NBS

if publications

Nb^iK /4-615

NATL INST. OF STAND &

Codeposition of Wear-Resistant

Particles Chromium & TECH /-

AlllDti MMTMDb

juiiii r. YOung

Corrosion and Electrodepositlon Section

Metallurgy Division

Institute for Materials Research

National Bureau of Standards

Washington. D. C. 20234

November 1974

Final Report

Prepared for Research Directorate

Weapons Laboratory

Rock Island Arsenal

Rock island, Illinois 61201

100

.U56

74-615

1974

NBSIR 74-615

CODEPOSITION OF WEAR-RESISTANT

PARTICLES OF CHROMIUM

John P. Young

Corrosion and Electrodeposition Section

Metallurgy Division

Institute for Materials Research

National Bureau of Standards

Washington D. C. 20234

November 1974

Final Report

Prepared for Research Directorate

Weapons Laboratory

Rock Island Arsenal

Rock Island Illinois 61201

mm »

U S. DEPARTMENT OF COMMERCE. Frederick B. Dent, Secretary

.NATIONAL BUREAU OF STANDARDS. Richard W. Roberts. Director

TABLE OF CONTENTS

Abstract

Objective

Introduction

Experimental Equipment

Procedure

Tests and Results

. Initial Experiments

Bornhauser Bath

Codeposition of Metal Powders

Vertical Cathodes

Codeposition of Diamond Powder

Sellable Additives

Effect of Particle Concentration

Controlling Thallium Ion Concentration

Plating Conditions and Thallium Concentration

Various Types of Particles

Various Bath Additives

Steel as Basis Metal

Lubricating Particles

Various Hard Particles

Bath Life Test

Corrosion Protective Deposits with Hard Particles

Cadmium 29

Zinc 30

Gun Tube 31

Heat Treated Deposits 32

Reactions of Thallium Nitrate 34

Discussion 34

Conclusions 42

References

Bibliography

Page

1

3

4

6

8

9

10,22

12

14

15

16

18

20

21,28

23

23

24

26

ABSTRACT

Efforts to include particles in deposits from standard chromium

baths over a wide range of plating conditions were futile. Inclusion

of particles was achieved only by adding any of a number of monovalent

cations to the chromium bath such as Tl, Ce, Na, NH, Li. Under the

plating conditions developed all particles that were added to the bath

were included from a few tenths to 5 wt.% in chromium deposit without

excessive loss of properties. Particles included were diamond, borides

carbides, nitrides, oxides, metals, graphite, and a sulfide. The more

conductive materials were more easily included. A bath-life test using

additives and particles was run for thousands of ampere-hours per liter

of solution with good bath performance. Wear tests of deposits having

included particles indicated improved wear-resistance. A caliber 0.30

tube was plated with chromitim having included particles which had good

particle distribution throughout the bore. Deposits of cadmium and

zinc with included hard particles showed improvement in wear-resistance

OBJECTIVE

The experiments described in this report were intended to improve

the wear-resistance of deposited coatings, mainly chromium, by incorporating hard particles in the deposits and determining the wear-resistance and other properties of such coatings and to develop a practical

bath and set of operating conditions whereby the inclusion of particles

in chromium could be accomplished on a more or less production basis.

CODEPOSITION OF WEAR-RESISTANT PARTICLES WITH CHROMIUM

INTRODUCTION

A search of the literature revealed that electrodeposited composite coatings with a metal (usually nickel) matrix and dispersed

particles have been used for wear-resistance, anti-friction, and

dispersion hardening. The characteristics of the usual electrolytes

for plating hard chromium, however, make the deposition of inclusions in chromium coatings difficult. The low efficiency of the

baths results in copious evolution of hydrogen causing vigorous agitation of the solution at the cathode surface. The consequent slow

rate of deposition further reduces the chance of retaining particles

in the chromium deposit. Maximum hardness and current efficiency

are primarily a function of electrolyte composition, bath temperature,

and current density. It has already been determined '• that higher

current efficiency is obtained at lower chromic acid concentrations

in the sulfate-catalyst bath. The surface concentration also affects

efficiency with the optimum chromic acid-sulfuric acid ratio being

in the range of 70 to 100 to 1. The bviild-up of trivalent chromium

over 5 or 10 g/1 in the bath likewise reduces efficiency because of

increased resistance in the solution.

The hardness of the chromium deposits is fortunately greatest

at lower concentrations of chromic acid, trivalent chromium and acid

catalyst. Unfortunately, non-soluble, hard particles added to the

bath coxild not be codeposited at these optimum conditions. The particles tried were smaller than 25 um and consisted of, oxides of

aluminum and titanium, silicon carbide and later, diamond dust. A

variation of the sulfate bath, the Bornhauser bath^, containing

sodivim hydroxide, gives deposits which are quite dull and soft by

hard chromium standards but did allow codeposition of particles.

Investigation has shown that soluble additives, both inorganic

and organic, can enhance the hardness and wear resistance, as well

as the brightness of chromium deposits'^. The most effective of these

additives was tried and, although it did slightly enhance the properties of the deposit, it did not promote the inclusion of particles.

-1-
Work done on the codeposition of particles in the copper sulfate

bath^, which, like the chromium bath, is highly acidic, showed that

bath-soluble salts of monovalent cations permitted extensive codeposition of bath-insoluble particles. The most effective of these

were thallium salts at a concentration of 5 to 10 g/1. The addition

of thallium was tried in the hard chromium plating bath and resulted

in the codeposition of hard particles in the chromium matrix. The

wear resistance of some of these composite chromium coatings was

substantially improved over the best of the standard bright, hard

chromium deposits. Powdered metals were also codeposited with chromium with the possibility of forming chromium alloys by heat-treating

the coatings. In nearly all cases, the codeposited particles amounted

to less than five percent by weight of the chromium deposit. In

cases where particle content of much more than 5% occurred, the

properties of the chromim deposit were seriously degraded. Other

types of particles tried included boron nitride, zirconium silicate,

two sizes of aluminum oxide and fumed aluminum oxide and silica.

Other monovalent cations, besides thallium, that were used included

salts of cesium, lithium, sodium, and ammonia. All of the particles were included in chromixim to a greater or lesser extent and all

of the additives tried were more or less successful in the incorporation

of particles in the deposits. Particles included in deposits on vertical

surfaces tended to average somewhat smaller in size and to be slightly

less niuEerous than in deposits on horizontal surfaces under similar conditions. In general, it was found that for best wear resistance, a minimum amount of additive should be used, particle concentration of over

60 g/1 was of little or no benefit, plating conditions about 55" and

50 asd usually resulted in fewer inclusions with the most effective range

40*720 asd to 45 "/SO asd. Wear was not directly proportional to hardness

or the amount of inclusion. Good wear resistance required a continuous

chromium matrix with well distributed hard particles. Diamond particles

resulted in the best wearing properties with aluminum oxide generally

the lowest in wear resistance, although the latter was more easily incorporated than most particles tried.

The main objective of some experiments was the development of a
practical bath and procedure for the incorporation of hard particles

in chromium on a more or less production basis, A bath-life test was

run to determine the effect of additives and particles on the longevity

of the chromium plating bath. Ammonium nitrate was effective as an

additive in the chromium bath-life test and only after several thousand

ampere-hours per liter of bath did deterioration of the bath begin as evidenced by the decreased wear-resistance of the deposits. As a practical experiment, a gun tube was plated with chromium incorporating

hard particles. In addition to chromium, deposits of cadmium and zinc

were made which included hard particles in cyanide baths <> Test deposits

were made on vertical cathodes of copper or steel and were heat-treated

after deposition to check the effects of heating on wear, adhesion, and

structure of the deposit. Particles were included in the cadmium and

zinc deposits without additives although addition of thalliimi salts to

the zinc bath increased the amount of particles included.

