Surface Treatment with Boron for Corrosion Protection

Naruemon Suwattananont1
Roumiana S. Petrova1
James L. Zunino III2
Daniel P. Schmidt2

New Jersey Institute of Technology1

University Heights
Newark, NJ 07102
U.S. Army RDE Command AMSRD-AAR-AEE-P2
U.S. Army Corrosion Office
Metallic Materials Technology Branch, Bldg 355
Picatinny Arsenal, NJ 07806-5000

ABSTRACT

This paper presents the effect of boronizing on metallic materials. The coatings were produced
by thermo-chemical treatment with powder mixtures at high temperature. The microstructure of
obtained coatings was investigated, the microhardness was measured, and corrosion resistance was
tested.
Microhardness of the obtained boron coatings was measured. Corrosion tests were performed by
using electro-chemical method. The corrosion rates from Tafel plots, the corrosion behavior of an
active-passive coating were observed by using potentiostat. The boronized and not treated coupons were
tested in salt fog, following ASTM B117.
Optical microscopy was used to investigate the microstructure and measure the thickness of the
diffusion boron coatings. To understand the structure, phase composition of the coatings XRD was used.
It has been shown that the properties of the diffusion layers depend on their thickness, structure,
chemical and phase composition as well as on kinetic parameters used in the process. The thickness of
the boride coating varies by the type of the substrate material.
Results indicated that the presence of boron coating on metallic materials improved their
microhardness and corrosion resistance.

Key words: corrosion, boronizing, microhardness, potentiodynamic method

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 INTRODUCTION

Material surface plays a key role to control the service life of materials that is deteriorated by the
environmental attacks, especially corrosion and wear. Annually, a large number of economy losses in
various industries come from the corrosion and wear damages on machines and components. For
several decades ago, a requirement to significantly improve the surface properties of engineering alloys
has led to a development of many surface treatment techniques, such as coating, CVD, PVD,
carburizing, nitriding, boronizing and so on.
Boronizing is one of the surface hardening methods, which is used to increase the surface
features of the engineering components for various industrial applications. Similar to typical thermo-
chemical treatments, boronizing, or called boriding, is a process by which the boron atoms diffuse into
the metal substrate and form the metallic boride on the substrate surface at the temperature between 700-
1000 C for 1-10 h. The formation of the metal boride will provide the excellent surface properties in
terms of high hardness, corrosion resistance, high temperature oxidation resistance up to 850 C, and the
length of service life up to 3-10 times [1]. Although the early main purpose of boronizing was to enhance
the wear resistance for automotive applications, a capability of boronizing to simultaneously combine
the properties of wear, lubricity, corrosion, and high temperature oxidation on one coating is recently
attractive to the military, industrial, and other new advanced applications.
A remarkable advantage of boronizing is to fill out the gap between the conventional method and
advanced high technology. It offers the low cost procedure for producing the high quality products. The
operational cost of boronizing is lower than that of general thermo-chemical treatments such as
carburizing, nitriding, and nitrocarbulizing. In addition, boronizing provides high surface hardness
between 1450 5000 HV[2] as well as the surface hardness of aluminum oxide ceramic at 2000 2050
HV and the surface hardness of PVD TiN coating at 1800 - 2500 HV or CVD TiC coating at 2500 -
2800 HV[3]. Furthermore, boronizing can be applied on different types of steels such as ferrous alloys,
nickel alloy, transition metal, and metal-bonded carbide [4-10].

