Recubrimientos Duros

para Protección al Desgaste

en Petróleo y Minería

Patricio F. Mendez
Professor
Director, Canadian Centre for Welding and Joining
Weldco/Industry Chair in Welding and Joining
www.ccwj.ca

1
 Buenos Aires
• University of Buenos Aires
– Mechanical Engineer
• Argentine “ONR”
– Research on wind turbines
• Tenaris
– Integrated steel maker

2
 Boston
• MIT
– MS in Materials Science and
Engineering
• Semi-solid metal processing
x
– PhD in Materials Engineering
• Welding at high currents
– Postdoc
• Mathematical modeling of materials
processing
• Semi Solid Technologies Inc.
– Startup
– Licensed to Ford
• Exponent
– Consultant / Litigation

3
 Boston: Semi-Solid Technologies

• Mendez, P.F. and Brown, S.B. Modeling of Selected SFF Process Limits. in Solid Freeform
Fabrication Symposium. August 8-10, 1994. Austin, TX. p. 299-306.
• Mendez, P.F. and Brown, S.B., Method and Apparatus for Metal Solid Freeform
Fabrication Utilizing Partially Solidified Metal Slurry. United States Patent # 5,893,404,
1999.
• Rice, C.S., Mendez, P.F., and Brown, S.B., Metal Solid Freeform Fabrication Using Semi- 4
Solid Slurries. JOM, 2000. 52 (12): p. 31-33.
 Boston: Welding
Welder Welding Engineer Manager

Niccolò Paganini Antonio Stradivari (1644 - 1737) Herbert von Karajan

(1782 – 1840) (1908 – 1989)

Ludwig van
Beethoven
(1770 – 1827)

5
Fantastic voyage into a weld
Alex the Welder

Weld

6
Fantastic voyage into a weld
Weld

Arc

Electrode
(Many types)

Weld puddle

7
 Fantastic voyage into a weld
electrode

arc

weld puddle

magne c fields

electrical current
magne c fields

24

welding arc: 20,000 K welding arc: 300 m/s

Hannes Alfvén,
Nobel Prize in
Physics, 1970
Magnetohydrodynamics

surface of the Sun: 6,000 K jetliner: 250 m/s

8
 Denver
• Colorado School of Mines
– Center for Welding, Joining, and
Coatings Research
x x
– Foundry research

9
 Edmonton
• UofA
– Canadian Centre for Welding and
x
Joining x x

10
11
 12
Moraine lake, Alberta
 History of the CCWJ
• Prof. Barry Patchet, NOVA Chair until 2004
• No coordinated welding focus between 2004 and
2009
• Weldco / Industry Chair created in 2007
• Patricio Mendez hired in 2009
• Weldco/Industry Chair announced on May 4, 2009
($3.5M endowment)
• Laboratory opened on May 5, 2010
– currently $3.5M in facilities
– $3.8M so far in external funding
– ~$300K annual budget (50% student salaries, 25% staff, 10%
travel)
– ~$100K in scholarships
• AMFI Created on Jan 1, 2011
• Leijun Li joined in September 2013
 CCWJ Sponsors •
• Industrial Advisory Board Equipment, consumables, research, and
– Weldco Companies training
– Acklands Grainger – Alberta Innovates Technology Futures
– Canadian Welding Bureau – American Welding Society
– CESSCO Fabrication and Engineering – Arctec
– Lincoln Electric Company of Canada – Babcock Hitachi
– Metal Fabricators & Welding Ltd. – CASTI
– Miller Electric – CLAC
– Suncor Energy – Canadian Welding Bureau
– Syncrude Canada – Canadian Welding Association
– Government of Alberta – Defence Canada
– HC Stark
– Hobart Brothers
– JV Driver
– Lincoln Electric
– Miller Electric
– Praxair
– Productivity Alberta
– Sulzer
– Syncrude
– Thermadyne/Stoody
– Totem Acoustic
– Tregaskiss
– Western Economic Diversification
– Wilkinson Steel
 People

• 2 Professors full time

– Patricio Mendez
– Leijun Li
– Collaborations with Medicine, Physics, ChemE, MechE, CivE,
Education, Comp. Sci.
• 3 Staff
• Current: 4 PhD, 12 MSc, 40 BSc, 5 HS, 1 MS=63
• 17 Nationalities (11 in photo)

15
youtube: CCWJ “this is welding”