EXPERIMENTAL-EQUIPMENT

The specimens were prepared in a one liter vessel immersed in a water bath for temperature control. The bath was heated by a radiant

heater and cooled during high current density rxins by chilled water

running through a coil immersed in the water bath. The anodes were

formed from lead sheet to conform roughly to three types of cathodes

used. The first type was made from stainless steel and "L" shaped

to present both vertical and horizontal areas for deposition. For

maximum viniformity of deposition, a one-quarter inch diameter copper

rod was made concentric vertically with a cylindrical lead anode.

Neither of these cathode configurations was suitable for abrasion

testing, so for most of the tests (unless otherwise stated) a circular, flat cathode of 25-30 mil thick copper sheet was used. It

roughly fitted the diameter of the plating vessel and was initially

suspended horizontally near the bottom of the vessel. The perforated

lead anode was positioned about one inch from the cathode and parallel

to it whether in the horizontal or vertical position.

The electrolyte was agitated by a magnetic stirrer with the

stirring magnet beneath the cathode and by an air tube immersed to

about the level of the anode. Continuous stirring was necessary to

maintain uniform temperature of the electrolyte and keep the parti-

-3-
cles in suspension. A cover prevented excessive loss by spray and

evaporation and supported the air line, as well as a thermometer

and the anode (Fig. 1). Current was supplied by full wave, rectifiers with bridge type circuits for minimum ripple. . The circular cathode fitted the Tabor Abraser unit used to test

the plated chromium coating for wear resistance. Abrasive wheels

used for most of the tests were of the rubber bonded abrasive type

(CS-17) . Hard vitrified abrasive wheels (H-10) were used for some

comparative testing but mostly to prepare a smooth, uniform surface

on the specimens to obtain comparative results with the rubber

bonded wheels (Fig. 2). Cross-sections were prepared, using standard

specimen plastic mounting and polishing equipment, for hardness

measurements and photomicrographs. Hardness of cross-sections of

the specimens was measured on a Wilson microhardness tester with

readings in Knoop Hardness Numbers. Visual microscope examination

and photographs were made on a Bausch and Lomb research metallograph.

Some early specimens were examined on a Steroscan scanning electron

microscope with attached Princeton Gamatic nondispersive spectrometer.

PROCEDURE

The specimen cathodes were prepared by applying an insulating

stop-off lacquer to areas not to be plated, the side away from the • anode and edges . The surface was then scrubbed with fine pumice

and/or dipped in hydrochloric acid solution to remove oxide films

from copper.

The electrolyte was made up according to the composition desired

and heated before introducing the specimens . Particles which were

very fine and showed a tendency to agglomerate were dispersed in

water by a high-speed blender before addition to the electrolyte.

The bath was then vigorously agitated with the magnetic stirrer,

while heating, to keep the particles in suspension. When the desired

temperature was reached, the cathode and anode attached as a unit

to a cover were lowered into the bath, the rectifier leads attached

and plating commenced. Additions to the electrolyte, such as thallium nitrate were then made after dissolution in water. There was

evidence that some of the additives were made ineffective by contact

with the strongly oxidizing chromic acid solution, so in addition
to being added after deposition started, some, especially thallium,

were added in increments during the usual four-hour run. After plating, specimens were measured by micrometer for deposit

thickness and checked visually. Those to be tested for wearresistance were smoothed mechanically with abrasive paper if the

surface was other than very smooth. It was found to be very important to have the surfaces of all specimens to be wear-tested as uniformly smooth as possible to obtain consistent and comparable

results. To this end the specimens were "worn-in" on the wear tester

for several thousand revolutions, using the hard vitreous bonded

wheel, if necessary, and the rubber bonded wheel before the actual

wear test was made (fig. 2) . Since the wear-test was the one most

important test for evaluating the deposits, it was done very carefully. Thickness of the deposits was such that the wear-test could

be repeated if desirable. The test consisted of 10,000 revolutions

of the specimen under the two abrasive wheels of the abrader with a weight of 450 grams on the surface of the specimen at the point of

impingement of each wheel. A magnification of the surface of an abraded chromium deposit containing inclusions is shown in Figure 3.

Before each test a fresh surface was obtained on the abrasive wheels

by rxinning them on abrasive paper. Most of the later specimens were

subjected to an additional test and then checked against the

first run. If a lower value was obtained the specimen was deemed

to not have been sufficiently prepared initially and the lower

reading was used. Wear was determined by weight loss of the specimen to a tenth of a milligram. On completion of the wear-test the

3 3/4 inch diameter specimen was cut in half. The deposit was dissolved in HCl from one-half of the specimen. Inclusions in the

resulting chromium chloride solution were filtered out, dried and

weighed to determine the percent of particles included, A small

section from the edge of the specimen was mounted in plastic for

microscopic examination and hardness measurements. Photographs were

made of the cross-sections of specimens which appeared to be of

interest, such as those containing voids, particles, unusual grain

structure, etc.

-5-
TESTS A>:D R£5UL75

Initial Experir.encs

The initial part of the work consisted of tr^'ing a vide range

of plating conditions and chroniiu.-:: plating bath concentrations in

an effort to include particles in the deposit. It had first neen

determined that particles could be deposited in a nickel r.atrix froni

the nickel bath without difficulty. Chroaium bath conposition and

plating conditions were varied as follows:

Or03 - 125 to 550 g/1

Cr03:H2S0i, - 100:0.5 to 100:1

Current density - 20 to 100 asd (with and w/o superposed AC on some tests)

Temperature - A8 to SO'C

With and w/o mechanical and/or air agitation of bath

Cathode-vertical and horizontal

In addition to the above variations, such procedures as stopping

deposition periodically to allow particles to settle oa the cathode

and periodically reversing the current for a short period were tried.

-6-
None of these bath concentrations or plating conditions resulted in

significant deposition of particles on vertical or horizontal surfaces. What were thought at first to be inclusions in the chromium

deposit on examination of the cross-sections of the deposits were

'later decided to be voids in the chromium or possibly inclusion of

other material, such as oxides of chromium, lead peroxide or lead

chromate from the anode (Fig. 4), because of negative analytical

results for the intended inclusions.

The next approach was to try additions of monovalent cations which

in the highly acidic copper sulfate bath had been found to enhance

the codeposition of fine bath-insoluble inorganic particles^. Therefore, thallium compounds were tried in the chromium bath, although

thallium chromate precipitates quantitatively fron chronium solutions.

Thallium chloride was first used, as it was available. It formed

thallivun chromate in the bath and apparent voids were formed in the

deposits similar to those in figure 4. Thallium sulfate was avoided

to prevent distortion of the critical sulfate ratio in the chromium

bath. Thallium nitrate salts were then obtained and used as the

addition to furnish the thallium ion. The salt was added as a water

solution but most of it was precipitated as thallium chromate and

only about 0.2 g/1 was soluble in the bath. This is likely a factor

in the small amount of material included during codeposition from

the chromium bath without formation of voids or excessively rough

deposits.

Early tests using 5-10 g/1 thallium were disappointing because

of the deleterious effects on the properties of the chromium

deposits, mainly the reduction of hardness, and the small amount,

usually less than 0.5%, of particles included in the deposits.

Later, more effective current density-temperature conditions and

thallium concentrations were found and the performance of deposits

from baths containing thallium improved.

