Materials selection for wear resistance

Sensible to adopt a systems approach. The materials aspects are part of the whole design problem.

Design Application Function Economic, etc. aspects Unalterable features (continuum) Alterable features more freedom to alter Overall shape Basic Materials Stress State Operating Environment Design Details Lubrication Method Surface treatments Wear rate Time to failure

(very loose categorisation, as most of the above mutually dependent to some extent) 1

Steve Roberts - Surface Engineering - Surface Engineering

Using design to reduce wear

Fretting Abrasive wear

Displacement control Reduce loads Lubricate Stress control Increase loads Use adhesives or fixings to clamp the components together Exclude oxygen Use steel rather than Al or Ti

Reduce loads Keep abrasive out Flush abrasive away Filter to keep abrasive particles small Use as intrinsically hard a material as possible without sacrificing ductility (Could be ceramic if clean system)

Erosion

Adhesive wear

Reduce gas speeds Keep abrasive out if possible Filter to keep abrasive particles small Design fluid flow to give low-erosion impact angle Use as intrinsically hard a material as possible without sacrificing ductility

HD, EHD or BL lubrication Reduce loads Smooth surfaces Use solid lubes, polymers, soft metals if HD lubrication impossible Select materials for low adhesion if lubrication failure. (see next) Design for most wear to be on replaceable part.

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Materials for adhesive wear

No liquid or solid solubility Some liquid, v. lowsolid solubility Limited solid solubility Extensive solid solubility Same metals N.B. - Pb, Sn, In against Fe and Al Steve Roberts - Surface Engineering - Surface Engineering 3

Better for adhesive wear applications

Using surface engineering to reduce wear

Fretting Abrasive wear

Displacement control Harden surfaces ? try to design out. Stress control Design it out !

Surface treat one or both components to harden Coat one or bothcomponents with v. hard metal (could use ceramic and try to keep particle sizes small) Depth of treatment might have to be large to cope with wear rates

Erosion

Adhesive wear

Coat with intrinsically hard material Low incidence - ceramic High incidence - v. hard metals ? or use ceramic and try to keep particle sizes small.

Surface treat one component to harden Coat one component with v. hard metal In both cases, use or coat other component with / of shearable, nonchemically combining material Depth of treatment can be small

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Surface Engineering Methods

Anodising Electrolytic Plating High T. spray processing Weld coatings Vapour phase methods Mechanical Transformation Composition unchanged Laser, E-beam Melting Thermochemical (solution) Thermochemical (reaction) MIG weld Carburising Nitriding, Metallising Ion Implantation Steve Roberts - Surface Engineering - Surface Engineering 5 CVD, PVD Shot peening, etc. Flame, Induction

Fusion

Surface Coating

Surface Modification

Composition changed

Mechanical methods

Any Metal: Work harden the surface

Use controlled impingement of: shot abrasive peening blasting

Must be able to get at all the surface to be treated. A low - cost, automatible process. Not much use for wear resistance: Adhesive wear: spoils surface polish Abrasive wear workhardening is part of the & erosion: wear process. Intentional w.h. has little effect. Very good for fatigue resistance. Examples: valve spring wire, leaf springs, gears

Steve Roberts - Surface Engineering - Surface Engineering

Transformation Hardening (1)

Steels:
Heat surface into austenite range and quench let cold bulk quench extra surface cooling Quench Medium Inlet

Flame Hardening. Oxy - actetylene or oxy-propane flame Depth - 0.25 - 6mm Induction Hardening. R.F. Heating: f = 3 - 500kHz Depth: 20/ f below 770C (Tcurie) 500 / f above 770C Induction Coil

Typically 0.5 - 5mm

Special coils for shaped components - e.g. gear teeth

Both these methods normally use water quenching - spray or bath. Steve Roberts - Surface Engineering - Surface Engineering 7

Transformation Hardening (2)

Laser Hardening.

