NASA Technical Paper 3066

1990

Electrochemical Studies of Corrosion Inhibitors

M. D. Danford George Marshall C. Marshall Space Space Flight Center Alabama

Flight

Center,

National Aeronautics and Space Administration Office of Management Scientific and Technical Information Division

TABLE

OF CONTENTS

Page I. I1. 111. INTROI)UCTION EXPERIMENTAL RESULTS A. B. C. I) Single AND ...................................................................................... ...................................................................................... DISCUSSION ...................................................................... I 1
-3

Salts ..........................................................................................

"3 "3

Molybdate-Containing lnhibitors ................................................................. Corrosion Inhibition by O.03M Na__B4()7 Plus ().()3M NaNO2 ............................... The Effect of Oxv,,en on Corrosion Inhibition Inhibition by Chemical Mixtures in Corrosive Water. ............................

E. Corrosion IV. CONCLUSIONS

4 4

........................................................................................

REFERENCES

..................................................................................................

iii PRECEDING P/_GY. ELAP{K ROT FILMr.D

LIST

OF

ILLUSTRATIONS

Figure 1. Exploded Corrosion 3. 4. Corrosion Corrosion view of the sample rate as a function rate as a function rate of 2219-T87 holder

Title ........................................................... number number I ................................. 3 ................................. in mils/year (MPY) ......

Page 7 8 9 10

of time for solution of time for solution aluminunl

with Mobay

inhibitor

iv

LIST

OF TABLES

Table 1.

Title Corrosion inhibition by single salts for type I010 steel in 3.5";._ sc,dium chloride i NaCI) ............................................................................. Corrosion inhibition by single salts for 5052 t gm/liter! 1010 steel aluminum alloy in 3.5g'i NuCI ................

Page

II II 12

3. 4

Composition Inhibition containing Inhibition

of chemical of corrosion solutions of corrosion

inhibitors lk_r type

................................................... by sodium molybdate (NaMoOa)

................................................................................. for 5052 aluminum alloy by' (NaMoO4) containing solutions ......

12 13

Cc, rrosion rates and percents inhibitor solutions contai'ning Corrosion number Inhibition solution rates 4 for type in air-purged 1010 steel,

inhibition for type 1010 steel in 0.03M Na__B40-7 plus O.03M NaNO .......................... and nitrogen-purged 5052 aluminum and allot,, inhibitor and copper solution .............................

13

14

of corrosion 4 for type

in air-purged 5052

nitrogen-purged alloy,

inhibitor ............................ ............................ and ......................... 15 14 15

1010 steel,

aluminum

and copper (gin/liter) steel

Composition Corrosion 5052

of chemical rates and

inhibitors

in corrc, sive water for type

percents

inhibition

1010

aluminum

alloy for corrosion

inhibition

by chemical

mixtures

TECHNICAL

PAPER

ELECTROCHEMICAL

STUDIES

OF

CORROSION

INHIBITORS

I. INTRODUCTION

Although may be different methods compare may not properly film or formation aluminum. the inhibitor several

the mechanism from in the evaluation

of the action of corrosion

of inhibitors, inhibitors.

when

studied of time,

by electrochemical it is of interest the electrochemical

methods, method

that in weight-loss

methods

over a period

to see how the of any oxide in the case of exposure to with in the

For example,

account for the incubation time, or for the period required tor breakdown of a protective layer on the specimen surface. This is particularly true results, over The when a period polarization based on a single However, provided method determination such after a very may method are subject made to this effect. of days, shortcomings

Electrochemical solution,

short

be overcome is employed since

measurements

that the proper is ideal surface, [1,2]. making

electrochemical

technique.

resistance

for this purpose repeated

it employs

very low currents which have little effect on the sample possible. This electrochemical technique has been described The effectiveness work, with measurements of single being salts as corrosion inhibitors

measurenlents

in various samples.

media

was determined

in this of multi-

made

on both steel and aluminum

The effectiveness

component mixtures was also investigated, method. A study of molybdate-containing study of inhibitors consisting of other determined for type 1010 steel, copper, sion inhibition for steel using a mixture These results are compared to those

and results are compared to those obtained by the weight-loss inhibitors for steel and aluminum was carried out, as well as a mixtures and the effect of oxygen on corrosion rates was and 5052 aluminum of borax (Na2B407) alloy. A study was also made of the corroand sodium nitrite (NaNO2) (each 0.03M).

chemical

by the weight-loss

method.