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Bomhauser Bath

It had been thought that the acidity of the chromium bath

inhibited the effect of the thallium. Work by Tomaszewski , et al^,

indicated that higher pH and Na"*" ions favored codeposition of particles. This inforamtion suggested a chromium bath with a higher pH

commonly known as the Bomhauser bath. The composition of the bath

was as follows: •

Cr03 - 400 g/1

H2S0^ - 0.8

NaOH - 58

Since the main difference between the standard bath and the

Bornhauser bath was the sodium hydroxide content, this was added in

increments to a standard bath to determine the affect of increasing

pH. Runs were made at 10, 20, 40 and 60 g/1 NaOH plus 20 g/1 silicon

carbide powder at 60°/40 asd with no thallium. No appreciable effect

was noted until the NaOH concentration was 60 g/1, as shown below:

NaOH Inclusions in Cr Hardness Wear Loss

10 g/1 0.13 wt. % SiC 882 9.1 mg

20 0 1005 9.4

40 0.03 1021 8.3

60 10.0 243 7029.2

0 0 (no SiC in bath) 935 5.6

At first it was thought that the action of the thallium in codepositing was enhanced by the Bomhauser bath, but it was later

found that the increase in included material was related to the

spongy nature of the deposit formed when non-soluble powders were

introduced to the bath (Fig. 5). Actually, the higher the concentration of thallium ion the lower the amount of particle codeposition.

This is opposite to the effect found in the standard hard chromium

bath (Fig. 6). The performance of coatings from the Bornhauser bath,

despite the high particle content, was disappointing. The deposits

-8-
were soft and the higher the percentage of inclusions the more

porous and granular the deposits became, until coherence was lost.

At 19% silicon carbide thv. deposit was too ^''^^^'^ to pormit a wear test. At 10% silicon carbide the wear was an exhorbiLant

7.03 grams and the hardness only 243 KHN200' With no particles in

the bath the wear was 0.0246 g and the hardness 460 KHN2co- Although

later tests with the Cr03 content of the bath under better control

gave somewhat harder deposits, the deposits from the Bornhauser bath

were usually too soft to have good wear resistance despite included

hard particles. With a low (5 g/l) concentration of particles in the

bath the addition of thallium to the Bornhauser bath seemed to improve

the hardness and thus the wear resistance of the deposits having

comparable amounts of inclusions, as shown by the following summary

of test results:

TINO3 Inclusions Hardness Wear Loss

0 g/l 0.79 wt. % 367KHN200 36.3 mg

5 1.15 580 25.4

10 0.69 655 6.9

0 1,63 343 34.2

Codeposition of Metal Powders

The Bornhauser bath was used successfully for the codeposition

of several metal powders in chromium. At 60**/40 asd using 5 g/l

TINO3, 8% tungsten powder was included in a deposit on a horizontal

cathode, but the hardness of the composite was only 157 KHN200 ^^"^ the wear loss a high 0.29 gram. On vertical cathodes the amount of

inclusions were less, but deposit properties were better. For

example, at 60*/40 asd and with 10 g/l tungsten powder in the bath

the deposit hardness was 761 KHN200 with 1.7% included materials.

The same conditions plus 5 g/l TINO3 gave a deposit hardness of

299 KHN200 snd 0.2% metal powder included for tungsten and 735 KHN200

and 0.05% inclusions for nickel. These results with TINO3 using a vertical cathode in the Bornhauser bath are more in line with results

-9-
under similar conditions wich SiC particles and a horizontal cathode

where TINO3 adversely affects codeposition than are the results mentioned above for metal powders on a horizontal cathod plus TINO3

.

The standard 400 g/1 Cr03 , 4 g/1 H2SO4 bath plus 5 g/1 TIXO3

was also used to deposit metal powders with the results shown below:

Metal Pwder. Cath. .TING 3 Included Hardness Wear Loss

10 g/1 Ni Hor. 5 g/1 4.6 wt. % 373 kh:;2oo 46.4 mg

10 Her. 0 0.14 479 15.0

10 Vert. 0 0.06 536

10 Vert. 5 0.04 250

5 g/1 Ti Hor. 5 1.4 788 52.0

10 g/1 W Hor. 5 0.3 511 11.3

It is seen that some metal powder is deposited with chromium on both

vertical and horizontal surfaces; that thallium enhanced the inclusion of nickel on a horizontal surface, but was ineffective on a vertical surface.

Vertical Cathodes

In addition to the tests using a vertical cathode described

above, a series of tests- were made to decrease the effects of uneven

current density on the codeposition of particles in several baths

under varying conditions and determine the effect of bath temperature on codeposition. The cathode was a 1/4 inch diameter copper

rod and the anode a concentric cylinder of lead sheet. The bath

was agitated during plating by air and magnetic stirrer.

Despite, the careful arrangement of the electrodes in the bath,

there was some difference in the deposits between the bottom,

center and top. Cross-sections of the three locations showed more

inclusions and/or voids at the bottom and center than at the top of

some of the deposits with variations in structure when thallium was

used. Results of the tests of effects of various temperatures at

100 asd in the 400 g/1 Cr03 standard bath are given below:

-10-
icIUp . Hardness (KliN'2 oo)

in Cr Ton pp n r p T Du u L urn

/. ^ nU 531 423 536

55 0 361 322 456 .305 0 —

55 5 g/1 654 761 772 429 100 g/1 Ti02 1.2 wt.%

*55 0 262 292. 328 266 0

65 0 622 685 659 641 0

65

*

10 966 925 971 1003 100 Pos. for Ti

Small (lOw) superposed AC current during deposition.

Data from various runs on vertical cathodes usually made in

connection with runs on horizontal cathodes using electrodes bent 90'

in the 400 g/1 standard and Bomhauser baths are shown below:

Temp/CD TING 3 Agitation Particles Hardness Inclusion

in Cr

60*/40 0 Air 10 g/1 Ni pwdr. 536 0.06 wt.%

60V40 5 g/1 Air 10 g/1 Ni pwdr. 250 0.04

60*/40 5 . Air + 5 g/1 dia. 605 1.7

stirrer pwdr.

60*/80 5 a+SiWiiOi+o Air + 5 g/1 Ni-dia. 556 0,05

stirrer pwdr.

60*/40 0 Air 10 g/1 Ni pwdr. 329 0.3

*60V40 5 Air + 10 g/1 W pwdr. 299 0.2

stirrer

*60*/40 (residual) Air + 10 g/1 W pwdr. 761 1.7

stirrer

*60*/40 5 Air 10 g/1 Ni pwdr. 250 0.04

Runs 2 and 3, as well as 5 and 7, indicate the critical effect of

stirring of the bath on a vertical deposit. The adverse effects of

thallium in the Bomhauser bath holds for the vertical cathode, as well as for the horizontal cathode which is demonstrated by the last

four runs.

-11-
Codeposition of Diamond Powder

Having had some success with the codeposition of several readily

available nonconducting powders, a selection of diamond powders was

obtained for further experiments. The size of the particles were

1-5 ym, 6-10 ym (Fig. 7) and 10-22 urn. The last was nickel coated

and the smallest size (nominally 15 m) that was obtainable from

General Electric Company through the Van Itallie Company. The

uncoated diamond particles were tried first, then five grams of the

6-10 size were nickel coated in an electroless nickel bath before

using in the chromium bath. From our experience with the metal

powders it seemed that nickel coating non-conducting diamond particles would increase the percentage codeposited. Runs were made

without nickel coating the 1-5 um size particles, with and- without

nickel coating the particles of the 6-10 um size and only nickel

coated 15 pm particles. Other tests made with baths containing

diamond powder included variations of thallium ion concentration and

current density-temperature combinations and use of the Bomhauser

bath mentioned previously.

