Surface Treatment for Erosion Resistance

28 July 2015
By Juthamate Jaruratchataphun
Faculty of Engineering Chulalongkorn University

Star Petroleum Refining Public Co., Ltd.

Objectives of Internship
To study and understand surface treatment application that is
available for industrial use.
To study of a coating application for slurry pumps
To provide recommendation or solution guidance for surface
treatment method for using in hot slurry system.

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Contents
Theory of Surface Hardening Methods
Case study on the coating application for slurry
pumps(16G204A/B/C)
Lab Results Summary
Recommendations

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Theory of surface hardening methods

Methods for surface hardening
Layer addition

Substrate treatment

Hardfacing
- fusion deposit
- Thermal spray process

Coating
- Electrochemical plating
- PVD
- CVD
- Ion mixing

Diffusion methods
- Carburizing
- Nitriding
- Sulphonitriding
- Nitrocarburizing
- Boriding
- Titanium-Carbon
- Toyota diffusion Process

Selective hardening
methods

- Flame hardening
- Induction
Hardening
- Laser Hardening
- Electron beam
hardening
- Ion Implantation

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Layer addition

Hardfacing is the deposition of a special alloy material

on a metallic part, by various welding processes, to

obtain more desirable wear properties and/or
dimensions

Fig1- cross section layer of hardfacing method

Fusion deposits : require melting of the substrate.

Ex. Gas Tungsten Arc Welding, Submerged Arc Welding, Flux Core
Arc Welding
Thermal spray process
Ex. Flame Spraying, Plasma Arc Spraying, High Velocity Oxy Fuel

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Layer addition
Weld Hardfacing
Advantages
Inexpensive
Applicable to large components
Localize coating possible
Excellent coating/substrate adhesion
High deposition rate possible
Disadvantages
Residue stresses and distortion can cause serious problems
Weld defects can lead to joints failure
Minimum thickness limit (It is impractical to produce layer less than
2 to 3 mm thick)
Limited number of material available, compare to thermal spraying
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Layer addition
Thermal spray
Advantages
Wide selection of spray/substrate materials
Fig 2- thermal spray method
Fast speed of coating formation
Wide range of substrate formation
On-site work possible
Coating can be from when keeping substrate at low temperature
Low environment impact due to dry process
Disadvantages
Thick coats are difficult to achieve
Low degree of adhesion (spray efficiency) on small
substrate/substrate with small curvature
Thermal spray coating does not always indicate the characteristics
of the original material
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Layer addition
Coating

Electrochemical plating
Chemical Vapor deposition(CVD)
Physical vapor deposition (PVD)
Ion mixing

Fig 3- electroplating method

Fig 4- PVD and CVD methods

Fig 5 ion mixing method

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Substrate Treatment
Diffusion methods

Carburizing
Nitriding
Carbonitriding
Nitrocarburizing
Boriding
Titanium-Carbon
Toyota diffusion process

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Carburizing
heat treatment process
increases strength and wear resistance by diffusing of carbon into
the surface at temperature condition about 800-950 C
maintaining toughness and strength of the core (work piece : low
carbon alloy steel 0.2-0.3 %C)
Type of carburizing
Gas Carburizing
Vacuum Carburizing
Pack Carburizing
Liquid Carburizing

Fig 7- pack carburizing method

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Carburizing
2CO C (in austenite) + CO2

(1)

CO C + 1/2O2

(2)

CH4 C (in austenite) + 2H2

(3)

CO + H2 C(in austenite) + H2O

(4)

Equation (1) and (4) are main reactions in Gas Carburizing.

Sometimes, enriched gas technique, addition hydrocarbon gas into
atmosphere, is used.
CH4 + CO2 2CO + 2H2
CH4+ H2O CO +3H2

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Caburizing
Advantages
Good combination of hard layer and tough core
Good adherence by diffusion
Disadvantages
dimensional deviations by the high temperature process and the
hardening treatment
Selective increase of the angle points; expensive machining
The dimension of the work piece is limited to the size which fits the
hardening furnace.

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Nitriding
Nitriding is conducted in atmosphere that decomposed
Ammonia to provide Nitrogen into the surface
Low process temperature (Around 500- 550 C)

Fig 8 - before and after Nitriding process structure

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Types of Nitriding
Gas nitriding
Liquid nitriding
Plasma nitriding

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Gas Nitriding
Gas Nitriding is a case-hardening process whereby nitrogen is
introduced into the surface of a solid ferrous alloy by holding the
metal at a suitable temperature in contact with a nitrogenous gas,
usually ammonia.