II.

EXPERIMENTAL

The

sample

holder

employed

is shown

in figure

!. Samples,

which

consisted

of circular

disks

!.43 cm (9/16 in) in diameter and approximately by wet sanding on 400-grit silicon carbide paper The samples were before polarization measurement a scan

0.16 cm (1/16 and subsequent

in) in thickness, were prepared for study degreasing in boiling trichloroethylene.

mounted in this holder and immersed in the appropriate medium tor at least 1 hour resistance measurements were made. The EG&G-PARC model 350A corrosion was employed The for the collection range of data. Data were collected at 0.5 mV intervals at measurement for all determinations was from -20 mV to + 20 mV

console

rate of 0. I mV/s.

with respect to ECORR, the normal stored on disk and then transferred rates made medium are determined first on a blank (sea water, [1,2], using (no inhibitor salt water,

corrosion potential of the sample in a given medium. The data were to computer memory for calculation of ICORR, from which corrosion POLCURR and then water, 138-ppm etc.). sodium [3]. Polarization on a sample bicarbonate The corrosive resistance contained to deionized measurements 148-ppm water. were sodium The perpresent) immersed water added in the inhibitor-containing

the program corrosive

sulfate, 165-ppm sodium chloride, and cent inhibition was determined by:

percentinhibition = (corrosionrate in blank - corrosionrate in inhibitor)/(corrosionrate in blank) 100.

For determination environment

of oxygen dry

effects,

corrosion

cells

were

purged

with

air to produce

an oxygen-rich

or with

nitrogen

to produce

an oxygen-free

environment.

III.

RESULTS

AND

DISCUSSION

A. The corrosion shown sodium in table nitrate inhibitions The exhibited percent

Single

Salts salt water (Na2B4OT) are and

by single

salts for type 1010 steel in 3.5-percent inhibitors was for steel except actually negative. borax

1. All salts investigated (NaNO3).

are good inhibition

corrosion

by NaNO3

this

Inhibitions case, sodium results, and

for type 5052 aluminum in the same nitrite (NaNO2), sodium chromate while Na3PO4 sodium gave silicate a negative (Na2SiO3), value

medium by the same salts are listed in table (Na2CrO4), and sodium nitrate (NaNO3) (Na2B4OT), for both steel and sodium inhibition and aluminum which phosphate while corrosion in this case. is acceptable

2. In give Thus, is

acceptable NaNO2

borax

(Na3PO4) NaNO3

are unacceptable.

for the percent

NavCrO4

are excellent

corrosion

inhibitors

acceptable for aluminum but not for aluminum. Caution must

but not for steel.

The reverse

is true for Na2SiO3,

for steel

be exercised

on inhibitor

effects

in the case of aluminum

alloys.

The samples several which

were hours show

exposed to the medium for only I hour before determination of the corrosion rates. Often, or several days are required for the inhibitor to have an effect. However, those inhibitors high effectiveness after only a short exposure can generally be accepted without too many

reservations.

B. This toxicity molybdate. inhibitors, work Tests was were undertaken made

Molybdate-Containing to study in hot four the

Inhibitors techniques inhibitor sodium for evaluating ingredient molybdate using corrosive low

use of electrochemical systems. having The basic different

corrosion

inhibitors

for use with of which

water solutions

is sodium containing water as

the composition

are shown

in table

3. All tests were made

the medium. Results for solutions 1 through 4 (table 3) are shown in table 4 for type 1010 steel. Studies were made at 30 and 60 C. As shown in table 4, corrosion inhibition at both temperatures is excellent for all solutions. Results for the inhibition of corrosion for type 5052 aluminum by sodium molybdate (NaMoO4)

containing solutions are listed in table 5. The percents and immediate at 30 and 60 C. Both of these solutions silicate is necessary rate to form quickly. a protective layer the corrosion

