CorrosionScience,Vol. 39, No. 3, pp.

453-463, 1997 0 1997ElsevierScienceLtd

Printed in Great Britain. All rights reserved 0010-938X/97 $17.00+0.00

PII: SOOlCr938X(96)00122-9

THE CORROSION BEHAVIOUR OF AISI 304L AND 316L STAINLESS STEELS PREPARED BY POWDER METALLURGY IN THE PRESENCE OF ORGANIC ACIDS
E. OTERO, A. PARDO, M. V. UTRILLA, F. J. P&REZ and C. MERINO

Department of Materials Sciences, Faculty of Chemical Science, Universidad Complutense de Madrid, Av. Universitaria s/n, 28040 Madrid, Spain Abstract-The corrosion rates of AISI 304L and 316L stainless steels prepared by powder metallurgy (P/M) have been studied by continuous current electrochemical methods, in organic acid solutions (acetic, formic, lactic and oxalic) at different concentrations. For comparison purposes a simultaneous study was carried out on cast AISI 304L and AK1 316L steels of similar composition. For this investigation polarization resistance was the technique chosen and values for the Tafel slopes and the StemGeary constant B were obtained. The sintered AISI 304L and AISI 3 16L steels had the highest corrosion rates. Subsequently, a kinetic study of the corrosion process has been carried out. A crevice corrosion mechanism for the materials tested in organic acid has been suggested in accordance with the results obtained for the P/M materials. The crevice attack is localized in the pore areas, close to the powder particle contact zone. 0 1997 Elsevier Science Ltd. All rights reserved
Keywords A. stainless steel, B. weight loss, B. polarization resistance, C. crevice corrosion.

INTRODUCTION The demand for P/M stainless steels has increased notably, this is fundamentally due to their good mechanical properties, ease of fabrication and the economic advantages they offer (especially where large numbers of complex objects are involved). The principal limitation of these materials, when compared with their cast counterparts, is their lower corrosion resistance. This is due to porosity which increases the area available for reaction.*- The variables of the fabrication process such as atmosphere, temperature, sintering time are being optimised, and the addition of alloying elements to the steels to increase corrosion resistance is being examined.- The organic acids belong to a group of products more frequently used in the chemical and food industries. These acids are fundamentally used as precursors for other substances. They are classified as weak acids as H + dissociation is slight in aqueous solutions. As a general rule the corrosivity increases when the alkyl group, attached to the acid, decreases in size. Formic acid has the largest dissociation constant and consequently is more corrosive. Numerous investigations on the corrosion behaviour of cast austenitic stainless steels exist but there are very few concerning P/M stainless steels. At low in the literature,i5 temperatures conventional austenitic stainless steels can be used in these environments. In the present work electrochemical methods have been used to study the corrosion behaviour of, and evaluate the effect of porosity on, AISI 304L and 3 16L stainless steels when exposed to different concentrations of organic acids at room temperature.
Manuscript received 3 April 1996; in revised form 14 July 1996. 453

454

E. Otero rr al

EXPERIMENTAL

METHOD

Materials This work was carried out on cast and P/M AISI 304L and AISI 316L austenitic stainless steels. Their chemical compositions are shown in Table 1. The P/M steels were obtained as follows: 15 g of prealloyed powder was uniaxially compacted at 700 MPa using zinc stearate as the matrix lubricant. Green densities of 6.40 and 6.43 g/cm were obtained for AISI 304L and 316L, respectively. Sintering was carried out in a vacuum furnace at 1603 K, with a vacuum pressure ~0.13 Pa, for 30 min. The heating and cooling rate was 5 K/min. The products were 25 mm diameter, 4.9 mm thick discs with densities of 6.90 and 7.03 g/cm3 for AISI 304L P/M and AISI 316L P/M, respectively. The cast steels were prepared by smelting two 40 kg ingots, of the desired compositions, in an induction furnace. The products were machined into specimens of dimensions 15mmx15mmx4mm. Solutions of the organic acids were prepared using 1, 25 and 50 wt% concentrations, except for oxalic acid which used concentrations of 1, 10 and 25 wt% (the last solution was practically saturated). Electrochemical tests A three-electrode cell was used to obtain electrochemical measurements. The working electrode was the chosen steel, the counter platinum and the reference a saturated calomel electrode (SCE). An AMEL potentiostat model 551, incorporating a model 567 function generator and model 500 recorder, was used to measure and register the results. A potential of &-10 mV was applied above the corrosion potential (scanning rate 2 mV/ s) for different testing times. The Tafel slopes were established from the active region of the corresponding anodic and cathodic curves. They were plotted by applying a ramp of + 100 mV to the signal generator with a polarization rate of 4 mV/s. When R, was known the Stern-Geary equation was applied to obtain i,,,,. Table 2 shows the values of B for the materials studied. The total test time was 360 h. Duplicate specimens were used in each test to show reproducibility. The corrosion rate (I/,,,,) was determined using Faradays law (ASTM G-102).16 At the end of each test, atomic absorption spectroscopy was used to determine the dissolved elements in the electrolytic solution and calculate the equivalent weight (IV,,). When the tests were complete the kinetic laws governing the corrosion for each experiment were calculated.