The effect of thallium ions on the inclusions of 6-10 um diamond

particles was proportional to the concentration of thallium. Tests

included 2 to 10 g/1 TINO3. Results are shown in figure 8. Varying

current density and holding bath temperature at 60 "C and with 5 g/1

TINO3 and 5 g/1 diamond powder, gave the results shown in figure 9

for the amount of inclusions obtained in both the Bomhauser and

standard baths. A heavily etched, nodular chromium deposit surface

with imbedded diamond particles is shown in figure 10,

Several tests were run with and without nickel coating on the

diamond particles. The amount of inclusions was definitely increased

by nickel coating using a number of plating conditions. Twelve runs with uncoated particles averaged 0.45 wt.% diamond inclusions in the

chromium deposits while ten runs with Ni coated particles averaged

1.19 wt.% with some overlapping of data. Segregating tiie results

obtained from three sizes of diamond particles and the nickel coated

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particles used in several tests gave the values shown in figure 11,

which are an average of several runs of each type. The fact that

the nickel coated 11-22 um size shows more than twice the amount of

included particles of the 6-10 um size may be due in part to the

quality of the nickel coating rather than purely an effect of the

size.

A comparison of the deposits from the standard 400 g/1 Cr03 bath

and the Bornhauser bath is shown below: (More data on deposits with

diamond powder are given in the section on thallium ion concentration

Bath Cond. Dia. Pwdr. TINO3 Included Hardness Wear

(5-10 g/1) wt.% KHN200 Loss

Std. 60V40 6-10 Mm 5 g/1 0.17 875 69.3 m

Std. 60V40 6-10 ym 5 1.56 592 12.2

Bomh. 60V40

(mag.

6-10 um ^ stirrer only)

5 0.26 598 78,1

Bomh, 60*/40 6-10 um 5 1.15 580 25.4

Std. 60V40 6-10 um + Ni 5 0.12 639 16.9

Std. 60''/40 6-10 um + Ni 10 3.35 595 14.3

Bomh. 60*/40 6-10 um + Ni 10 0.69 655 6.9

Bomh. 60''/40 6-10 um + Ni residual 0.79 367 36.3

Bomh. 60V60 6-10 um + Ni 5 0.64 10.4

Bomh. 60V80 6-10 um + Ni 5 0.55 652 18.0

Std. 60V60 6-10 um + Ni 5 0.08 407 18.2

All other runs with air plus stirrer.

This series of tests does not show much difference between the

standard and the Bornhauser baths in the amount of included particles

obtained. However, the effect of higher thallium ion concentration

Is more pronounced in the standard bath. The Bornhauser bath appears

less sensitive to current density variations which could be important

when plating a service item. The deposit from the Bornhauser bath

with 10 g/1 TING shows surprisingly good wear resistance and may

result from a hardening effect that can occur with a relatively low

concentration of particles in the bath. This effect was noted in a

-13-
deposit from the standard bath plated at high current (100 asd) . A

striking difference in the appearance of cross-sections is noted in

figure 12 between deposits with (b) and without (a) 5 g/1 TINO3 in

the bath under otherwise similar conditions. The diamond inclusions

in B averaged about 1.6 wt.% of the chromium.

A test was made of the effect of variation of the current density

on inclusions from a standard 200 g/1 Cr03 bath at 55*0 plus 1 g/1

TINO3 and 18 g/1 of 15 ym, nickel-coated diamond powder. Figure 13

shows the resulting wear loss (the values at 50 asd were the best

obtained thus far) and hardness of the deposits. The weight percent

of inclusions in the chromium deposit ranged from 0.39 for 40 asd

to 1.32 for 60 asd.

Soluble Additives ; . The data obtained up to this point in the work indicated that

hardness of the chromium matrix in' which the particles are deposited

was an important factor in the wear properties. Since the use of

thallium and the inclusion of particles almost invariably reduced

the hardness of a chromium deposit, including those with excellent

wear resistance, soluble additions to the electrolyte were tried

which had been reported to have hardened and increased the wear

resistance of chromivmi . The most effective chemicals described

were potassium permanganate (KMNOi+) and silicotungstic acid

(HitSiWi204o) • The KMNO^ was added to a 400 g/1 CrOa bath containing

no particles and the Hi^.SiWi2040 added to a 200 Cr03 bath containing 10 g/1 SiC. Initial tests showed no marked improvement in

hardness of the deposit with or without the thallium ion present

as shown below in lines 1 and 2 , 6 and 7 , 4-5 and 14

-14-
H^SiWl20l,o TINO3 Temp. /CD Inclusion Hardness Wear Lo

wt.% KHN200

0 5 65V40 1.75 297 10.3

5 5 65VA0 2.41 336 9.9

5 5 55V50 1.57 471 9.8

1 0 55V50 0 1054 9.3

1 0 55 V50 0 1067 6.3

0 1 55V50 0.30 785 15.3

1

' 1 55V50 0.25 599 11.5

1 2 55V50 0.41 560 18.3

1 3 55V50 0.48 641 33.2

1 4 55V50 0.51 533 24.2

1 5 55V50 0.88 609 16.8

2 2 55V50 0.08 545 7i6

3 3 55"'/50 0.41 688 13.7

9 0 55V50 0 1053 7.9

KHMOtt

40 ' 0 30V20 0 817 12.5

Figure 14 is a graphical representation of the effect on the

amount of included particles of increasing the thallium ion concentration in the 200 g/1 CrO^ electrolyte plus 1 g/1 Hi+SiW]^20uo • Perhaps the most valuable result of the soluble bath addition

tests was the discovery while making a comparative run without

soluble addition that 1 g/1 TINO3 was effective in codepositing

particles and did so without the usual formation of voids (Fig. 15).

Succeeding runs were therefore made with 1 g/1 TINO3 and the best

wearing deposits obtained thus far in this work were obtained.

Data from these runs are given in the next section.

Effect of Particle Concentration

This test was run with SiC particles because of the limited

supply of diamond powder available. The SiC concentration was

varied between 10 g/1 and 75 g/1. Figure 16 shows the effects of

particle concentration on amount of included materials. Other data

-15-
from the test, including temperature/current density variations, are shovm below:

SiC

e/1

TING 3 2/1Temp. /CD Inclusions

wt .%

Hardness

KHNonn C. '7 V Wear Loss

meO

10 1 SS'/SO 0.30 785 15.3

20 1 55''/50 1 41 614 3.4

JU 1 OUo J . o

• 50 1 55V50 0.68 871 7.5

75 1 55V50 1.07 639 4.6

75 2 65VA0 0 653 32.6

75 2 65V60 0.55 644 7.8

75 2 65V80 0.08 889 . 15.2

The effect of even a small amount of inclusions on wear is demonstrated by the runs at 65/40 and 65/60. The former yielded no inclusions and showed up poorly in the wear test. The latter deposit

contained only about one-half of one percent SiC but wear is 75% less

for about the same deposit hardness.

Controlling; Thallium Ion Concentration

The cross-sections of a number of deposits showed the inclusions

grouped in a band or layer parallel to the basis metal. Sometimes

the band was quite narrow or it could have the width of one-half of

the deposit thickness as in figure 17. Apparently the thallium ion

was used up or rendered ineffective a short time after its introduction to the plating bath. Higher concentrations of thallium initially usually caused excessive distortion of the deposit as in

figure 19, but with most of the particles still in a band of limited

width. Introduction of the TINO3 increments might result in more

uniform distribution of the hard particles and thus improve wear

performance. Tests were run varying the amount of TINO3 added per

unit time and the total amount used for a test. Figure 20 shows the

particle distribution achieved by adding the TINO3 in three increments with one-half the total amount (1 g/1) added as the first

increment. Figure 21 shows the effect of varying the number of

-16-
equal additions during the A-hour plating time from 2-16. Some

tests were also run using unequal additions as initial deposits

indicated a minimum concentration below which no codeposition

occurred. The data obtained from several of the tests at 55'/50

and with 75 g/1 SiC in the 200 g/1 CrO bath are shown below:

Increments

Total

TING 3 (g/1)

Inclusions

wt.%

Hardness

KHN200

• Wear Loss

mg

2 1 1.07 639 4.6

4 1 0.63 ____ - 607 13.3

8 1 0.32 663 14.0

16 1 0 06 1071 XX . X 8 0.5 0.19 995 8.5

8 0.25 0.07 1040 5.6

4 1 (dilute)

* 0.02 1067 7.4

*TINO3 dissolved in 480 ml

used in other tests.