Laser Hardening. High - power (1-10 kW cm-2) electron beam (2-3mm spot size), scanned over surface by electromagnetic deflection. No surface coating needed. Effects like laser treament. Power Density (Wcm-2)

High - power (0.5 - 15kW) continuous beam CO2 laser (2-3mm spot size), scanned over surface by mirrors. Surface is coated with graphite or iron oxide to absorb light. Heating rate: ~106 K s-1 Cooling rate: ~104 K s-1 Surface is quenched by thermal conduction into substrate. V high cooling rates can give martensite even with low C content - avoids distortion and possible surface cracking. Higher power densities can lead to melting (laser glasing)

108 1.1

1.0 0.9 106 0.8

104 0.7

Laser / e-beam treatment Laser melting Induction / Flame Hardening

10-8 1 10-6 3 10-4 5 10-2 7 8 9 1 0 2 4 6 Interaction time (s) 8

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Surface Melting
Useful for wide range of materials:
Basic effect is grain refinement - though in steels can also get transformations. Needs very high input power density, by: 17% Al - Si alloy

electron beam laser beam T.I.G. welding

Good for: medium carbon steel (0.4 - 0.9% C) (low carbon ! soft retained - ferrite) S.G. cast irons (TIG process) - gives tough core with hard surface Cast Al alloys:

50m As cast: hardness 80 kg mm-2 wear increased by fracture of large Si platelets.

50m Laser melted: hardness: 160 kg mm-2 Si platelets now below critical size for fracture

Steve Roberts - Surface Engineering - Surface Engineering

Thermo - chemical treatments

Principally for ferrous alloys

Interstitial elements (carbon, nitrogen) diffused into surface

Interstitial elements (carbon, nitrogen, boron) and substitutional elements (e.g. chromium) diffused into surface. Hardening by formationof hard reaction products Either:

Hardening by solutes Quench and temper to get surface martensite

hard layer or fine hard precipitates

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Carburising (case hardening)

Done in austenite phase field: Typically take surface of medium - low C steel (0.15 - 0.2%) to 0.7 - 0.9%C Either: or Quench immediately and light temper Cool slowly, machine and then heat - treat. Will always be Get: some dimensional change (try to minimise as this is final process) (wear resistance) hardening (fatigue resistance) surface compression

Gas Carburising ~900C

Atmosphere: CO / H2 / N2 or CH3OH / N2

Case Carburising ~900C

Pack in box with charcoal. (& energiser .. BaCO3) C + residual O2 !CO

Vacuum Carburising ~1050C

Components heated, low P CH3 or C5H12 added. Further diffusion heat

Plasma Carburising ~1050C

Components heated, in low P CH3; glow discharge deposits C on -vely charged surface. Further diffusion heat 11

Steve Roberts - Surface Engineering - Surface Engineering

Carburising (2) and Carbonitriding

Comparison of typical carburising treatments on 0,18% plain C steel.

Carbonitriding
Carbon and Nitrogen diffused into the steel: Quench and temper.

1000 Hardness (kg mm-2) 800 600 400 200 0 0 0.5 1 1.5 2
Plasma 52 min / 1050C Vacuum 45 min / 1040C Gas 45 min / 900C
350 mm Hg

Often can Oil quench, as treated surface has higher hardenability; reduces risk of cracking. Better wear restance than carburising. Gas Carbonitriding: add ammonia to Gas Carburising mixture Salt Bath Carbonitriding (Liquid Carburising) immerse in molten salt bath, typically 45% NaCN, 40% Na2CO3, 15% NaCl ~880C / 1hr.

20 mmHg

Depth (mm)

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Compound - forming surface transformations

Nitriding:
Diffuse nitrogen in to form fine nitrides with Al, Ti, V, Mo, etc. Done at ~400C, i.e. in ferritic regime for C steels. (can also do ne austenitic stainless steels that contain nitride formers) Typically on ~0.4%C alloy steels that have been heat-treated before nitriding. Ideally on steels which temper at the nitriding temperature. Hardness produced by nitriding retained up to ~500C (higher than decomposition T of martensite produced in carburising - 200C) Produces compressive stresses - good for fatigue resistance. Can get brittle white layer (iron nitrides). Careful process control needed to avoid.

Gas Nitriding
Heated in ammonia 400 - 550C May need 3-4 days to get layer 500m deep Cr - Mo steel Cr - Mo - V Cr - Mo - Al 650 kgmm-2 900 kgmm-2 1100 kgmm-2

Plasma / ion Nitriding

Component in used as cathode at 500 - 1000V in 10-4 - 10-1 atm H2 / N2. Plasma forms, heats surface Nitrogen ions diffuse in. ~3x faster than gas nitriding, ... can be used down to 350 C, so useful for temper-sensitivesteels.

