oys to protect against corrosion and wear

Certain nickel or cobalt-chromium aIloys stand up to corrosion and the various types of wear found in processinc plants* Paul Crook and A Asphahani, Cabot Corp. &
Wear of equipment is a major problem in industry. Not only does it mean replacement or repair of components but it often involves substantial and costly downtime. In the chemical process industries (CPI), wear is hastened by mrrosion and by limitations imposed upon lubrication. To minimize w a r , one must look at the causes of wear and at what types of materials work best under various conditions, Before these topics are discussed, let us very briefly cover how various types of alloys perform in preventing wear: The commodity allays-for example, Type 316 stainless steel-have limited resistance to wear. The alternativm to using commodity alloys are either to coat critical components with wear-resistant a1loy-s or to manufacture the components entirely out of these special alloys. Wear-mistant alloys best suited for corrosive environments are based on cobalt and nickel. These alloys are, of course, relatively hard and can be applied by welding as coatings. They are therefore known as hardfacing
materials.

phase that is dispersed throughout a softer metallic matrix--e.g., chromium boride in a Ni-rich matrix. For such alloys, abrasion is more complm, and depends
upon the size, shape and hardness of the abrading species, as well as the hard phase. Contrary to popular belief, abrasion resistance of t h e e alloys is not necessarily related to their overall hardness. A high volume fraction ofthe hard phase and a coarse structure, in fact, generally p r ~ r n o t e abrasion resistance [2].

Metal-to-netat wear
Traditional theory states that adhesion is the cause of metal-ta-metal wear. Such wear, which is caused by the sliding of unlubricated metal surfaces over each other, is often therefore called adhesion. Strong interfacial bonds may occur at deformed surface asperities (surfam high spots), and mechanical degradation results from shear failure of the weaker of the two metal mating surfaces [33. Newer theory postulates another mechanism-that subsurface crack nucleation and growth follow asperity shearing and flattening [4,.5]. Oxide films may protect most metals and alloys h m m~rosion and metal-to-rnetal wear. In sliding systems where oxide films do not break down, true metal-tometal contact never happens. Mild wear occurs at low loads, and is controlled by oxide-film breakdown and repair; its debris is a n oxide.

Then thew are aIloys that are chiefly known for mrmsion resistance, but have moderate resistance to wear. These high-performance alloys include formulations of Ni-Mo, Ni-Cr-Mo, and Ni-Si 111. Now, we will discuss the types of wear: abrasion, metal-to-metal wear, and erosion.

Abrasion
Abrasion is caused by hard particles or protuberanmoving and pushing against a solid surface. Such wear is common in oiI-extraction machinery used in the food-processing industry. T h e abrasion process can be described as plowing (far ductile surfaces) or chipping (for brittle surfaces). Since plowing involves mainIy plastic deformation, the resistance to abrasion of ductile, single-phase materials is closely related to their hardnws. For brittle materials, the fracture characteristics determine the extent OF material removal. Hardfacing materials are typically made up of a hard

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craters that are surrounded by cleavage cracks on brittle surfaces for normal impact. For materials that contain a hard phase-i.e., wearresistant alloys-it is this phase that mntrols impingement by solids. In liquid impingement/cavitation emsion, the softer matrix is most important [ 8 ] .

Methods of protection
Wear-resistant alloys are applied by weIding them to surfaces. Welding technique affects w s t and perfomance. In welding, high deposition rates cause high dilution of the molten weld p o l by the substrate. Thus, large components, which require high deposition rates for reasons of cast, require multilayer deposits. PIasma-transferred arc welding offers the best balance of deposition rate and dilution. This method allows for the use of preallayed powder consumabEes with mechanized welding systems specifically designed for hardfacing (see Fig. 2). Wear-resistant alloys have limited ductility and aw rarely made into structural components. Usually, cast, powder-metallurgy or wrought limited-size parts are inserted at critical points in a process. For example, cast or powder-metallurgy valve-seat inserzs are brazed into valve bodies, and wrought mbalt-based alloys are used as cutting edges in the pIastics processing industry.
Automated hardfacing machine a t work on a seat valve