H2O before adding to bath, 48 ml H2O

3

(3/4 first addn

1

.)

0.29'*' 595 8.7

3

(1/2 first addn

1

.)

O-IS"** 443 4.0

3 1 0.43"^ 507 2.6°

'*"l8 g/1 Ni-coated, 15 ym diamond powder used in these tests.

°This deposit gave less than one-half the wear loss of the best

deposit without inclusions.

These data indicate that there is a relatively narrow range between

minimum and maximum concentration of the thallium ion for effective

codeposition of particles in the chromium deposit at a given set of

plating conditions. The table shows that a minimum concentration

of TINO3 must be maintained in the bath to effect codeposition of

particles. With the addition of amounts of 1/16 g/1 or less the

concentration of TINO3 in the bath was apparently below the effective

minimum

.

-17-
Plating Conditions £nd Thalliur'. Concentration . .

A number of deposits using 30 g/1 boron carbide in the bath with

varying anounts of thalliusi nitrate and at various temperatures and current densities were tried in an effort to expand the range of conditions

for effective incorporation of particles in chroTniun and to, perhaps,

find conditions resulting in a deposit with wear-resistance superior to

previous results. Previous work indicated that a chromium plating bath

containing 200 g/1 chromium trioxide and 2 g/1 sulfuric acid was advantageous in several ways so these concentrations of the basic constituents

were used for all the tests during this period. At least 1/2 g/1 thallium

was dissolved in water and placed in the bath at the beginning of the run and the remainder, if any, was added in equal increments during the course

of the run.

Figure 26 surxiarizes our results for the amount of included B^C in

the chromium as a function of the thallium concentration, the temperature,

and the current density. That the data suggests only vague trends or

correlations is evident. Tliis may be, in part, because the particle

-18-
inclusion is not very sensitive to the three operating variables. It may

also be because the experiments were not highly reproducible. This is

suggested by the duplicate values plotted in Figure 26, which show a sizable spread. This lack of reproducibility was given considerable

attention and we have been unable to identify the cause. The current

density, temperature, and bath geometry were closely controlled. We

believe our analytical method is satisfactory. Agitation is nominally

the same, maintaining particles in suspension continuously. The trivalent

content of the baths is gradually changing, though maintained within

limits, and this may be significant. Also, the possible build-up of

decomposition products of the additives during operation and aging of

the bath may be a factor, as well as variations in depletion rate under

varying conditions of operations.

The data show that inclusions are found in the chromium if thallium

is present. It suggests that 0.1 to 1% of inclusions will be obtained

with 1 to 5 g/1 thallium at 30°/20 asd to 65°/75 asd.

The effect of thalliim concentration alone on the wear-loss and

hardness of chromiim deposits with no particles added to the bath is

sho\7n in Figure 27. The spread of temperature and current density combinations giving a wear-loss of about 6 mg or less per 10,000 abrader

cycles is shown in Figure 28. The concentrations of thallium nitrate in

the bath for deposits having a wear- loss of less than 6 mg are plotted in

Figure 29. It may be noted that a slightly lower average weight-loss was obtained with 3 g/1 thallium. There were other deposits plated using

the same bath composition and conditions which did not have similar low

weight-loss values.

These exploratory tests of temperature, current density and thallium

concentration variations did not reveal a set of conditions more beneficial than those previously tested. It has been observed that at the

higher temperature-current density condition a given amount of thallium

results in the incorporation of fewer particles (Fig. 26) and has a less

deleterious effect on the properties of the chromium deposit. Conversely,

about twice as much thallium may be used at 55^/50 asd as at 40*/20 asd

without causing excessive discontinuities or granular chromium deposits

that are useless.

-19-
Various Types of Particles

Several types and sizes of particles were used for incorporation in

chromium deposits in an effort to obtain maximum wear resistance as follows

Diamond

Silicon carbide

Aluminum oxide

Zirconium silicate 40 ym

- 5, 10 and 15 um (Prevlo'osly reported)

- 25 ym (Previously reported) and 15 um

- 5, 9.5 yn and fumed (very fine - "Alon")

Boron carbide

Silica

- 15 ym

- fumed (very fine - "Cab-O-Sil")

The following data show the overall average wear resistance for those

deposits containing 0.1 wt.% or more of particles, including all plating

conditions and amounts of additive used:

Particle Size

ym

Nominal Particle

Hardness

(KHN)

Number

Deposits in

Average

Least

Wear-Loss

m?

Average

Wear-Loss

mg

5 2000 9 11.6 16.7

9.5 2000 11 6.2 11.4

Alon 11 6.1 12.8

B,C

4

15 3000 - 5000 45 2.0 7.9

C (diamond) 10 7000 14 2.6 6.9

C (diamond) 15 7000 7 2.6 5.7

Cab-O-Sil 6 14.8 18.2

SiC 15 2500 9 3.8 15.6

SIC 25 2500 18 3.4 8.6

ZrSiO^ 40 7 5.5 15.7

Although the best wear for a single deposit is for one containing B^C,

the more significant best average wear is for deposits containing diamond

particles. Of course, absolute optimum conditions may not have been

selected for any or all types of particles because of practical limits

to the number of tests that could be rxm, but we believe that the general

relative merits of the particles have been obtained. A summary of the

Individual tests as regards additive concentration, particle concentration and plating conditions and their effect on the amount of particles

included is shown in Figure 30. It suggests that the concentration of

-20-
particles in the bath caused changes in the amounts of ZrSiO^ and kl^O^ -

5 ym included in deposits.

The average wear resistance of deposits with incorporated B^C (shc/m

in the tabulation above), though not as good as that for diamond, was

better than the wear resistance for any of the other particles tried.

Therefore, B^C should have favorable consideration for use as a practical

wear-resistant particle for inclusion in chromium deposits.

Various Additives

Several additives were tried in addition to thallium that would hopefully promote increased incorporation of particles in the deposits while

having a lesser deleterious effect on the properties of the chromium. -The

following monovalent cations were tried: cesium, lithium, ammonium and

sodium. Again, there is no certainty that the absolute optimum conditions

have been used, but the general relative performance of each is shown

below:

Additive

Number of

Runs in

Average

Most

Inclusions

(wt.%)

Average

Inclusions

(wt.%)

Least

Wear-Loss

(mg)

Average

Wear-Loss

(mg)

TINO^ 21 1.54 0.43 3.2 7.6

CeNO^ 22 0.88 0.43 3.5 9.6

CeNO^ + TINO^ 4 0.65 0.39 3.5 5.0

LiNO^ 7 0.67 0.41 7.8 12.4

NaNO^ 7 . 1.85 0.88 3.8

* 17.4

4 3

1 .68 11.3

*Five deposits in average.

Several deposits were made using ammonium nitrate as an additive, but

in only one was an amount used which produced a continuous chromium plate.