Fig 9 - Gas Nitriding process

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Liquid nitriding
Nitriding in a molten salt bath employs the temperature range as
gas Nitriding (510-580 C).
fused-salt bath containing either cyanides or cyanates

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Plasma Nitriding
Apply voltage between batch and furnace wall in gas Nitriding
process.
A glow discharge with a high ionisation level (plasma) is generated
around the parts. Active nitrogen permeates into the surface.

Fig 10 - comparison structures between salt baht, Gas and Plasma Nitriding

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Sulphonitriding
Surface modification treatment that can be used to treat objects with
complex shapes that are not suitable for salt bath Nitriding.
Effective with regard to changes in dimensions and distortion due to
low process temperature.
Sulphonitride layer improves seizing resistance, galling resistance
and dissolved loss resistance.
Hard Nitride layer contributes to wear resistance.

Fig 11 Sulphonitriding typical structure, plain carbon steel base.

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Sulphonitriding
Advantages
Improve wear resistant, galling resistant, seize resistant, dissolved loss
resistance.
Less dimension change, distortion due to low temperature.
Can be applied with every contours

Disadvantages
If a part is accidentally overheated the loss of surface hardness is
permanent
Nitride layer is hard but brittle.

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Boriding
Thermochemical surface hardening process which gives very hard
surface layer (1400-1900 HV in ferrous metal) and case depth
0.0005-0.020 mm.
Boriding process involves the use of specially formulated boronyielding material heated to temperatures between 1300 and
1830F(700-1000 C). Boron atoms diffuse into the substrate,
forming very hard borides within the surface of the material.

Fig 12 - Boriding typical structure of carbon steel base material.

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Hardness comparing

Fig 16- Range of hardness levels for various materials and surface treatments. EB, electron
beam; HSLA, high strength, low-alloy

Source : ASM Surface Hardening of Steels: Understanding the Basics

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Case study
The surface treatments for slurry pump(16G204A/B/C)

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Objective
To study about increasing erosion-corrosion resistance
for slurry pump parts by Multi-nite technique.

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Factors of Erosion-Corrosion

Erosion - Corrosion
-

Flow rate/ Velocity

Size of particle
Angle of impact
Material/ Hardness

- pH
- Temperature
- Corrosive product
ex. Sulphur
- Material

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Material
SS410 (CA6NM) Is a hardenable Fe-(11-14%)Cr-(3.5-4.5%)Ni-(0.41%)Mo alloy, martensitic stainless steel. SS410 type has high
corrosion resistance properties. Therefore, main problem of failure
is from Erosion.

Fig 17- Stainless steel 410 round bars

Fig 18 - Stainless steel 410 sheets

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History of failure
16G204A/B/C are the slurry pumps in A4 (RFCCU). The pumps
made from CA6NM (SS410 mod).
Fluid inside the pump is mainly Heavy hydrocarbon with sulfur 1.76
wt% at operation temperature around 350 C
Fine catalyst, contaminated product which accelerates erosion, size
20- 50 microns, which main compositions are Al2O3 and SiO2 is
increasing in the system. Results in severe erosion on parts of slurry
pumps. The pump service life was about 6 months.

Fig 19- damaged impeller

Fig 20 - damaged volute

Fig 21- damaged casing

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Why selects Multi-nite ?

Source: khun Findlay

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Selective method
Surface treatment for increase erosion resistant by multi-nite
technique (Sulphonitriding)
Multi-nite is a thermochemical process to add nitrogen and sulfur
into surface of materials to form compound layer, and hard diffusion
zone layer

Fig 22- Multi-nited impeller

Fig 23- Multinited volute

Fig 24- Multi-nited Casing

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Erosion

Multinite
pressure

temperature

Diffusion
zone

Hardness
time

material

N2 , NH3 and NM gases

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Multi-nite Process
Receive
works from
customer

Shipping
to customer

Incoming
inspection

Issue
inspection
report

Issue
HTOS

Hardness
inspection

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Vacuum
Washing

Heat
treatment
(Multi-nite)

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Multi-nite reaction equations

NH3 = 1/2 N2 + 3/2 H2
N2 = [N]
[M] + [N] = MN
2[Cr] +[N] =Cr2N
M: Alloy elements ex. Al, Mo, Fe
= Austenite matrix/phase

Fig 25 - Schematic cross section of nitriding region of an iron-base ferritic

specimen/component showing the compound layer and the diffusion zone with
their (possible) constituents

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Diffusion of nitrogen

Fig 26 Schematics of phase distribution within a nitrided case on steel and

accompanied nitrogen depth concentration.

