ J.W., Acta Phys. Pol.

A63

/1983/ 53 6. HANECZOK G., POLOCZEK T., MORON J.W., J.Physique 42 /1981/ C5-811 7. UOZUMI K., HONDA H., YOKOTA H., EBISU H., Thin Solid Films

2

/1976/ 221

8. PIETRZYK J., BRAWUSKI J., Pomiary Automatyka Kontrola No 9 /1976/

3 2 5

9. NOWICK A.S., BERRY B.S., Anelastic Relaxation in Crvstalline Solids, Academic Press, New York 1972