EXPERIMENTAL PROCEDURES

Low carbon steel (AISI 1018), high strength alloy steel (AISI 4340), and austenitic stainless steel
(AISI 304) in the dimension of 10 10 3 mm were used to study in this work. In the sample
preparation procedure, the sample steels were grinded on the SiC paper of 120, 220, 400, and 600 grits
to remove the oxide and dirt on the steel surface and to get the smooth surface, followed by cleaning
with acetone in the ultrasonic bath. The cleaned sample steels were packed in the crucible filled with
the boronizing powder mixture of B4C, KBF4, and Al2O3 and then heated at 850C for 4 h under the
argon atmosphere. After boronizing, the boronized sample steels were removed from the crucible and
cleaned with acetone.
To investigate the boronized coating, the steel samples were mounted in the epoxy resin. The
mounted specimens were grinded on 180, 320, and 600 grit SiC paper and polished on 6 m diamond
lapping, 0.3 and 0.1 m diamond compounds, and 0.05 colloidal silica suspensions, respectively. Then,
the microstructure and thickness of the boronized coating were observed by using the AxioTech
Microscope attached to the Pixelink (PL-A662) digital camera. The coating thickness was measured by
using AxioVision 4.4. The phase identification of boronized coating was detected by using XRD Philips
model PW 3040 MPD DY715. The microhardness of coating was measured by using Leco
Microhardness Tester LM 700 with 10 gf load.
The corrosion tests were evaluated by following the procedure on ASTM standard B117 test
method (Salt Spray (Fog)) and ASTM standard G5 test method (Potentiostatic and Potentiodynamic

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Anodic Polarization Measurement). Following ASTM standard B117, the experimental test coupons of
high strength alloy steel (AISI 4340) in the dimension of 12.7 76.2 1.59 mm (1/2 3 1/16 in.)
from Metal Samples were used for this study. The test coupons were prepared and boronized as the same
procedure described above. The boronized and unboronized test coupons were exposed in a salt fog
chamber with 5% NaCl solution for 500 h operated by Concurrent Technologies Corporation. The test
coupons were installed in the sample racks at an angle of approximately 15 degrees from the vertical.
After 49 h, 114 h, 210 h and 500 h the coupons were removed from the chamber, cleaned and weighed.
The weight loss after 500 h was detected and calculated the corrosion rate.
Following ASTM standard G5, the boronized and unboronized sample steels of low carbon steel
(AISI 1018), high strength alloy steel (AISI 4340) and austenitic stainless steel (AISI 304) in the
dimension of 10 10 3 mm were studied as well as the electrochemical corrosion measurement was
investigated by using PARSTAT 2263 Potentiostat of Princeton Applied Research with PowerCorr
Software for detecting the data and calculating the corrosion rate. The electrochemical experiments
were tested in 1N H2SO4 deaerated solution with the exposure area 0.41 cm2 and the potentiostat
scanning rate at 0.16 mV/s.

RESULTS AND DISCUSSIONS

Microstructure and Coating Thickness

The microstructure of boronized coating on low carbon steel and high-strength alloy steel
exhibits a saw-tooth structure as illustrated in Figs. 1 2 whereas the boronized coating on austenitic
stainless steel shows the smooth microstructure as seen in Fig. 3.

Figure 1 The saw-tooth structure of boronized Figure 2 The saw-tooth structure of boronized high
low carbon steel (AISI 1018). strength alloy steel (AISI 4340).

Figure 3 The smooth structure of boronized austenitic stainless steel (AISI 304).

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 It has found that the amount and type of the alloying elements in the steel substrate have an
effect on the appearance of coating microstructure and thickness [2, 6, 11]. The chemical composition (as a
result of the amount and type of alloying elements) of low carbon steel (AISI 1018), high-strength alloy
steel (AISI 4340), and austenitic stainless steel (AISI 304) is illustrated in Table 1. In case of low
carbon steel and high-strength alloy steel, the high-strength alloy steel has a slightly different chemical
composition from the low carbon steel and causes the saw-tooth tips of boronized high-strength alloy
steel to be blunt relative to the sharp tips of boronized low carbon steel, including the thinner coating
thickness of high-strength alloy steel compared with that of low carbon steel. In case of austenitic
stainless steel (AISI 304), the amount and type of alloying elements (especially, 8% wt. Ni and 18%
wt.Cr) are to flatten the microstructure from saw-tooth to smooth structure and deplete the coating
thickness. The comparison of coating thickness among three substrate steels is illustrated in Table 2,
which the experimental results are explicit that the coating thickness is reduced if the amount of alloying
elements is higher. This is due to alloying elements impeding the diffusion of boron atoms into the steel
substrate [11]. Furthermore, retarding the growth of boronized coating layer by alloying elements can
cause to the increasing of FeB or B-rich phase formation [6]. This is shown by phase identification of
XRD in Table 2, which FeB was only one phase observed on the coating of austenitic stainless steel,
while outer FeB and inner Fe2B were observed on the coating of high-strength alloy steel and low
carbon steel.