inhibition for solutions contain sodium silicate. surface

2 and 4 are both excellent It is apparent that sodium rate in order to reduce

on the aluminum

at a rapid

The corrosion with time, as shown

rate for solution by figure

1 shows

a great

increase

over that for corrosive during

water,

but declines and decreases

I. The corrosion

rate drops

rapidly

the first 6 hours

slowly thereafter, reaching a rate of 0.786 mils/year after a period of 24 hours. The rate eventually drops to about the rate observed for solutions 2 and 4. Thus, an incubation period is required to obtain effective inhibition. The change rate of corrosion in corrosion in this case rate for solution increases 3 is shown in figure to 7.75 2 as a function mils/year during of time at 30 C. The the first 3 hours of

from 6.3 mils/year

sample immersion. The corrosion rate drops beyond that point, reaching a value of 2.2 mils/year after about 24 hours. The corrosion rate thus drops more slowly than that for solution 1 and yet does not approach the values obtained for solutions 2 and 4. It appears that the presence of Na2B407 in solution 3 actually enhances the corrosion rate for a rather long period of time. However, when Na2SiO3 is added to this solution, the corrosion rate drops immediately, as evidenced by the result obtained for solution 4. Thus inhibitors 1, 2, and 4 are effective for 5052 aluminum alloy, with an induction period being required for inhibitor 1. methods in electrical [4], where multimetallic samples contact were placed in hot water (1100 aluminum, type (82 C) for a period of I

It was found in weight-loss 1010 steel, and 321 stainless steel) year, that all inhibitor solutions results. However, in the case

were effective for type 1010 steel, of 1100 aluminum, only solutions

in agreement with the electrochemical 1 and 4 were effective in the multi-

metallic system, with solution 1 being the most effective. results, which indicated that solutions 1 and 4 were effective, must be remembered that the electrochemical determinations the weight-loss tests were made on electrically connected

This is compared to the electrochemical but also included solution 2. However, it were made on 5052 aluminum only, while multimetallic systems.

C. This wherein months study

Corrosion was

Inhibition

by O.03M

Na2B407 tests

Plus carried

O.03M out by

NAN02 conventional methods,

undertaken

to supplement

other

type 1010 steel samples were immersed in solutions containing the inhibitor and corrosion effects determined by the weight-loss method [5]. Electrochemical in inhibitor solutions prepared in table 6. In all three cases, using tap water, the effectiveness

for a period of 14 tests were made deionized water, of the inhibitor or in

on type 1010 steel samples immersed corrosive water. Results are shown preventing in which

corrosion is excellent. These results are in agreement with those from the weight-loss no corrosion was observed over the 14-month immersion period.

method,

D. The The corrosion The while corrosion effect rates of substitution water

Effect

of Oxygen

on Corrosion

Inhibition system systems indicate is quite dramatic. The

of a nitrogen-purged (H20) for air-purged is greatly

for an air-purged and nitrogen-purged considerably These results

rates in corrosive rate

are shown that

in table 7. system, of

for 1010 steel and copper for aluminum

are decreased increased.

in the nitrogen-purged

the corrosion

the absence

oxygen has a favorable tive effect in inhibiting ing the ways possible.

effect in inhibiting the corrosion rates of type 1010 steel and copper, but a negathe corrosion rate of 5052 aluminum alloy. This may be understood by considercorrosion of aluminum can occur. Two mechanisms are thermodynamically

with which

(I) (2) The

4AI+30_+6H,O 2AI+6H20 potential

4AI(OH)_

E"c_n E"ccll is greater

2.06V

= 6Al(OH)3+3H: of the first reaction

= 0.832V. than that for the second reaction, so that corrosion is depleted, the (!), so that the

proceeds by that mechanism second reaction predominates. corrosion rate Inhibitor oxygen lowest air-free is increased solution

when oxygen is present. Reaction (2) proceeds in the absence 4 (table of oxygen. 3) was As table solution,

However, when the oxygen supply at a much faster rate than reaction

number

selected 7 shows, and

as the medium the corrosion suggest

for investigating rates for copper systems that copper

the effect be kept

of as

on the effectiveness in the nitrogen-purged as possible. The percent inhibition

of inhibitors. inhibitor

are by far the

it would

in air-purged rates Generally,

and nitrogen-purged observed in air-purged inhibition rates the percent

solution

4 in corrosive

H20 is shown corrosive

in and

table

8 and is based

on the corrosion temperatures. although

and nitrogen-purged is comparable considerably.