Table

I.

Chemical

composltmn

of the stainless steels Element (wt%)

Material Cast Cast AISI AISI AISI AISI 304L 316L 304L 316L P/M P:M

< 0.018 0.01 I 0.017 0.023

Si 0.83 0.75 0.62 0.82

MIl 0.76 0.14 SO.05 0.18

Cr 18.4 17.1 18.2 16.3

Ni 11.0 12.9 11.5 13.8

MO 0.01 2.33 2.15

P 0.006 0.007 0.024 0.018

s 0.004 0.006 0.007 0.007

Corrosion behaviour of P/M stainless steels in organic acids Table 2. Variation of the Stern-Geary constant (B) for the steels studied B (mV/decade) Material 304L P/M Concentration (%wt) Acetic 39 26 24 39 36 36 102 75 73 89 66 61 Formic 24 29 24 27 32 20 81 94 86 87 66 73 Lactic 28 17 19 33 32 37 92 75 127 98 126 92 Oxalic 13 19 24
15

455

Concentration (%wt) 1 10 25 1 10 25 1 10 25 1 10 25

1
25 50

316L P/M

1 25 50 1 25 50 1 25 50

13 31 13 19 24 15 13 45

Cast 304L

Cast 316L

EXPERIMENTAL

RESULTS

AND DISCUSSION

From the electrochemical results, using polarization resistance, the current densities were calculated. Figure 1 shows the evolution of current density with time for cast and P/M AISI 304L in acetic acid. It can be seen that the P/M specimens have current densities of two orders of magnitude greater than those of the cast specimens. The corrosion rates were calculated from Fig. 2 which represents the integration of the results, expressed as weight loss/area vs time, for cast and P/M AISI 304L in acetic acid.
0.0120

E 0.0000 omo100 Z
8 Z ! 0 00060 * oB040 0.0020 0.0000
0

+cAsT3w;SO%

+PPM304;

loo

200

Time 09
Fig. 1. Variation of the current density as a function of time in acetic acid for P/M and cast AISI 304L.

456

PI&. 2

Variation of the corrosion rate with tune in acetlc acid far P/M and cast AN 304L.

Similarly, the corrosion densities for cast and P/M AIS1 3 16L were calculated. Figure 3 shows the corrosion rate expressed as a function ofweight loss per unit area vs time, in acetic acid. Comparing Figs 2 and 3 it can be seen that P/M AISI 316L has a greater corrosion resistance in this environment than P/M AISI 304L; however, both are inferior to the cast steels. The weight losses are similar for both the cast steels and of order 20 times smaller when compared with the P/M AISI 304L. The corrosion densities were measured for all the tests in all the solutions so that the corrosion rates could subsequently be calculated.

0.50

+ cAsT318;
0.40

1%

PM316;1%

8 CAST 318; 25% G CAST316;50%

* PM 316; 25% + PM316;50%

0.30
0.20

0.10 0.00 0 100 150 200 Time (h)

Fig. 3 Variation of the corrosion rate with time in acetic acid for P/M and cast AISI 316L.

250

300

350

40

Corrosion behaviour of P/M stainless steels in organic acids

451

25.00

1 z ii

20.00

CAST304;25% * PMm=% + CAST304;50% + PM304i5OK

10.00 15.00

I 5.00 0.00

Fig. 4.

Variation of the corrosion rate with time in formic acid for P/M and cast AISI 304L.

2500 2000 1.500 1.000 0.500 0.000 f3 CAST316;25% * PM316;25% e CAST316;50% + PM31s;50%

nrfw 0
Fig. 5. Variation of the corrosion rate with time in formic acid for P/M and cast AISI 316L.