Fig. 2

Cobalt-base alloys
The first Co-rich wear alloys were developed a t the turn of the century by Elwood Haynes [g]. Experimenting with cobalt and chromium, he discovered that binary alloys containing more than about 10%Cr had excellent resistance to oxidation and corrosion plus outstanding hardness at elevated temperatures i about o 1,OOOC(1 ,800F). Tungsten and molybdenum were added to increase streng-th. The Co-Cr alloys used today are similar to those designed by Haynes (see Table I). The alloys listed in the table wntain carbon, which promotes the formation of Cr-rich carbides during solidification. These alloys differ by carbon level, hence, by carbide volume-fraction. The best protection from abrasion is p r o v i d d by aIIoys having a high percentaKe of carbides and by those hardfacing techniques {or parameters) that promote a coarse carbide grain-structure [ 2 ] . The properties that distinguish Co-Cralloys from all other hardfacing materials are their outstanding resistance to liquid impingement and cavitation erosion, and

Severe wear is characterized by rnetaIlic debris at higher Ioads. Gross damage is termed galling. For wear alloys, the softer matrix seems to be most important in controlling metal-to-metal wear [6,7].

Erosion may be caused by solid particles or by a liquid, which may cause cavitation erosion or impingement erosion (see Fig. f ). Cavitation can take place wherever there are high-pressure turbulent fluids. Liquid-impingement erosion and cavitation erosion are closely related Cavitation is the formation and collapse of bubbles within a liquid. When the bubbles collapse, liquid jets arise from implosion to damage surface. The response of a surface to solid particles-whether they are in a gas or a l i q u i d 4 e p e n d s on the nature and momentum of the particIes, as well as their angle of attack. Particles result in craters on'ductile surfam, and

Erosion

Nominal composition of prime oobalt-chromium alloys, and typical processing applications

% by weight
Co

Table l

Alloy

American Welding Soc. rod { R ) dmignetion

Typical hardfacine Mo

Cr

W
13 4.5 8.5

Alloy Alloy Alloy Alloy

No. 1

No. 6 No. 12 No. 21 *

R CD Cr-C R Ce Cr-A R Co Cr-B

Bal.

Bal.
Bal. Eal.

31 28

C
2.45 1.0 1.5 0.25

applications

Screw components. pump ateevcs Vaive, pump and screw components

Cutting edges Valw s a t s

30
27

5.5

'Aerospace Matarial Speclf rcation AMS 5385b

CHEMICAI. ENGINEFRINC;JANUARY 10, 1W1

-Nominal composition of nickel-base hardfacing a l l o y ~ They are for mildly aggressive applications

>

Table I I

Alloy

American Welding Soc. rod (R) designation

R Ni Cr-B R Ni Cr-C

$6 by w i g h t

Typicnl hnrdfacing

Ni
Bal.
Bal.

Cr

Si
4 4

B 2.5

Fe 4
4

applications

Alloy No. 50 Alloy No. 60

12
15

35 .

0.45 0.75

Cutting edges le.g., pulp knives)

Pump parts and pipe elbows

CO-CKwear alloys generally offer superior corrosion resistance, compared to the Ni-based formulations
Gas-tungstenarcdeposits

Table 1!t

Acetic acid

Formic acid

Nitric acid

Phosphoric acid

Sulfuric
acid

Alloy

Concentration and tempemtur%

309C
boiling

80% boiling

S5%, 150' F (6t3OcI

60%. 1 5 0 ' ~
(6s"CE
E E

5%. 1 5 0 & ~

1~6"~) E
E E E

Alloy Alloy Alloy Alloy

No. 1 No. 6 No. 12 No. 21

G
E G

E
E

5 U

E
E
U U

E
U U

Alloy No. 50 Alloy No. 60 Ni-17Cr-17Mo-6Fe-SW

s
G
E

u
U
E

Note. Five 24-h t e s t periods. beterrnlned in laboratory tests. I t Is recommended that samples be r m e d under ncruat p l a n t conditions.