H_O at

the corresponding nitrogen-purged

for the air-purged

systems,

the corrosion

are effected

E. Corrosion The effect type Results agreement aluminum weight-loss agreement chemical figure I()1() steel with alloy, study. are tabulated

Inhibition

by Chemical mixtures The

Mixtures on the inhibition mixture were

in Corrosive of corrosion compositions are effective for a period

Water was investigated are listed for type of i year. in table 1010 steel, for 9. in

of four different and 5052 in table aluminum

chemical alloy. results study

chemical samples

10. These studies

show that all inhibitors studied that that mixture indicated

weight-loss However,

[6], wherein

For 5052 with the in dis-

the electrochemical

indicated study

i was best, mixture

also in agreement

the weight-loss

3 was also effective,

with the electrochemical method, using 2219-T87 rate drops

result. A study was therefore made for this inhibitor by' the electroaluminum alloy, as a function of time [7]. The curve is shown in rapidly fronl a very high initial value to about 0.002 mils/year after 30 methods into agreement. The caution corrosion electrochemically is again

4. The corrosion

day's of exposure, bringing the weight-loss and electrochemical which must be exercised in studying the inhibition of aluminum illustrated.

IV.

CONCLUSIONS

As the results which inhibitors Caution period, may be much are very must which

show,

corrosion

rates

may be considerably steel and 5052 of steel corrosion. in corrosion

affected aluminum rate

by single alloy. when

salts,

the effects vary.

of

different solutions,

for type a rapid

I010

Molybdate-containing the effects NaeSiO_ For the is present.

effective

in the prevention

For aluminum, is noted

molybdate-containing

decrease

be exercised in the study of corrosion inhibitors for aluminum. Frequently an incubation may be several hours or several days, is required for an inhibitor to become effective.

However, if an immediatedecrease of corrosionrate is observed,the inhibitor can generally be consideredeffective.If theobserved percentinhibition is 50.0or less,the inhibitorcanusuallybeconsidered ineffective. Steelalmost always exhibits an immediateresponse to the addition of inhibitor. In oxygen-freesolutions,corrosionratesaregreatlydecreased for type 1010steelandcopper,but are increasedfor 5052 aluminum alloy. This is attributedto the two possiblemechanisms by which aluminum can oxidize. However, corrosion inhibition is generally comparablefor oxygen-rich and oxygen-freeinhibitor solutions.
In general, screening effectiveness, chemical inhibitors. methods the results However, cannot of this study in many show that the electrochemical cases, long-term more exposure than one metal method is necessary in electrical is an effective to establish contact where means for

inhibitor electro-

especially

in systems

containing

be employed.

REFERENCES

1.

Dean, 1977,

S.W., p. 52.

Jr.: "Electrochemical

Methods

of Corrosion."

NACE

Symposium,

R. Baboian,

Ed.,

2. 3. 4. 5. 6. 7.

Danford, Gerchakov, Humphries, Humphries, Humphries, Knockemus,

M.D., S.M., T.S., T.S.: T.S.:

and

Higgins, L.R.,

R.H., and C.:

NASA Mansfeld,

Technical F.:

Paper

2459, Vol.

April 37,

1985. 1981, p. 696. April 1983.

Udey, and

"Corrosion." Memorandum

Spitler,

NASA/MSFC

EH24 January

(83-19), 1984. TM-78180, August

NASA/MSFC DOE/NASA Summer

Memorandum Technical Research

EH24

(84-5),

Memorandum Participant,

DOE/NASA

August 1985.

1978.

W.W.:

Huntington

College,

KNURLED F LAT TEFLON WASHER

THUMB

NUT

LAT WAS H ER WORKING ELECTRODE HOLDER

_..--"O-RING TEST SPECIMEN

SAMPLE

HOLOER

8OOY

HOLDER PLUG

O--RING

SAMPLE

HOLDER

CAP

Figure

I.