Steve Roberts - Surface Engineering - Surface Engineering

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Nitrocarburising

Cheap and nasty process - deliberate white - layer like formation. Usually on low alloy or mild steels. 500 - 650 kg mm-2 ~20m

Thin hard layer of Fe (C,N)3 Substrate hardened by nitrogen diffused in Low C / low alloy substrate

Traditional processes (e.g. Tufftriding ) uses salt bath (~2hrs) - sodium cyanide and cyanate (typical applications - crankshaft bearings) More modern processes use less toxic baths or adapted gas or plasma nitriding processes

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Boronizing
Diffuse boron into surface to form iron boride layer Outer layer: FeB Sub surface layer: Fe2B Have different T, so careful process control needed to avoid cracking. Hardness ~ 1500 kg mm-2, (SiO2: 750- 1200), so useful against abrasive wear. Process: Iron boride layer on low - C steel Layer is strongly keyed to substrate

Like case hardening: surround component with mixture of: source of Boron B4C, SiC / Al2O3 - inert diluent vapourises, decomposes on steel surfcae and injects boron KBF4 K and F reform KBF4 by reaction with B4C Typically, 900 C, 6 hrs : i.e. in austenite field - can heat treat substrate afterwards. Also can be done in molten salts baths, or by plasma boronizing Can do to : WC / Co : borides in both Co and WC Ti & alloys: TiB (hardness 2500 kg mm-2)

Steve Roberts - Surface Engineering - Surface Engineering

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Metallizing / Metalliding

Chromising:
Case - harden steel Pack, Gas phase or salt bath at ~950C to diffuse Cr into surface Hard layer of Cr23C6 formed ~40m thick Hardness ~ 1500 kg mm-2 - abrasive wear resistant. Hardness kept up to ~700 C.

Hard layers on non-ferrous alloys:

Deposit alloy on surface electrolytically. Heat treat to interdiffuse and react. e.g. Sb / Cd / Sn on brasses: Interdiffuse at 400C 20-30m layer with hardness 450-600 kg mm-2

TD process:
Hard layers of V, Ti, Nb carbides formed, ~10m thick Salt bath Hard layers of Cr23C6 formed at 8001000C to diffuse metals into surface Quench direct from bath Hardness >3000 kg mm-2 - abrasive wear resistant. Steve Roberts - Surface Engineering - Surface Engineering

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Ion Implantation
Process:
Accelarators used to inject ions into surfaces at 50 - 100kV - gives typical penetrationof <0.5m. Typical doses >1017 ions / cm2. ! 10-20% solution of implanted species. Low temperature process ~200 - 300C from bombardment heating. Line of sight - complex shapes may be problematic Can inject any atomic species into anything. - gas ions (e.g. nitrogen) easiest to make sources for Can use neutral ions (e.g. Ar) to knock-on a coating into substrate. - ion mixing Displacement damage in substrate gives high diffusion coefficients - can heat to allow chemical reactions after implantation Extra volume of injected matter gives very high compressive stresses. Effectively no dimensional change - final process

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Ion Implantation - applications

Typical applications:
Nitrogen into steels Ti into steels Ti, B into steels N into ceramics: N into WC / Co Cr into steels ! fine surface nitrides (?): hard and wear resistant surface ! low friction surface: modifies surface oxides (?) ! fine TiB2 - hard, wear resistant surface ! soft, amorphous surface: abrasive wear resistant ! increased wear resistance ! increased corrosion resistance
Unimplanted

Unimplanted

Steel :
abrasive wear on rotating pin N - implanted

SiC:
50g diamond point wear track

20m
N - implanted

20m Steve Roberts - Surface Engineering - Surface Engineering 18

Summary of Methods for Steels

1100

Temperature (C)

1000
Boronizing

900
Carbonitriding

Laser & electron beam Carburising

Vac. & Plasma carburising Flame & induction hardening

800 700 600 500 400

Nitrocarburising

Gas Nitriding Plasma Nitriding

Ion Implantation

10

100

1000

10000

Depth (m)
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Steve Roberts - Surface Engineering - Surface Engineering

Coatings - Plating & Anodising

Plating
Typically Cr or Ni on Steel. Hard Chrome / Nickel Typically 10s m to several mm plated (c.f. ~ m for decoration) Cr: 850 - 1250 kgmm-2: Ni: 400 kgmm-2: In electroplating, must take take not to hydrogen-embrittle the steel. Can also electroless plate Ni: Use bath with Ni ions and a reducing agent catalysed on the substrate. Reducing agents contain P and B Ni / P: 500 kgmm-2: Ni / B: 700 kgmm-2: Can also H - embrittle. Can adapt both process to include second phases (e.g. SiC, C, Al2O3) in film. Steve Roberts - Surface Engineering - Surface Engineering

Anodising
Develop thick (hydrated) oxide layer on Al. Can be done for decorative purposes (dyes in the oxide layer) For wear resistance, produce layer 25 150mm thick: Hardness:350 -600 kgmm-2 (v. soft for an oxide) Can only use alloys with low alloying element content (< 5% Cu, 10% Si).