Code: E Las than 5 rnilslyr (rnpy) (<0.13 rnrnlyr) G 5 rnpy (0.13 mrnlyr) to 20 mpy (0.51 mmlyr) S Over 20 rnpy (>0.51 rnrnlyr) t o 50 rnpy (1 .ZJ mrnlyr) U More than 50 rnpy (>V .27 rnrnlyrl

their excellent self-mated antigalling behavior. Both features are due to the same matrix characteristics-an extremely low stacking-fault energy (a property of the atomic structure that influences deformation behavior) and a tendency to transform or "twin" u n d a stress [7,8,10,1 I]. (Time transformation is from n face-centered cubic to a hexagonal close-packed structure.)

Flanges that have been hardfaced w ~ t h allay No. 60 in bore and alloy 6 in sealing face

It is not we11 understood how the above properties affect the behavior of the alloys to mechanical degradation. Planar slip of the structure daring deformation and twinning tendencies, however, may restrict crack initiation and propagation [5,10,IZ]. OF the hardfacing alloys, the Co-Cr ones respond best to welding. They are readily deposited by arc processes, and are typically applied to components, by means of the oxyacetylene p&cess (with a 3 x flame). Manv allow have been derived fmm the CD-Crmixturm for specific uses and to conserve cobalt, which has periodically been scarce and expensive. Among the alloys designed to conserve cobalt are those containing cobalt-iron-chromium, which have many af the propeAes as do the Co-Cralloys [13]. The iron-containing alloys have relatively high amounts of molybdenum to compensate for the increase in matrix stacking-fault-enerKybrought about by the partial replacement of C o by Fe. Also, there are alloys that, during solidification, form hard metallic compounds rather than hard carbides. Two such are Tribaloy * T-400 (8.5Cr-28.5Mo-2.6% balance Co} and Tribaloy T-800 (17.5Cr-28.5Mo3.45-bal. Co). The high Mo and Si levels help to form the hard metallic phase. T-800 has a higher chromium content and resists corrosion better.

same

Fig.

*Tribaloy is a registered trademark o l Csbat Corp.

CHEMIC4I. FNFIFEERTNC JANUARY 10, 1!H>

such material is 60% (wt.) tungsten carbide and 40% Ni-Mo alloy.

Ni-base high-performance alloys

These alloys, as mentioned earlier, are designed primarily for corrosion resistance, not for wear-although they do have moderately good wear resistance. The Ni-Mo alloys are typically used in reducing environments; the Ni-Cr-Mo alloys are used in oxidizing and reducing media. The Ni-Si alloys have excellent resistance to sulfuric acid at nearly all concentrations and

temperatures,

Applications
In the CpI. wear and its mechanisms are varied. and
it is difficult to generalize about when specific materials should be used. Therefore, it is hard to precisely measure the economic advantages of using wear-resistant alloys. However, some typidal applications are: Co-Cr alloys Nos. 6 and 12 have been used to protect the teeth and fliqhts of screw-type mixers (see Fig. 4). These alloys are also used as valve-trim materials, par-

Teeth of this mixer are protected with Alloy No. 12: the flight has Alloy No. 6

Fig. 4

~ickel-base hardfacing alloys

Of the Ni-rich alloys designed to resist wear, the most widely used are those containing Ni-Cr-Si-B (Table 11). Compared with the Co-Cr alloys, these only moderately resist corrosion, and are therefore used i mildly aggresn sive environments (Table 111). Carbon steel flanges that are hardfaced with Alloy No. 60 (and also Alloy No. 6) are shown in Fig. 3. These alloys have a complex microstructure, which is described in Ref. [ I # ] . However, they essentially contain a high volume of boridc-which imparts excellent resistance to abrasion-in a Ni-rich matrix. Si and 3 affect welding characteristics: The molten weld pool is highly fluid and these alleys are self-fluxing during gas welding-hallmarks of this claqs of alloys. To conserve mbalt, attempts have been made to develop Ni-Cr equivalents to the Co-Cr alloys. However, such alloys lack sufficient resistance to galling and cavitation erosion. Their abrasion resistance is equivalent to the Co-Cr alloys. The Ni-Cr alloys have better mmsion resistance than do the Ni-Cr-Si-B alloys. Rather than relying on hard-phase formation during solidification of the alloys, it is possible to protect surfaces by using composite welding consumables. O n e