16
 Costs of wear
• Cost of wear to Canadian industry
– $2.5 B/yr
• In oil sands of Northern Alberta: down time in
any production line
– $3–6 M/day
• For oil sands operator, wear replacement parts
and labor
– $40 M/yr
• Similar for Mendez, P. F. et al, Welding Processes
– mining and pulp for Wear Resistant Overlays.
Journal of Manufacturing Processes,
2014. 16: p. 4-25
17
• Steels
– Pearlitic steel
–

Materials Systems
Austenitic manganese steel
– Austenitic stainless steel
– Low carbon martensitic steel
– Tool steel
– Martensitic stainless steel
– High carbon austenitic steel
– High carbon martensitic steel
– High carbon martensitic steel with primary alloy carbide
• Chromium White Irons
– Austenitic iron
– Martensitic iron
– Austenitic chromium carbide iron (23XX)
– Complex chromium carbide iron includes types containing up to 45% tungsten
– Martensitic chromium carbide iron
– Low chromium white iron
• Tungsten Carbide Composites
– Carbide chips in Cu alloy matrix, > 4000 μm
– Tungsten carbide granules in an Fe rich matrix, >. 850 μm, 425-850 μm, 150-425 μm, <150 μm
– Tungsten carbide granules in a Ni-B matrix < 75 μm (36XX)
• Cobalt Alloys
– Complex Co-base solid solution
– Hypo-eutectic Co-Cr-W alloy
– Hyper-eutectic Co-Cr-W alloy
– Co-Cr-Ni-W alloy
• Nickel Alloys
– Complex Ni base solid solution
– Low melting point Ni-B alloy
– Tungsten carbide (<45wt%) in a Ni-B matrix
– Solid solution
• Copper Alloys
– Phosphor bronze (4-6% Sn), (7-9% Sn)
– High tensile brass (Cu-Zn-Mn)
– Nickel bronze (9-13% Ni)
– Aluminium bronze (9.5-14% AI)
– Nickel aluminium bronze
– Complex aluminium bronze (Cu-Mn-Fe-Ni-AI)
WTIA Technical Note No. 4

18
• Iron-base alloys
– Ferrite with second phase
– Low-alloy martensite
–
–
–
Tool-steel martensite
Stainless-steel martensite
maraging steel
Materials Systems
– martensite and austenite
– martensite with alloy carbides
– martensite with eutectic
– nominally austenitic stainless steel
– ferritic-austenitic stainless steel
– austenitic manganese steel
– austenitic chromium-manganese steel
– austenitic manganese steel containing alloy carbides
– primary austenite with eutectic
– near eutectic
– primary carbides with eutectic (PKE)
– primary carbides, alloy carbides and eutectic
• Non-ferrous hardfacing deposit types
– cobalt solid-solution alloy
– primary cobalt solid-solution alloy with cobalt alloy/carbide eutectic
– near-eutectic mix of carbides and cobalt solid-solution alloy
– primary carbides with eutectic
– cobalt solid-solution alloy with Laves phase particles
– nickel alloy solid solution
– nickel borides
– chromium borides in nickel alloy/boride eutectic
– Nickel-base alloy solid solution with Laves-phase particles
– Solid-solution bronzes
– two-phase bronzes
– tungsten carbide in an iron matrix
– Tungsten carbide in a nickel-base alloy matrix (W-Ni)
ISO/TR 13393
19
 Materials Systems
Particle of sand
Path of particle

WC
Ni matrix

Steel component

Ni-WC
Wear performance

Cr-Carbide
(CCO)
Q+T

Cost
20
 CCO vs WC
• CCO • WC
– Cr carbides ~ 1200-1800 Hv – W carbides ~ 2200-3100 Hv
– Toughness: KIC<1 – Toughness: KIC~6
– CCO matrix: steel – WC matrix: Ni or Co
– Cost: more affordable – Cost: very expensive
(~$50/kg) (~$150/kg)
– G65: 0.2 g – G65: 0.05 g
– CCO form during – WC external, dissolves in molten
solidification metal.
– Fe Matrix – Ni/Co matrix (Cu?)
– Density: 7 g/cm3 (~same as – Density: 16.5 g/cm3 (~double
molten Fe) molten Ni)
– Mainly Cr7C3 – Many types
– Application: – Application
plates ground engagement, drilling
21
 Chromium Carbide Overlays
• Chromium carbides
– (Cr, other)7C3
– hexagonal rods, often with a Fe (austenite?) core
– parallel to T gradient, perpendicular to basal plane
• Matrix of eutectic
– (Cr, other)7C3+Fe
• Evolution
– carbides nucleate
from melt
Borle, S., Deposition of Chrome Carbide Overlays Using Submerged Arc Welding. MSc,
Chemical and Materials Engineering, University of Alberta, 2013. P.F. Mendez advisor.
22
 Chromium Carbide Overlays
• The estimated
annual market for
CCO is estimated to
be in greater than
$30 million in
Alberta alone