More tests with this additive should be made. In comparing the average

performance of the various additives there are several factors that should

be kept in mind. The results for thallium and most of the results for

cesium were from deposits on horizontal surfaces. At this point a series

of tests were made on vertical surfaces. It was found that almost equal

-21-
amounts of inclusions could be obtained in deposits on vertical surfaces

(as is shovm in the next section) so the remainder of the additives were

used in conjunction with vertical cathodes. The results for thallium are

from deposits with included boron carbide while those for cesium included

some runs with aluminum oxide and silicon carbide as well. Therefore,

considering the slightly better wear performance of boron carbide, the

results of thallium and cesium are very close. For practical use, thallium

would probably be the choice of the two as the price of cesium salts is

about four or five times that for thallium. A few runs on a vertical

cathode (Fig. 31) indicated cesium is slightly more effective than thallium

in incorporating silicon carbide in a chromium deposit. Figure 32 shows

the slightly greater disruption of normal chromium structure by thallium

than by cesium. This poorer deposit contains discontinuities (large

irregular dark areas with no "trail" of raised chromium) , rougher surfaces

and fissures near surface.

The three other additives: lithium nitrate, sodium nitrate and

ammonium nitrate, all seemed to have a more deleterious effect on the

properties of the chromium for equivalent amounts added than did thallium

or cesium (Fig. 33) . However, used in smaller quantities, they were effective in including particles in the deposits. Figure 31 summarizes some

of the results obtained in relation to the amount of additive used. These

additives are much less expensive than thallium or cesium and should not

be ruled out for practical use. One of them (NaNO^) , when used for including particles, has shown that it can result in better wear than standard

bright chromium. Figure 34 compares chromium structure at two levels of

sodium nitrate concentration with about the same amount of included

material in each deposit. The deposit made with the greater amount of

sodium additive is believed to contain some discontinuities in the chromium in addition to inclusions.

Vertical Cathodes

At one point in our investigation, a number of tests were made to

determine whether electrodispersion of particles in chromium could be a practical process for general application to articles other than flat

-22-
pieces that would involve vertical surfaces as well as horizontal areas

.

Several tests were made on vertical surfaces using thallium in the chromium bath. Overall results are shown below:

No. Maximum Average Least Average

Particle Runs Inclusions Inclusions Wear-Loss Wear-Loss

(wt.%) (wt.%) (ma)

Horizontal B.C

4

21 1.54 0.43 3.2 7.6

Vertical ' SiC 18 1.62 0.39 4.5 12.4

The better wear performance of horizontal deposits could be at least

partially the result of the harder boron carbide particles, although the

average of included material in vertical deposits is slightly below that

in deposits plated horizontally. Because the results were close and to

obtain more data and experience, se\teral of the additive tests were run on vertical cathodes, as indicated above, and all resulted in the effective

inclusion of particles (Fig. 35).

Steel as Basis Metal

Several test deposits were made on carbon steel substrates. The steel

was plated with and without a preplate etch in the plating solution.

Adhesion to the steel was good in both cases, as indicated by 180° bend

tests, and no difference in other properties could be detected between

these deposits and deposits on the usual copper substrate.

Lubricating Particles

Several tests were made with molybdenum disulfide or fine graphite

in the bath alone and in conjunction with hard particles. Deposits from

baths containing molybdenxm disulfide were very poor and after two or three

runs the bath, became incapable of producing continuous chromium deposits.

As much as 0.12 wt;% of the graphite was included in deposits by using

1 g/1 lithium nitrate. Wear-loss averaged 11.4 mg, substantially more

than that for bright chromium with no particles.

-23-
Various Hard Particles

Up to this point in our investigation, chromium deposits with incorporated diamond particles resulted in the best wear-resistance. The next

best wear characteristics were given by incorporated tetra-boron carbide

particles. An effort was made to find particles that would impart greater

wear-resistance to chromium deposits than B^C. One of the large abrasive

suppliers especially prepared without charge six super-hard particles aiui

a seventh type of hard particle was purchased from another company. The

particles were as follows: AlB.-,, B.C, B,C, CrB., SSiJV,, TiB-, and TiC.

The average size of the particles was about 25 pm. Scanning electron
micrographs of two of the t>^es of particles (Fig. 36) show a rather wide

range of sizes which is not considered detrimental for our purpose.

The particle resulting in the best wear of a chromium dcDOsit by a

small margin was B,C. The special B.C and the AlB,. were verv close in

o 4 IZ

imparting wear-resistance. Commercial silicon carbide particles of about

15 ym in size were used for comparison. The 200 g/1 CrO^ bath and a

vertical cathode were used for all tests. Three or four runs were made

using each type of particle at one or two temperature -current densities

and with two types of chemical additives. A summary giving the averages

of the results for tests of each type of particle is given below:

Particl e Deposit

T>^e Hardness Hardness IVear Loss • Inclusions

AlB.^ 2300 KHN 675 KHN200 7.7 mg 0.18 wt

B4C 2800 669 7.5 0.27

BeC 3000 695 6.3 0.30

BSi3N4 3000 677 12.9 0.33

CrB2 3500 604 11.2 0.61

TiB2 2700 662 7.8 0.59

Tic 2500 640 12,2 0.83

Sic 2500 749 10.2 0.85

Glass powder 616 11,3 0.20

The detailed data from the tests indicated that specific combinations

of plating conditions and additives resulted in increased inclusion rates

of some particles. For example, TiB^ was included in substantially greater

amounts using LiNO^ at 45*/30 asd than at 55/50. Using TINO^ and LiNO^,

larger amounts of TiC were included at 45/30 than at 55/50. These instances

conform with the general observation throughout the program that fewer

particles are normally included at higher current density and temperature

conditions but this is not true for all combinations of particles and additives. Therefore, it cannot be taken for granted that an additive or a -25-
set of plating conditions will result in the best particle inclusion rate

for a given particle because it is best for several others.

None of these special hard particles showed enough improvement in

wear-resistance when included in chromium to warrant their use in place

of some of the best of the more readily available particles already tested .

although the B^C shows some superiority over all the others tested except

diamond.

During the tests of the CrB^ particles, some of the thallium and

cesium additions to the chromium baths were made in the crystal form.

The usual procedure was to add these components as a water solution in

four equal increments during the run* Additions as crystals did not

form the usual yellow precipitate and the effectiveness of the additives

seemed to extend throughout the run of 4 or 5 hours without partial periodic

addition to the bath as had been previously practiced. In a water solution of CrO^ the crystals were observed to dissolve very slowly,

Bath Life Test .

The initial phase of this test consisted of eight runs. A new bath

was used for each of the first three runs; then five consecutive runs

were made in the same bath. All eight tests were made with 30 g/1 B^C

and 3 g/1 TINO^ in the baths. The wear -resistance was good for the three

runs in the new bath, about one-half the weight loss for hard, bright

chromium without inclusion, and the results are quite close. The tests

in the "used" bath indicate a slight decrease in wear-resistance for each

successive run as an increasing amount of current is put through the solution as shown in Fig. 37. Bath component concentration levels were maintained and no substantial decrease in the amount of included material in

-26-
in the deposits occurred throughout the test. Since the trivalent chromium

content of the bath remained within acceptable levels, it is probable that

the slight decrease in wear-resistance of successive deposits was due to

build-up in the bath of Tl or Tl compounds. Deposits and amounts of

included material did not appear to be adversely affected.

The second phase of the bath-life test consisted of 58 tests for a

total of 5100 ampere-hours per liter of chromium plating solution. Components of the solution were renewed as necessary to maintain the nominal

bath composition of 200 g/1 CrO^, 2H2S0^ and 30 g/1 B^C . Ammonium nitrate

at 1 g/1 was used as the monovalent cation additive for most of these tests.