Table 1 Chemical Composition of Steel Samples

Chemical Composition (% Weight)

Steels C Mn P S Si Cu Ni Cr Mo Al V Co N

AISI 1018 0.200 0.720 0.008 0.008 0.016 - - - - 0.065 - - -

AISI 4340 0.400 0.750 0.008 0.005 0.230 0.140 1.67 0.84 0.27 0.028 0.004 - -

AISI 304 0.022 1.58 0.030 0.028 0.41 0.490 8.05 18.20 0.440 - - 0.110 0.090

Table 2 Coating Thickness and Phase Present of Boronized Sample Steels

Thickness Phase Presents Microhardness

Sample Steels
(m) by XRD (HK)

Boronized low carbon steel AISI 1018 75-80 FeB, Fe2B 2100-2250

Boronized high strength alloy steel AISI 4340 50-55 FeB, Fe2B 1800-2000

Boronized austenitic stainless steel AISI 304 18-20 FeB 1900-2100

Salt Fog Test (ASTM Standards B117)

The test coupons were divided into 3 categories: unboronized test coupon, boronized test coupon
and boronized-scribed test coupon. After 500 h time exposure, the weight loss of test coupons was
measured and the corrosion rate (mpy) was calculated by using the below formula:

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 SampleWeight Loss ( g ) 5.34 105
Corrosion Rate (mpy ) = ,
Sample Density ( g / cm3 ) Sample Area (in 2 ) Time Exposure (h)

where,
density of high strength alloy steel AISI 4340 is 7.85 g/cm3;
density of boronized coating is 7.43 g/cm3;
time exposure is 500 h;
sample area is 3.38 in2.

Table 3 Corrosion Rate of Unboronized and Boronized High-strength Alloy Steel Test Coupons

Test Coupons Weight Loss (g) Corrosion Rate

after 500h time exposure (mpy)

Unboronized high strength alloy steel AISI 4340 1.119 45.04

Boronized high strength alloy steel AISI 4340 0.981 41.72
Boronized-scribed high strength alloy steel AISI 4340 0.774 32.91

By salt fog testing (ASTM B117), the boronized test coupons demonstrate better corrosion
resistance than the unboronized test coupons as observed by the corrosion rates in Table 3. The
corroded surfaces after cleaning are shown in Fig. 4. The boronized coating remains on the surface of
the boronized-scribed coupon to protect the substrate from the corrosion, while the unboronized coupon
corrodes severely on the surface.

Unboronized test Boronized test Boronized-scribed

coupon AISI 4340 coupon AISI 4340 test coupon AISI
4340

Figure 4 Optical images of cleaned test coupons after 500h time exposure in salt fog chamber.

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Potentiodynamic Measurement (ASTM Standards G5)
The electrochemical measurement was determined by the tafel analysis on a polarization curve.
The tafel plots illustrate that after boronizing, Ecorr of boronized sample steel shifts to positive potential
as well as icorr of boronized sample steel shifts to less current density corresponding to unboronized
sample steel. Thus, boronized sample steel becomes more noble and has lower corrosion rate than the
unboronized sample steel, which proves that the uniform corrosion resistance of the boronized samples
is improved as compared with the unboronized samples. The comparison of the tafel plots between
boronized and unboronized samples is shown in Figs. 5-7. The corrosion rate calculation follows
Faradays law in ASTM standard G 102 and is defined as:

icorr
CR = K1 EW

where,
CR is a corrosion rate, milli-inches per year (mpy);
icorr is a current density, A/cm2;
is a density of sample steel and coating that is used in the corrosion test, g/cm3;
K1 is a constant value in Faradays law, which is 0.1288, mpy g/A cm;
EW is an equivalent weight of sample steel and coating in dimensionless.

The tafel plot results and the corrosion rate calculations are illustrated in Table 4.

Table 4 Corrosion Rate of Boronized and Unboronized Steel Samples.