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Assumptions of case study

The higher temperature results in the thicker diffusion zone
nitrogen and sulfur affect to surface hardness of materials. By
forming compound with base material, nitrogen and sulfur make
surface of materials harder.

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Parameters
Materials: SS410 (CA6-NM)
Process time: Std. time Vs Std.+ minutes
Temperature: 510 and 560 C
testing technique : SEM
Indicated by : thickness of band of diffusion zone

Volume of N2,NH3, NM gases (fixed)

Vacuum Pressure (fixed)

510 C
Std. exposer time

560C
Std. exposer time +
additional time

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Samples

(a)

(b)

Fig 25

the 1st sample

Non Multinite
Part:
Volute
Material:
SS410
Sample sizing: 1x1x0.5 cm
Testing:
Hardness
SEM JSM-5410LV
EDS
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Samples

Fig 26 -

the 2nd sample

Multinite at 5100C
Part:
Volute
Material:
SS410
Sample sizing: 1x1x0.5 cm
Testing:
Hardness
SEM JSM-5410LV
EDS
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Samples

Fig27 -

the 3rd sample

Multinite at 5600C
Part:
Volute
Material:
SS410
Sample sizing:
1x1x0.5 cm
Testing:
Hardness
SEM JSM-5410LV
EDS
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Steps of testing
Hardness test
Tested sample number 1,2 and 3 by micro vicker hardness testing
machine. collected the hardness of diffusion layer and base material,
present in graph
Hardness VS case depth graph (by vender)

SEM JSM-5410LV

Take the photos of microstructure of sample number 1,2 and 3 for

study the thickness of compound layer, diffusion zone and base
material.

EDX

Use spot analysis techniques to collect elements component of sample

1,2 and 3

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Results
Microstructures, x100, of the 1st sample (a)
Existing
Coating ?

140 m

Fig 28- inner cross section

Fig 29 intermediate microstructure

inner
outer

Hardness
(HV)

Fig 30 outer cross section

Point 1

Point 2

Point 3

Base
Material

501.74

560.54

597.90

397.62

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Results
Microstructure, x100, of the 1st sample (b)

Fig 31 inner cross

section

Fig 32- intermediate

microstructure

Fig 33 outer cross section

outer
inner
Hardnes
s (HV)

point1

point2

point3

average

356.48

347.62

361.04

355.05

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Results
Microstructures, x100, of the 2nd Sample

22 m

24 m

Fig 34-inner cross section

Fig 35- intermediate microstructure

inner

Hardness
(HV)

Fig 36- outer cross section

Point 1

Point 2

Point 3

Base
material

1149.17

1149.17

1149.17

393.93

outer

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Results
Microstructures, x500, of the 2nd Sample

22 m

24 m

Fig 37 inner cross

section, diffusion zone.

Fig 38 outer cross

section, diffusion zone

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Nihons lab Result

Fig -Microstructure at surface of 2 nd

Samples batch

Fig- case depth hardness graph of 2 nd samples batch

Compound layer 5.0 m

Diffusion zone 42.5 m
Actual Hardness 1172 HV

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Results
Microstructures, x100, of the 3rd sample

78 m

75 m

Fig 39- Inner cross section

Fig 40 Intermediate microstructure

inner
outer

Hardness
(HV)

Fig 41- outer cross section

Point 1

Point 2

Point 3

Base
material

1007.15

1007.15

1007.15

322.95

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Results
Microstructures, x500, of the 3rd sample

78 m

Fig 42 inner cross section,

diffusion zone.

70 m

Fig 43 outer cross section, diffusion

zone.

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Nihons lab Results

Fig -Microstructure at surface of 3 rd

Samples batch

Fig- case depth hardness graph of 3 rd samples

batch

Compound layer 5.5 m

Diffusion layer 91.9 m
Actual Hardness 1190 HV

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Results
Hardness Test
1

Diffusion zone

Base material

Load HV 0.3
Point 1

point2

point3

3 points avg

point4

1st sample

510.74

560.54

597.90

556.39

397.62

2nd sample

1149.17

1149.17

1149.17

1149.17

393.93

3rd sample

1007.15

1007.15

1007.15

1007.15

322.95

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Results
EDX test the 1st sample (a) (base)
Elmt Element%

Atomic%

Si
Cr
Mn
Fe
Ni
Au
Total

100.00

0.83
13.07
0.54
73.44
3.75
8.37
100.00

1.73
14.68
0.58
76.80
3.75
2.48

Fig 45- microstructure of the 1st base material

Fig44: EDX Spot analysis on the 1st samples base material

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Results
EDX test the 1st sample (a) (grey band)
Elmt Element%