Near the end of the experiment several tests were made without addition of

NH.NO„ and hardness of the chromium deposit returned to about 100 KHN„^-,

4 3 200

and inclusions in the chromium dropped below 0.1 wt.% indicating approximately normal deposits that would be expected from a standard chromium

bath. However, after about 3200 amp-hours per liter had been passed

through the bath, the spread of wear-resistance values obtained increased

substantially (as shown in Fig. 38) and the average wear-loss had about doubled at the end of the test or at 5100 ampere-hours. There were visible

encrustations on areas of the bath container where the bath was subject

to evaporation. This was assximed to be the result of the build-up of

NH^NO^ or its decomposition products. It was definitely not CrO^. At the

end of this series of tests, a total of nearly 40 grams of NH^NO^ had been

added to the bath.

The above indicates that there is probably a limit to the life of a

chromium bath when using NH^NO^ as an additive beyond which deposit properties would not be acceptable. For all practical purposes even 3200 ampere-

-27-
hours per liter of bath represents a very long bath life in the practical

chroTiiu.-n plating bath. In addition it is entirely possible that the products of the additive could be rer.oved from the bath by a simple procedure

such as cooling and decanting as they seen to be much Jess soluable than

Cr03.

During the bath-life experiment the use of a new wear-test abraser

was started. Comparison of the results obtained on the new and old machine

showed some difference in wear-resistance values so a factor was used to

make results com.patible. .

.

Various Additives

A number of runs were made using the additives previously tested to

some extent. As indicated in the section above, NH,NO_ was used in a

considerable number of tests and was found to be effective for incorporating particles in chromium deposits. However, the bath would tolerate only

about one-third as much NH^NO^ as TINO- and still produce continuous, hard

deposits. More runs were also made using LiXO_ and CeNO- and, of course.

TINO^. A general summary of the relative performance of the additives

during these tests is shown in Fi g.39 and is tabulated below:

Additive No. of Runs

in Av.

Most

Inclusions

(wt

Av. Inclusions

(wt %)

Least

Wear -Loss

(mg)

Av.

U'ear-Lc^

Crag)

NHA'Oj

4 o 39 3.89 0.762 3.9 8.2

LiN03 12 2.29 0.60 6.4 11.5

CcN-03 4 1.65 1.26 8.2 10.0

TIN'O, 45 1.41 0.41 3.0 8.6

-28-
All of the above deposits were r.ade on vertical surfaces but include sc-.oral

different t>'pcs of particles and plating conditions of froni 45°C/20 asi to

55/50. Several, but not necessarily all, of the conditions were used icr

each tv-pe of additive. Figs. 39 to 41 show the relative amounts of

inclusions and wear-loss respectively for lithiu-n nitrate as compared

to thalliun nitrate for runs under similar conditions. The lithiuu-n shc.s

wider fluctuations in both categories than does thallium nitrate.

Corrosion Protective Deposits Containin': Hard Particles

Cadmium . A number of cadmium and zinc deposits were made which incorporated B^C and •^12*^3 ^^^^ particles in an attempt to improve the wearresistance of a soft, protective coating. No chemical additives were

needed to include particles in cadmium' and zinc deposits although one -half

to one gram per liter of thallium salts in the bath increased the amount

of included material in zinc.

The cadmium specimens were plated in a bath of the following nominal

composition:

Cadmium oxide, CdO 22.5 g/1

Sodium cyanide, N'aCN 100

Sodium hydroxide, NaOH 14

Gulac (organic grain refiner) 0.4

To this bath was added the ^^2^3 '^^^ ^4^ varying amounts from 10 to

30 g/1. The current density used for a particular deposit seemed to have

more effect on wear-resistance than the t>'pe or amount of hard particle

incorporated. All runs were plated at about 24''C. Below is a summary of

the cadmium deposits tested:

-29-
Current No. Type of Majc. Av. Least Av.

Density Runs Particles Inclusions Inclusions Wear -Loss V.'ear-Lo

(asd) (wt ^i) (wt %) (mg)

1 2 — - —

53.8 35.9

1 2 0.69 0.67 29.4 39.

2 4 II 1.06 0.9S 19.3 25.9

3 I

11 — 1.11 27.

S

4' 1

II — 1.48' 32.0

5 1

f 1 l.OS 25.2

1 2

2 3

0 .5S 0.38 53.8 64.7

2 4 II 0.64 0.58 33.3 43.

S

3 3

II O.SS 0.62 34.8 56 .

3

5 1

It 0.60 47.1

The improverient in wear-loss for deposits with included particles was b " 1 1 £

than two to one over deposi ts without particles for the best series 0 IT

tests. The B^C particles were incorporated inore readily and resulted in

the greatest Lv.prove.'nent in wear-resistance. Average inclusions per run

for B,C was

4

1.06 wt %, for A1_0,, 0.55 wt

2 0

% . Average wear-loss for 5 ,c

4

was 29.6 mg, for A1^0_, 48.0 rag. Figs. 42-44 are graphic presentations

of data from tests of Cd deposits. Refin'ir.ent of bath composition and

plating conditions could quite possibly further improve the wear -resistance

of cadmium coatings.

Zinc . The zinc bath used had the following composition:

Zinc sulfate, ZnS04 240 g/1

Ammonium chloride, NHiCl 15

Ammonium sulfate, (N'H4)2S04 30

Licorice (grain refiner) 1

To this bath up to 30 g/1 B^C and Al^O^ particles were added. Also,

several tests were run in a zinc bath containing thallium salts as well

as hard particles which did increase the amount of inclusions in the deposits. A series of runs was made in the zinc bath with varying amounts

of particles in the bath and at several current densities as well as a

-30-
few runs using thai liun. A surjnary of the tests is shouTi below:

Current Xo. Type of Max

.

' Av. Least Av

.

Dens it

V

Runs Particles Indus ions Inc lus ions Wear -Loss V. 3 n r - 1 OS?

(asd)' (Ut ^o) (Wt ^o)

2 2 — 34 .

9

36 .

5

3 2 40.6 42.0

2 1 A1^0„ 0.13 23.4

3 4

2. o 1.05 0.50 30.3 42.9

5 1 " — Oo 13 - =• 22.5

2 3 1.96 0.99 20.5 25.9

3 5 0.43 0.31 19.5 23.2

5 2 0.59 0.43 26.0 26.7

2 4 B^C-^Tl , 1.82 0.78 21.0 27.7

3 6 1.79 0.9S 17.4 25.3

5 2 0.58 . 0.53 23.0 25.2

Since the current density seened to have more effect on the wear-loss than

the amount of particles in the bath, all runs at a particular c.d. were

averaged together from baths containing ten to thirty g/1 of particles.

The improvement in wear-resistance for deposits containing hard particles

was not as great as for cadmium but there was some imDrovement at 2 and

5 asd with A1^0» and with B^C in the bath. (See Figures 46-48 for

graphic representations of the data.)

Thallium increased the amount of included material at 3 asd but was

not effective in these tests at 2 and 5 asd. Wear-resistance was very

close with or' without thallium, about two-thirds that of deposits without

inclusions. Average inclusions per run with •^l2'^3 0.32 wt %, with

B^C, 0.70 wt %. Average wear-loss for ^"^-p-x^ ^^'3-s 36.6 mg, for B^C, 25.0

mg. Data from deposits formed with thallium in the tine bath are shown

graphically in Figures 49-50.