Exploded

view

of the sample

holder.

40"-

32SOLUTION 30C
2_m

NUMBER

>.
1.

24I< a Z O
o 0 a

0 R, O J

16-

12-

I 4

i 8

I 12 TIME (HRS)

I 16

l 20

I 24

211

Figure

2.

Corrosion

rate

as a function

of time

for solution

number

I.

SOLUTION

NUMBER

30OC
>.

ttl .< a= Z 0
cn

0 0 _J

I 8

i 12

I 111

I 20

l 24

I 211

"rll_ Figure 3. Corrosion rate as a function

(Hall of time for solution number 3.

>.

.,m

E .=_
L--

E .=_

oo

[.r',4

Q
4....* Z.....

.o
0

OlD

8
P

10

Table

I.

Corrosion

inhibition sodium

by

single chloride

salts

for

type

1010

steel

in 3.5%

(NaCI). Percent

Chemical*

c0rvos_on mils/year

R_te

Inhibition

NaNO Na2CrO Na2SiO

2 4 3

1.950 0.275 2.575 26.12 4 3.734 112.7

96.4 97.6 95.3 52.1 93.1 --

Na2B407 Na3PO NaNO 3

All

solutions

contain

percent

salt.

Table

2.

Corrosion

inhibition

by

single

salts

for

5052

aluminum

alloy

in 3.5%

NaCI.

Chemical*

Corrosion mils/year

Rate

Percent Inhibition

NaNO Na2CrO Na2SiO

2 4 3

0.302 0.275 5.26 7.648 4 175.2 0.324

97.4 97.6 55.0 34.6 -97.2

Na2B407 Na3PO NaNO 3

*All

solutions

contain

percent

salt.

11

Table

3.

Composition

of chemical

inhibitors

(gm/liter).

lo

1.2

Na2MoO

2H20,

1.0

NaNO 3,

2.0

NaMBT*,

2.3

Na3PO

4-12H20.

2.

Number

1 plus

2.3

Na2SiO3"9H20.

3.

Number

1 plus

1.9

Na2B407"IOH2

O.

4.

Number

1 plus

2.3

Na2SiO3.9H20

plus

1.9

Na2B407.10H20.

* Sodium

Mercaptobenzothiazole.

Table

4.

Inhibition

ofcorrosion

lortype containing
CorrosioD

1010

steel

by s)dium

nlolybdate
Percent

(NaMo04)

solutions.
Rat_ Inhibition

A, Corrosive 1 2 3 4 H20

30C 21.24 0.128 0.102 0.313 0.108 -99.4 99.5 98.5 99.5

B.

60_

Corrosive 1 2 3 4

H20

53.89 0.155 0.105 0.284 0.109

-99.7 99.8 99.5 99.8

12

Table

5.

Inhibition

of corrosion

for 5052

aluminum

alloy

by NaMoO4
Percent

containing

solutions.

Solution

orrosioD mils/year

hate

Inhibition

A,

_0"C

Corrosive 1 2 3 4

H20

0.303 36.41 0.087 6.348 0.083

--71.3 -72.6

S.
Corrosive 1 2 3 4 H20

60_
7.948 81.27 0.071 67.92 0.052 --99.1 -99.3

Table

6.

Corrosion

rates

and

percents 0.03M

inhibition Na2B407

for type plus

1010

steel

in inhibitor

solutions

containing

0.03M

NaNO2.
Percent

Solution

corrosion

Rate

Inhibition

mils/year

i.

(a) (b)

Deionized With

H20

0.551 0.014 97.5

Inhibitor

2.

(a)

Tap

Water

3.948 97.7

(b)

With

Inhibitor

0.091

3.

(a) (b)

Corrosive With

H20

5.339 0.131 97.5

Inhibitor

13

Table

7.

Corrosion

rates

in air-purged steel,

and nitrogen-purged 5052 aluminum

Air-Purue mils/year

inhibitor and

solution

number

4 for type

1010

alloy,

copper.
Nitrouen-Purae mils/year

Material

A. i010 5052 Copper Steel Aluminum

30"C 0.071 0.159 0.029

0.108 0.083 0.162

B. i010 5052 Copper Steel Aluminum

60C 0.095 0.438 0.074

0.109 0.052 0.141

Table

8.