Figures 4 and 5 show the corrosion rate, expressed as a function of weight loss per unit area with time, in formic acid. As this is the most aggressive of the acids used, the increase in concentration causes increases in the difference between the corrosion rates of the P/M and cast materials. Again P/M AISI 316L has better corrosion resistance than P/M AISI 304L. The weight loss per unit area was similar for both the cast steels tested. Figures 6 and 7 show the corrosion rate, as weight loss vs time, in lactic acid. The smallest differences between the rates for all the steels were observed in this environment.

458

E. Otero el al.

0.60
0.60

0 +

CAST304;26% CAST304;60%

t +

PMm25% PM304;50%

Fig. 6.

Variation

of the corrosion

rate with time m lactic acid for P/M and cast AlSl 304L

0.60 0.60 0.40 CAST 316; 26% ++ CAST318;60% + PM316;50%

200

Time m
Fig. 7. Variation of the corrosion rate with time in lactic acid for P/M and cast AISI 316L

A similar behaviour is shown in oxalic acid, Figs 8 and 9, where similar rates are found for the P/M steels. The cast materials had lower corrosion rates than the P/M materials. The relatively high corrosion rates observed in oxalic acid are due to the fact that the 10 and 25% tests were agitated to maintain a homogeneous dissolution. Tables 3 and 4 show the calculated kinetic laws for all the tests; as may be seen, in all cases the kinetics follow linear behaviour. The kinetic constants calculated for the cast steels are small and similar, as would be expected in the solutions tested at room temperature.

Corrosion behaviour of P/M stainless steels in organic acids

459

8.000 7.000 8.000 5.000 4.000 3.000 2000 1.000 0.000 0 50 100 150 ZOO 250 200 350 400 0 cAsl304;10% + cAsT304;25%
* PM30410~ + PM3G9;25%

Fig. 8.

Variation of the corrosion rate with time in oxalic acid for P/M and cast AISI 304L.

8.000 = 1' g d !iI =F 5000 4.000 3.000 2000 1.000 0.000

8 +

cAs1316;10%

*PM +

316;10%

CAST 31625%

PM 316;25%

Fig. 9.

Variation of the corrosion rate with time in oxalic acid for P/M and cast AISI 316L.

Comparing these results with those obtained for the P/M steels, differences of up to two orders of magnitude in formic and oxalic acids, and one order of magnitude in acetic and lactic acids, may be observed. In general the slopes increase with increasing acid concentration, the P/M materials showing the most significant increases. A sharper increase in the kinetic constant values is observed for the cases which present the greater corrosion rate (formic and oxalic), and fundamentally for P/M AISI 304L. The kinetic constants for P/M AISI 3 16L are always lower than those calculated for P/M AISI 304L. A corrosion mechanism for the P/M stainless steels, exposed to the organic acids, is

460 Table 3. Corrosion

E. Otero er al. kinetic equatjons for the P/M steels Kinetic law [Acid] AISI 304L P/M I= -8.9x IO a 6.4x 10 / r = 0.9954 lob-: t r-0.9910 I AISI 316L P/M -2.2X 10-2+9.4x I = 0.9947 lo-4r

Acetic acid

I o/o

25%

2.5x

I 8 x IO 7r

~~-1.6xl0~+lO-t I = 0.9983

SO;0

,-m--0.291

6x 10.

,=-1.8x10~+1.4x10 r = 0.9926 y= -6.9x 10m+2.1 I = 0.9950

?t

r = 0.9865 Formic acid I% y== -0.36+ 8.8~ IO-/ r = 0.9898

J :

x IO- I

2 5 O/o

-2.68-t

8.5 x 10

4 -0.13-5.3x i-= 0.9966 ? -0.47+7.9x r=0.9898

lo- ?!