ticularly for handling petroleum products. Alloy NO. 3 is used in proportioning pumps. Co-CraIloys are used in the pulp and paper industry for spray nozzles, defiberizing-unit blades and agitator-shaft sleeves. The hiih-performance Ni-base corrosion-resistant alloys are used for wear and corrosion, when corrosion is the main problem. Applications include valves and pumps-here the alloy I GCr-16Mo-4W-bal.Ni is eften used.

".

References
1. Asphahani, A. I , and H o d g ~ ,F .

Riclamd G r a m , Editor

G., "Proceedings, Alloys for the 8 0 ~ : Ctimax Molrbendurn Co. symposium, p 329, 1980 2. S~lence,W. L., J O J I . J L JTmllllldo~, KIC~~ Vo1. 100,NR 3, 1978, p. 428 3. Rabinowicz, E, ''Friction and Wear or Material&" John wlcy br Sons, New York, 1965. 4. Suh, N. P., Wtm, Vol. 25, 1073, p 111. 5. Rignry, D. A,, and Glaescr, W. A , "Wcar of Materials-1977," Amer Soc of Mechanical Enginms, p, 41. 6. Bhansali, K, " W a r of Materials-1979," ASME, p. 146. J., 7 Bhanmli, K J , and Mllltr, A. E., "Wear of Material+lSBl,* A S m , p. 179. 8. h t o n y , K. C., and S i l c n W L , " P m Fifth Intl Conf. on Emion by ~ Liquid and Solid Impact," Cambridge Unrvcmlty h a , 3979, p. 67 1. 9. Gray, R D., AHisror)l of the Hrynes Stellitc C o ,Cabot Corp. pub., p 18. 1 . Woodford, D A,, M~~llarrgrcol 0 . Trm~~tirns, V01 3, p I I 37. T 972 11. Hrathcock, 6. J., et at., 'Wcar of Materials-lX1,'' ASME, p 597. 12 Rcrny, L., and P i m u , A,, MOW& S c h w mul EngincmiR& Vol. 26, 197& p. 123. I 3 Crook, P., "Wcar o f Matdals-TSal," ASME, p. 202. 14. Knotck, 0 and Lugschtidcr, E., W~ldmg , Rcsrmh S u f l l m l , Oct. 1976, p. 314,

The authors --Paul C

ass&atc

Cabot Gorp.. 1020 Wcrt g r k A v t , Kokomo, IN 46901. Tel: (317) 4566241

H e 1 a m e m h o the firrn's Wear s f Group, and hr? mponsibilltim am design and tmting OF war-m~stant mattnals C m k holds mctalluw and

d is scnior enginming In the Technolo Dcpt, o f

Aziz Asphahani is director of the Technology a p t . at Cabot Corp., 1020 \.Vest Park Avc., Kekomo, I 46901. N Tcl: (31 7) 456-6230. He joinal Cabnt in

physim d-

(including a Phb.)f o rm

thc Uniwrsi~y Manchuta (England), at m d i s a m t m k ol the h e r . SK. for Mctsls and tht Amtr, Soc. for %ring and Materials.

1975, upon completion of his doctoral work at M,I,T, 1Ic serves as chairman of the Natl. Asn. of C m i o n Enginerrs (N?\CE] Comm~tteeT-3E (Stress C o r m i o n CrachnlZ). and 1 a member s or tht NACL S t r a t c ~ r Planning Comm!ttcc. He i s also active in the
Matmals Trchnology Inst. as manager of the Comsion Bnginccrin Section

and

a4

a rncrnbcr of the '~ec$lnical

A d v i s q Council.

CHEMICAL ENCIIU6ERING JAh'llAKY 10, l9aI