Oil Sand Sizing Screen

Chute liners 2
3
 Microstructural Evolution of CCOs

For CCOs the area of interest in the Fe-Cr-

M7C3 C phase diagram is between 2-6% Carbon
and 8-35% Chromium
35
Chromium wt.%

Hypereutectic
This leaves gives three possible
γ solidification paths

A-Hypoeutectic
Hypoeutectic
8 C B- Eutectic

M3C C- Hypereutectic

2 6
Carbon wt.%

24
 Microstructural Evolution of CCOs
Hypoeutectic
L→γ
L → γ + M7C3
This microstructure is less wear resistant
but has better toughness and corrosion
resistance in most cases

25
 Microstructural Evolution of CCOs
Eutectic
L → γ + M7C3
The wear resistance of eutectic
alloys is usually in between that of
hypoeutectic and hypereutectic

26
 Microstructural Evolution of CCOs
Hypereutectic
L →M7C3
L → γ + M7C3
Hypereutectic alloys usually have the best
wear resistance of all three of the
microstructures

27
 Chrome Carbide Overlays
• Interesting features
– Effect of cooling rate
– Dilution (Layered Structure)
– Rod vs. Blade

28
 CCOs: Effect of Cooling Rate
• Conventional Wisdom:
– fast cooling (low HI) reduces carbides

29
 CCOs: Effect of Cooling Rate
• There was no clear trends
from the effect of cooling
rate samples
• The average size of the
primary carbide was
expected to increase
• Dilution stayed relatively
constant through the
samples

Total VF VF VF Primary Average Primary

Preheat Carbide Hypereutectic M7C3 Size (um) Dilution
25⁰ C 26.99% 30.40% 1.69% 389 27%
50⁰ C 23.59% 31.24% 1.84% 427 25%
100⁰ C 25.35% 46.12% 5.02% 542 26%
150⁰ C 24.54% 19.89% 0.66% 252 25%

30
SAW MCAW
46 kJ/cm 8 kJ/cm
4 kJ/g 6 kJ/g

PTAW LBW
13 kJ/cm 20 kJ/cm
1.3 kJ/g 1.4 kJ/g

31
 CCOs: Effect of Cooling Rate
• Conventional wisdom:
– fast cooling (low HI) reduces carbides
• Evidence so far
– cooling rate seems to be a secondary factor
– dilution seems to be much more important

32
 Dilution in CCOs
• Get different microstructure
throughout CCO’s
• In MCAW this is often overcome
using multiple layers
• In SAW this is not always
practical

BY Y. F. ZHOU, Y. L. YANG, D. LI, J. YANG, Y. W. JIANG, X. J. REN, AND Q. X. YANG; Effect of Titanium Content on Microstructure
and Wear Resistance of Fe-Cr-C Hardfacing Layers, August 2012 AWS Welding Journal

33
Dilution in CCOs
LBW
• Banded structure
– Dilution
• along depth
• along width
– Segregation
– Dynamics of powder
addition

34
Dilution in CCOs

35
 Rod vs. Blade

Barnes, N., Borle, S., Dewar, M., Andreiuk, J., and Mendez, P. F.,
3D Microstructure Reconstruction of Chrome Carbide Weld Overlays
Science And Technology Of Welding And Joining, 2014. 19 (8): p. 696-702.

36
Rod vs. Blade

300μm

60 m
0μ 0μ
m 60

37
 Typical processes for CCOs
• Typically with higher heat inputs, large
deposition rate, less expensive equipment
– SAW
– MCAW

38
SAW of CCOs

39
SAW of CCOs

flux
alloy
powder

40
 Effect of AC Balance
25%

30,0

20%
28,0

Carbide Diameter (um)

Volume Fraction
Primary Carbide

Average Primary
15%
26,0

10%
24,0

5% 22,0

0% 20,0
50% 55% 60% 65% 70% 75%

Volume Fraction Carbide Size

Borle, S. D., Gall, I. L., and Mendez, P. F., Primary Chromium Carbide Fraction Control with
Variable Polarity Saw. Welding Journal, 2014.