Inhibition

of corrosion in air-purged and nitrogen-purged inhibitor 1010 steel, 5052 aluminum alloy, and copper.
Percent Percent Inhibition

solution

4 for type

Matevial

Inhibition Air-Purue

Nitrogen-Purge

A. I010 5052 Copper Steel Aluminum

30C 99.7 81.6 93.5 88.4 95.0 83.0

B. I010 5052 Copper Steel Aluminum

60"C 99.8 94.5 74.0 75.9 98.2 73.9

14

Table

9.

Composi/ionofchemicalinhibimrsincorrosive
3, 2.0 Na3PO4.12H20, O, 1.0 NaOH 2.5 NaMBT*, by

waler(gm/liter).
3.0 Na2B407, Motors).

la

1.0 1.0

NaNO

Na2SiO3.OH2

(formulated

General

2.

1.5

NaNO3,

2.0

Na3PO4.12H20,

2.5

NaMBT*,

4.0

Na2B407.

3.

20.0

Mobay

Product

OC2002-sodium

benzoate

base.

4.

3.7

NaNO2,

1.9

Na2HPO

4,

1.9

NaH2PO

4.

Sodium

mercaptobenzothiazole.

Table

10. Corrosion

rates

and

percents

inhibition inhibition

tor type by chemical

1010

steel

and

5052

alun_inum

alloy

for

corrosion

mixtures.
Percent

Inhibitor

Number

Corrosion

Rate

Inhibition

mils/year

A.

i010

Steel

0.153

99.2

0.239

98.7

0.273

98.2

1.218

93.3

B.

5052

Aluminum

0.157

81.8

3.157

--

0.811

5.8

0.460

46.6

15

NationalAeronauticsand Space Administration 1. Report No. NASA TP-3066

_1_

Report

Documentation
Accession No.

Page
3. Recipient's Catalog No.

2. Government

4. Title and Subtitle

5. Report Date

Electrochemical

Studies

of Corrosion

Inhibitors

November 6. Performing

1990 Organization Code

7. Author(s)

8. Performing

Organization

Report No.

M.D.

Danford
10. Work Unit No.

9. Performing

Organization

Name and Address

11-653 11. Contract or Grant No.

George Marshall
12. Sponsoring

C. Marshall Space

Space

Flight

Center 35812
13. Type of Report and Period Covered

Flight

Center,

Alabama

Agency

Name and Address

Technical Administration
14. Sponsoring

Paper
Agency Code

National Washington,
15. Supplementary

Aeronautics

and Space

DC 20546

Notes

Prepared by Corrosion Engineering Directorate.

Research

Branch, Materials

and Processes Laboratory,

Science and

16. Abstract

The has been copper.

effect

of single

salts,

as well as muhicomponent for 5052, exhibit was found effect can oxidize. an immediate,

mixtures, positive

on corrosion aluminum effect effect alloys;

inhibition and for can

studied

for type 1010 period

steel;

1100, and 2219-T87 before

Molybdate-containing The absence by which

inhibitors may be required of oxygen but a negative aluminum environments.

for steel corrosion, inhibitor (smaller corrosion similar metals, for with

but an incubation be determined. rate) sible mechanisms oxygen-rich

for aluminum

the effect a positive inhibition

of a given

to provide Corrosion

for steel and copper, and oxygen-free

for aluminum.

This is attributed show

to the two pos-

is generally of single

The results

of this study

that the electrochemi-

cal method is an effective means of screening inhibitors caution to be exercised in the case of aluminum.

for the corrosion

17

Key Words (Suggested

by Author(s))

18. Distribution

Statement

Corrosion

inhibitors,

electrochemical

methods, Unclassified - Unlimited

effect of oxygen on corrosions, con'osion of steel and aluminum

19. Security Classif. (of this report) 20. Security Ctassif. (of this page)

21.

No. of pages

22.

Price A03

Unclassified
NASA FORM 1626 OCT86 For sale by the National

Unclassified

24

Technical

Information

Service,

Springfield,

VA

22161-2171

r_xsx-t,_]ey,

1_0