Can impregnate film with PTFE or MoSi2: High(ish) hardness & low friction.

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Hardfacing - Weld Coats

Generally applied to Steels. Coating applied by standard welding methods - Oxy-acteylene, Arc, MIG, TIG, etc. Deposits are typically several mm thick - can be a lot thicker. Typically: Austenitic (Mn) steels Martensitic steels Cast irons contining carbide formers WC / Co

Generally used to apply sacrificial material where rher is high abrasive wear.

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Spraying - Flame Spraying

~100m/s
Air Oxy - Acet. Mixture

Feed

~200C

~2000C (particles)

~3000C (flame)

(Also electric - arc spraying similar)

Oxyactelyene flame melts the wire & heats the particles Additional air is to accelerate the particles. Feed can be: Metal wire Metal tube containing alloying elements or refractory metal powder WC / Co powder Ceramic rod

Can reheat by flame or R.F. to remove porosity in the coating.

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Spraying - Plasma Spraying

Powder ~250 - 500m/s Ar + He / H

+
~200C ~2000C + (particles) ~15 000C (plasma)

High plasma temperature makes it possible to spray ceramics and refractories Inert gas prevents oxidation. Trapped air gives some (1-10%) porosity. Needs good surface preparation (grit blasting) to key coating on. Often use bond-coats (Ni / Al) as intermediate layer if ceramics (typically ZrO2) sprayed.

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Spraying - Vacuum Plasma Spraying

APS ZrO2 8%Y2O3 Thermal barrier layer (porosity aids thermal shock)

Avoids trapped air problems: Low porosity - generally better tribological properties for ceramic coatings.

Can spray Ti and Al based materials - explosive in air. More as new processing route than for surface engineering)

VPS CoNiCrAlY bond coat (Oxidation resistant near fully dense) VPS aluminised layer Ni - superalloy 100m

VPS Unit at Oxford Steve Roberts - Surface Engineering - Surface Engineering 24

Physical Vapour Deposition

Evaporation
Target vacuum Liquid Heat Vapour from source condenses onto target. Only useful for low m.p. coatings - optical films etc. Weak adhesion; can (re)heat target to interdiffuse. Ar ions sputter atoms from source, hit target with few kV - good adhesion. Use of a.c. allows nonconductive source. Can do in reactive gas to deposit nitrides, carbides, oxides.

Sputtering

Ion Plating

0.5 - 5 kV

Target 0.1 - 10Pa Ar glow discharge Solid

Target 1 - 10Pa Ar glow discharge Liquid Heat 0.3 - 3 kV

Evaporated atoms become ionised in plasma, attracted to target. Can do in reactive gas to deposit nitrides, carbides, oxides. e.g. Ti in N2 / Ar to deposit TiN at ~400C onto steels (without affecting temper).

Steve Roberts - Surface Engineering - Surface Engineering

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Chemical Vapour Deposition

Pass reactant gas(es) at low pressure over heated substrate. Reaction occurs on the substrate. Typically: 0.1 - 1m / hr 500-1000C 1 - 10m thick layers Columnar microstructures.

SiC
Many possible reactions: Most common is methyl trichlorosilane (MTS) H2 CH3(SiCl3) ! SiC + 3HCl MTS is toxic, very inflammable but not (like other possibles) explosive on contact with air... < 1200C: amorphous SiC > 1200C: - SiC, with increasing grain size as T increases

TiN / TiC
Peoples Choice for abrasion resistance TiCl4 + N2 + 2H2 ! TiN + 4HCl ! TiC + 4HCl TiCl4 + CH4 TiCl4 + C + 2H2 ! TiC + 4HCl (using C in high C steel or WC / Co) PACVD Use an RF or microwave plasma - brings deposition temperature down to < 500C

Diamond
~ 600C: deposit from methane / H2 / O2 Need microwave plasma so the H can etch away graphite, leave diamond. Narrow band of CH3 : H2 : O2 to get diamond

Steve Roberts - Surface Engineering - Surface Engineering

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Diamond Films

The initial stages of nucleation of diamond on a Ni substrate.

For more information: http://www.tlchm.bris.ac.uk/~paulmay/diamhome.htm

Top & side views of a polycrystalline CVD diamond film grown on a Si substrate. Process gas mixture was 1% methane in H2.

Steve Roberts - Surface Engineering - Surface Engineering

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Steve Roberts - Surface Engineering - Surface Engineering

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