41
 Ni-WC Overlays
• Tungsten carbides
– WC, W2C, WC1-x, and combinations
– equiaxed angular, spherical, reprecipitated
• Matrix of austenite and eutectic
– 1ry Ni, Ni + Ni3B/ Ni3Si
• Evolution
– carbides are second
phase
– must avoid dissolution

42
 Tungsten Carbide Types
• Monocrystalline WC • Eutectoid W2C/WC
– ~1200-2000HV – ~2200-2400HV
– More resistant to – More impact resistant, W2C
dissolution prone to dissolution

WC

W2C

43
 Tungsten Carbide Types
• WC-coated Eutectoid • WC1-x
– WC resists dissolution – 2700-3400HV
– W2C/WC increased hardness – Metastable requiring very
fast cooling rates

Eutectoid WC coating

44
 Nickel Matrix
• Nickel-based matrix alloyed with Cr, B, Si to increase hardness
– Cr: 0-13 wt%
– B: 1-3.5 wt%
– Si: 3-6 wt%
• Primary Ni dendrites (~350 HV)
– Lighter regions
• Ni + Ni3B/ Ni3Si (~700 HV)
– Darker regions
Eutectoid
• Purchased on bulk/matrix hardness
Primary Ni Ni + Ni3B W2C/WC
– 30, 40, 50, 60HRC variants

45
 Challenges in Ni-WC
• Low carbide fraction
– Conventional wisdom
• Reduce heat input

46
 Effect of Chromium
brittle reprecipitated carbides

with Cr no Cr

Just, JMPT, 210 (2010)

47
 Challenges in Ni-WC
• Low carbide fraction
– Conventional wisdom
• Reduce heat input
– Reduce Cr!

48
 Typical Processes for Ni-WC
• Low heat input / cool weld pool
• State of the Art and Alternative Processes
– PTAW
– LBW
– GMAW
– HWGMAW
• HWGTAW
– Oxyacetylene flame brazing

49
State of the Art in Ni-WC: PTAW
– Powder melts right over
the plate:
• little overheat
– Challenge: settling
– No position overlays
– No field repairs
– ~8-10 lb/hr
– ~2-4mm thick and 10-
30mm wide
– At CCWJ: 450A system
for >20 lb/h

50
State of the Art in Ni-WC: PTAW

51
 State of the Art in Ni-WC: LBW

off-axis feed coaxial feed

• very little dissolution

• very little dilution
• highest volume fraction
• can use metastable spherical carbides
• most expensive equipment
• low “cachment”

52
State of the Art in Ni-WC: LBW

53
 Summary
• CCOs
– different than casting
• cooling rate might be secondary
• dilution is primary
• “rice krispies,” halo, stars, banded microstructure
• 3D analysis
• Ni-WC
– State of the art: PTAW, has limitations
– LBW: coming up very fast
– Alternatives: tubular wires
• GMAW
• HWGMAW
– similar performance to PTAW
– higher productivity
• New developments
– Small hard phases
• Needle-like
• Equiaxed

54
 Alternative: Tubular Ni-WC Wires
• Not flux-core, not metal core
• Pure Ni sheath, tungsten carbide and alloy powder core
• Very diverse!

55
 Alternative: Tubular Ni-WC Wires
• Carbide volume fraction varies considerably

56
GMAW of Ni-WC wires

57
 GMAW of Ni-WC wires
• Challenges
– Carbide bouncing!
• Mitigation
– Short circuit
– Hot wire approach

Guest, S., Chapuis, J., Wood, G., and Mendez, P. F., Non-Wetting
Behavior of Tungsten Carbide Powders in a Nickel Weld Pool: A
New Loss Mechanism in GMAW Overlays. Science And
Technology Of Welding And Joining, 2014. 19 (2): p. 133-141.

58
 Manganese Steels
• transform to martensite on deformation
• dominant for cone-crushers

59
 Manganese Steels
• acs

60
 Wear Plates

air hardening
tungsten carbide steel

cobalt binder
(between carbides)

tooth core carbide

chips
gap between
wear bar and
tooth core

61
New Developments
Black dots: MC type of carbides (M=V with
small amounts of Mo). White lamellar
phase: M3B2 (M=Mo with small amounts of
Fe). Gray (both as matrix and as eutectic
lamellae): Fe –based martensite

62
Small equiaxed hard phases

63
Impact resistance of small equiaxed
hard phases

64