Atomic%

O
Si
Cr
Mn
Fe
Ni
Au
Total

100.00

18.28
1.25
17.97
0.43
48.05
5.49
8.54
100.00

45.03
1.75
13.62
0.31
33.90
3.68
1.71

Fig 47- grey band at inner surface

Fig 46: EDX Spot analysis on the 1st samples grey band

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Results
EDX 2nd Sample (diffusion zone)
Elmt Element%
Si
Cr
Mn
Fe
Ni
Au
Total

Fig 48: EDX Spot analysis on the 2nd samples diffusion zone

0.83
13.07
0.54
73.44
3.75
8.37
100.00

Atomic%

1.73
14.68
0.58
76.80
3.75
2.48
100.00

Fig 49- diffusion zone at inner surface

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Results
EDX 2nd Sample (base material)

Elmt Element% Atomic%

Si
Cr
Mn
Fe
Ni
Au
Total

Fig 50: EDX Spot analysis on the 2 samples base material

nd

0.92 1.93
12.45 14.11
0.70 0.75
72.50 76.45
3.91 3.93
9.51 2.84
100.00
100.00

Fig 51- the 2nd base material

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Results
EDX 3rd Sample (diffusion zone)
Elmt Element% Atomic%
Si
Cr
Mn
Fe
Ni
Au
Total

1.34 2.80
17.20 19.38
0.60 0.64
67.69 71.00
3.23 3.22
9.93 2.95
100.00
100.00

Fig 53 diffusion zone at inner surface

Fig 52: EDX Spot analysis on the 3rd samples diffusion zone

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Results
EDX the 3rd Sample (base material)
Elmt Element% Atomic%
Si
Cr
Mn
Fe
Ni
Au
Total

0.73 1.53
12.52 14.17
0.72 0.78
72.85 76.76
4.02 4.03
9.16 2.74
100.00
100.00

Fig 55 the 3rd base material

Fig 54: EDX Spot analysis on the 3rd samples base material

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Discussions
Sample

Diffusion
thickness

hardness

% hardness

2nd (510C)

23 m

755.24

192%

3rd (560C)

74 m

684.2

212%

Hardness : (hardness of base metal) ( diffusion zones hardness)

Hardness results form laboratory and vender are not exactly

amount, but are in the same trend, because of measuring
techniques.
Maximum hardness at surface for each sample are closely because
it depends on base materials
Temperature at 560 C results in thicker diffusion zone than lower
temperature at 510 C
Labs surface preparing affects to destroyed compound layer. So,
we could not see compound layer form microstructures pictures.

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Discussion
EDX spot analysis technique might not proper to detect volume of N
due to limitation of Carbon coating is not available in the laboratory.
EDX line scan may be a proper method for detecting the volumes of
elements in diffusion zone.
XRD may be a good alternative to analyze compounds at the
surface for test a result between chromium compound and
hardness.

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Summary
Mult-nite process improves surface hardness by forming
compounds
at compound layer and diffusion of elements in
diffusion zone.
Multi-nite process improves surface hardness of CA-6NM. At 510
C, hardness increases from 393.93 HV to 1149.17 HV (192%). At
560 C, hardness increase form 322.95 HV to 1007.15 HV
(212%)
Muliti-nite process at 560 C gives thicker case depth and higher
hardness than process at 510 C.

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Recommendation
Multi-nite process at 560 C is an optimum method for improving
erosion resistance on 16G204A/B/C because this process was
proved that can increase about 3 times hardness at the surface
without distortion problems.
To inspect the pump parts after start running, by follow the previous
interval, to confirm erosion rate and effectiveness of Multi-nite.

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Reference

[Link]
id=1awuxJ5v2ucC&pg=PA290&lpg=PA290&dq=sulphonitriding+disadvantage&source=bl&ots=vF
Alexx8qV&sig=zLrslK8sGqBCvWkde8aImh1iLqg&hl=th&sa=X&ei=huKdVZS4L8TluQTUgKHYDA
&ved=0CCEQ6AEwAA#v=onepage&q=sulphonitriding%20disadvantage&f=false
[Link]
[Link] p3
[Link]
[Link]
[Link]
[Link]
/
[Link]
[Link]
David Pye (2003) Practical Nitriding and Ferritic Nitrocaburizing, 1st edn., United State of
America: ASTM International
http://
[Link]/resources/elements/12/101812/Application%20Notes%20Nitrided%20coatings%
[Link]
[Link]
[Link]
[Link]
[Link]
[Link]

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Thank you

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