I = 9938 500/o J = -2.43-i 4.2 x 101 r = 0.9848 ~~--4.7xlo~+5.7xlo~4f. I< 140 h, r=0.9950; y= -0.24+ 2.Tr. r>l40h,r=0.9993 2 5 70 11 - I .6 x IO +7.5x I -=0.998 I ,= - I.2 X IO IO-r J= -3.8

10vJt

Lactic acid

I%

~.=-11.6x10~~+1.2x10~~t r = 0.9990

x 10 2+1.5x r = 0.9848

lo-?/

SOD/o

- 7.7 X IW ?(

v=8.3x

10 If 5.8 X 10-41 r = 0.9787 X lo-j/

Oxalic acid

I o:,

I= -0.18+ lo-?1 I z 0.9990

,)

1= 1.9X lo-+9.1 I = 0.9996

IO90

5x IO r7x

IO :/

1=0.28-t 1.2x lo-:/

r=0.9910 1.1 -0.39-1 1.7x lo-{ r-0.9902

r=O.Y93I 2 5 30 _i: --Cl.33 4 2.3 * IO :I r = 0.994 I

proposed based on the test results and microstructural observations. Figure 10 is a schematic diagram of the proposed mechanism. The acid penetrates into the pores [Fig. 10(a)] where it produces an elevated number of protons, this giving rise to dissolution of the passive layer. An appreciable decrease in the partial pressure of O2 in the crevices is produced, which prevents the formation or regeneration of the passive layers in these regions. The attack continues from the crevice along the edges of the original powder particles, eventually interconnecting all the pores and causing partial structural disintegration of the material. This eventually leads to generalized

Corrosion behaviour of P/M stainless steels in organic acids Table 4. Corrosion kinetic equations for the cast steels Kinetic law [Acid] Acetic acid 1% Cast AISI 304L y= -3.8x 10-+2.2x r=0.9945 10-3+1.4x r = 0.9984 lo-? Cast AISI 3 16L y= -4.7 x 1O-3+2.8x r = 0.9966 y= -2.2 x 10-3+2.5x r= 0.9994
y= -2.4x

461

10-4c

5%

y=3.ox

10-41

10-42

50%

y= -4.9x

10-+ 2.6 x 10-4t r = 0.9943

1O-3+2.4x r = 0.9975 -+1.9x 0.9994

1O-4f

Formic acid

1%

y= -2.2 x lo-3+ 1.5 x 10-42 r = 0.9999 y=-1.5x10 -=+2.9x r=9781 10-4t

y=-7.7x10
r=

lo-4t

25%

y=2.5 x 1O-3+7.3x r=0.9980

l0-4r

50%

y= -2.5 x 10-3+ 1.8 x 10-4t r = 0.9998 y= -2.6x 10-4+ 1.3 x 10-4t 0.9984

y= -5.1 x 10-4+ 1.5 x lo-4t r = 0.9983 y= -6.8 x 10-4+ 1.3 x 10-42 r = 0.9996 y= -2.6x 10-3+2.1x 0.9873 10-41

Lactic acid

1%

r=

25%

y= -2.6x

10-3+2.1 x 1O-4r r = 0.9894 10-3+2.1 x 1O-4f

r=0.9985

r=

50%

y= -6.2x

y= -5.7x

10-3+3.1 x lo-4r
r = 0.9996

Oxalic acid

1%

y=-1.2x10

-3+ 1.6 x 10-4t

r = 0.9996

y= -3.7 x 10-3+3.2x r = 0.9990 y= -8.5x

10-4t

10%

y= -5.9x

10-3+2.5x r=0.9913 10-3+2.9x r = 0.9692

10-4t

10-3+ 3.7 x lo-4t r = 0.993 1 10-3+4.7x r = 0.9892 lo-4t

25%

y= -6.6x

1O-4r

y= -2.9x

corrosion, caused by a mechanism due to crevice corrosion [Fig. 10(b) and (c)l. This justifies the high corrosion rates. The effect is much more acute when the initial concentration of acid is increased. CONCLUSIONS (1) The porosity of the P/M steels causes the corrosion rates, in the acids tested, to be higher than for conventional steels. This is due to a generalised corrosion process induced by a crevice corrosion mechanism. In the pores, high concentrations of protons are found, producing the dissolution of the passive layer in the crevices.

462

Fig.

IO.

Proposed corrosion mechanism for the P/M stainless steels: (A) acid interconection of pores; and (C) detail of B at higher magnification.

attack;

(B)

(2) In all test conditions P/M AISI 304L showed corrosion rates slightly higher than those of P/M AISI 316L. (3) The lowest corrosion rates for the P/M steels were found in acetic and lactic acids. (4) The absence of pores in AISI 304L and 3 16L was the reason why the corrosion rates for these materials were of two orders of magnitude lower than those of the P/M steels.
Ackno~,lrdgmtmf.r--The authors (Project MAT-0181-1993-959). wish to express their gratitude to CICYT for financial support of this work

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Corrosion behaviour of P/M stainless steels in organic acids

463

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