Sample Steels Ecorr Icorr icorr Corrosion Rate

(V) (A) (A/cm2) (mpy)

Unboronized low carbon steel -0.440 540.7 1.310 10-3 598.8

AISI 1018
Boronized low carbon steel -0.346 8.199 1.986 10-5 6.357
AISI 1018

Unboronized high strength -0.415 138.2 3.348 10-4 154.7

alloy steel AISI 4340
Boronized high strength alloy -0.400 79.23 1.919 10-4 58.17
steel AISI 4340

Unboronized austenitic -0.287 6.176 1.496 10-5 6.092

stainless steel AISI 304
Boronized austenitic stainless -0.271 1.121 2.723 10-6 0.758
steel AISI 304

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 Figure 5 Tafel plots of boronized and unboronized low carbon steel AISI 1018.

Figure 6 Tafel plots of boronized and unboronized high strength alloy steel AISI 4340.

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 Figure 7 Tafel plots of boronized and unboronized austenitic stainless steel AISI 304.

To investigate the corrosion behavior of boronized and unboronized sample steels, the
potentiodynamic anodic polarization method was used. The polarization curve indicates that the
additional boron atoms in the substrate steel as a coating can cause a more noble corrosion potential of
boronized sample steels in terms of the positive shift above Ecorr of unboronized sample steels, however,
the coating does not provide the protective film for the passivation region. This incident is obvious in
low carbon steel in Fig. 8. Because of few alloying elements (less than 1% wt.) the main electrochemical
reaction on the low carbon steel substrate is the result from the anodic reaction of iron. After
boronizing, the positive potential shift (about 0.1V) of boronized low carbon steel correlative to
unboronized low carbon steel indicates that adding boron atoms as a coating constituent to the substrate
steel causes the boost of corrosion potential in boronized low carbon steel. In boronized high strength
alloy steel (Fig. 9) and austenitic stainless steel (Fig.10), the alloying elements involve in the
electrochemical reaction of both substrate steels as in high-strength alloy steel the anodic reaction
combines between the reactions of iron and nickel and in austenitic stainless steel the anodic reaction
composes of the reactions of iron, nickel and chromium. The result shows that the alloying elements
increase the corrosion potential of high-strength alloy steel and austenitic stainless corresponding to low
carbon steel. This effect might be stronger than the effect of boron atoms, leading to a few potential
shifts (~ 0.015 V) of boronized high-strength alloy steel and boronized austenitic stainless steel different
from the corrosion potential of unboronized ones. Moreover, some oscillations were observed in the
polarization curve at potentials above 0.5 V, which could suggest the breakdown of the passive film, like
one occurring during repassivation. The explanation for the oscillations in boronized low carbon steel
(Fig. 8) and boronized high strength alloy steel (Fig. 9) is the possible effect of a metastable pitting as
well as the pits were observed by the optical microscope in Figs. 11 a-b. In contrast, the oscillations
were not detected in boronized austenitic stainless steel and the pits were not detected on the surface
either as shown in Fig.11c.

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Figure 8 Polarization curve of boronized and unboronized low carbon steel (AISI 1018).

Figure 9 Polarization curve of boronized and unboronized high strength alloy steel (AISI 4340).

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Figure 10 Polarization curve of boronized and unboronized austenitic stainless steel (AISI 304).

(a) (b) (c)

Fig.11 The optical image of pits on (a) boronized low carbon steel, (b) boronized high-strength alloy
steel, and (c) boronized austenitic stainless steel.

CONCLUSIONS

1. After boronizing, the corrosion rate of boronized low carbon steel is 6.357 mpy, which is about 100
times lower than the corrosion rate of unboronized one based on the electrochemical measurement.
2. The boronized high strength alloy steel and austenitic stainless steel have the corrosion rate about
58.17 mpy and 0.758 mpy, which is ~3 times and ~8 times lower than the corrosion rate the
unboronized ones, respectively. These results are based on the electrochemical measurement.
3. In salt fog testing, both boronized and boronized-scribed test coupons of high-strength alloy steel
demonstrate the better general corrosion resistance than the unboronized high-strength alloy steel
test coupons.

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4. Adding boron atoms on the steel substrates as a boronized coating can improve the corrosion
resistance, however, to lengthen the service life of components, the thicker coating thickness might
be considered.

ACKNOWLEDGEMENTS

We greatly acknowledge the support from RDECOM-ARDEC Picatinny, NJ, U.S. Army Corrosion
Office on Project: DAAE30-03-D-1015, and R. Gerry Miller, Ph.D., P.E., Concurrent Technologies
Corporation, Largo, FL for the corrosion testing in salt fog.

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