Gun Tube

A 0.30 caliber machine gun tube furnislicd by the Rock Island Weapons

Laboratory was plated on the inside with chromium incorporating hard

-31-
particles by adding thallium and B^C powder to a standard 200 g/1 CrO^

bath. First, several steel tubes of approximately the sar.e inside diar.eter

as the gun tube were plated experinentally to determine the correct equip-

•ment or fittings and plating conditions necessary to- obtain a r.ore or less

uniform coating on the tube bore. To obtain approximately the same deposit

thickness distributions as the original chromiam plate in the tube bore,

0.0053" at the m^uzzle and 0. 13025" at the breach, it was necessary to form

a one-eighth-inch diameter anode from pure silver wire and then copper

and lead plate it for protection from' attack. Using this anode and a

temperature-current density ratio of 43/30, it was found that a reasonably

uniform deposit incorporating B^C particles could be applied to the simulated gun tubes. The gun tube bore, plated in a vertical position at

these conditions, had a deposit thickness at the muzzle of 0.0031" and

at the breech, 0.0027". The simulated gun tubes were sectioned and revealed inclusions of hard particles in the rather rough deposit even at

the top of the tube. Fig. 51 shows cross-sections at the top and the

* bottom of one of these test specim.ens in which the distribution of the

chromium was rather poor but otherwise similar to the deposit in the gun

tube. It was later learned that the chromium deposit with incorporated

particles in the gun tube was broken from the bore surface rather quickly

under firing test conditions without much of a determination of its

"wearability .

Hcat-Trcatcd Deposits

Several particle-containing chromium deposits plated on copper were

heated in air to determine the effect, if any, on adhesion to the substrate
and wear qualities. After heating, raild bending of the specimens cracked

the chroraiur. but no flaking, indicating loss of adhesion, occurred, ''.'earresistance was sor.ev.hat diminished on those deposits heated above 230"

C

as is shov.n in the dat^ below:

V Initial Heat- Resultant

Wear -Loss Treatr.ent Wear -Loss

(mg)

12.8 400**C - 1 hr 17.3

13. 5 " " " 17.3

10.6 600''C " 15.5

13.6 250°C 2 " 12.9

•The normal he at -treatment of chroniun plated parts to relieve possible

hydrogen erabrittlenent of the substrate is in the 200-300*C range so

chromium deposits with included particles should not be adversely affected.

Cross-sections of the heated deposits are shown in Fig. '^2.

-33-
Reactions of TlNO^i

Several tests were conducted in an effort to better understand

the action of the thallium ion in promoting particulate codeposition

in chromium. A solubility test revealed that about 0.2 g/1 of TINO3

dissolved in a 400 g/1 chromic acid plating bath at room temperature.

Slightly more went into solution at plating temperature. The remainder formed thallium chromate (Tl2Cr0i^) . Tl2CrOi+ .introduced to a warm,

fresh plating bath of similar concentration dissolved in the amount

of 6% by weight or a little over 0.1 g/1. This does not explain the

severe effect on the chromium deposit when thallium is used in the

higher concentrations of 5 to 10 g/1.

Further isolation of the reaction was attempted by depositing

chromium from a bath containing thallium and with the cathode and

anode separated by a porous ceramic partition. After 60 ampere-hours

of electrolysis, the thallium chromate precipitate was recovered

from the anolyte except for about 0.2 g/1 which was presumed dissolved.

This agreed with the solubility test described above. .An accurate

measurement was not made in the catholyte because of other material

formed during electrolysis.

Thallium chromate introduced into a plating bath in a porous

envelop resulted in having no effect on the deposit discemable as a change in structure, appearance, properties or the codeposition

of particles. Results of these tests were not very informative and

further checking is planned.

DISCUSSION

With the simple addition of particulate matter (SiC, Ti02, diamond, AI2O3, etc., powder) to a conventional chromium plating bath,

there is very little codeposition of the particles. By adding TINO3

to the bath as others have done with other plating systems, we were

able to codeposit the particles in significant quantities. Unfortunately, most of our deposits had a poor wear resistance compared

to ordinary hard chromium. These deposits were made over a wide

range of plating conditions. If we consider those deposits with a

-34-
wear rate of less Chan 9 mg (standard chromium 55°/50 asd, 20U g/1)

(Tables on pp. 15 and 16) we note that 2 g/1 or loss of T1N0-, were

used in every case. Whenever 5 or 10 g/1 was used in tiie conventional bath, the effect on wear resistance was negative. Our data

is not sufficient to pinpoint the optimum range of thallium nitrate

addition, as related to current density and bath temperature.

A graph of wear vs inclusions (figure 18) taken from the first

five lines of data in the table on page 15, shows a close relation

between wear and particulate inclusions for a given system; that is,

if everything else is the same. It appears that when other variables

are changed, the wear changes, as with current density (figure 13).

Hence, to obtain good wear qualities, more than just the amount of

codeposi.tion must be considered. The process by which the particles

were incorporated into the deposit is critical.

The nature or properties of the codeposited particles is, of

course, a factor also. But how important is this factor? With the

present achievement of 2% or less cod'eposition in the bes.t wearing

deposits, only a very small percent of the deposit surface (the

wearing surface) consists of exposed particles. The balance of the

' surface is chromium with its own wear characteristics and it can be

expected to wear away between the included particles, at least by

the Taber Abraser with the semi-rigid, rubber-bonded abrading surface

but which is more responsive to the amount of included particles

than the hard, vitrious-bonded wheel mentioned earlier in this report

The mode of action of the thallium nitrate is not clear. Presumably the partial solubility of thallium chromate provides ions

which were adsorbed on the particulate matter and perhaps the solid

chromate has the detrimental effects. In any case, a better underStanding of this reaction could facilitate improvement of the process

In other plating systems, cations other than Tl"** are effective,

though Tl"*" is stated to be the most effective. Perhaps another ion

would be more effective than Tl"^ in the chromium bath. Na"*" has been

found effective in a copper bath, hence, we included the Bornhauser

-35-
bath in our experiments. Apparently it works insofar as codeposition

is involved, but the basic wear properties of the Bornhauser chromium

are poor. It may be possible to formulate a suitable chromium plating

bath in which sodium ions will be effective and the deposit will be

more wear resistant.

A summary of the effects obtained by the inclusion of particles

from a variety of chromium baths and plating conditions is shown in

figures 22-31. By plotting the bar graphs with hardness on one side

and wear loss opposite, the distance between the inside ends of the

bars is a general representation of the effect of the included particles on wear resistance. For example, a deposit with high hardness

would have good wear resistance and the hardness bar would extend

far to the left. The wear loss bar would be shorter than for a softer deposit but the distance between the ends of the bars would

not be as great as it would for a short bar for a soft deposit and

a short wear-loss bar because of included particles. Although the

distance between the ends of the wear-loss and hardness bars is not

in every case entirely due to the effect of the included particles,

an overall picture of some of the various tests can be seen. Generally, those deposits showing poor wear but having appreciable amounts

of inclusions contained the -inclusions in voids or agglomerates, or were chipped or cracked.

-36-
The experiments > using additives, have shown an inertial and a residual effect. That is, the full effect of the additive is not realized curing

the first run in a bath v;ith no previous addition. Also, a bath that r.cs been run with an additive vill continue to codeposit particles (occasicr.-

ally in larger ar.ounts) for one or nore runs, as though an addition hzd

been made. This residual effect is usually considerably reduced after one

run without a nev addition, but is scr-e tines effective enough to include

some particles for several runs. The effect can be eli-inated by heating

the bath to £0°C for an hcur or t:ore r.-.d by the process used for reducir.-

trivalent chrcniun: ions to hexavalent ions during which the bath is also

heated to about cO°C and operated at high cathode current density.

For a given amount of included particles, low tenperature and current

densities require the least ancunt of additive and at these conditions

the physical properties of the chroniun are more seriously affected by a given anount of additives. These lower tenperatures and current densities

(40*/20 asd to ^5°/3Q asd) are the conditions most likely to be useful

for practical applications of chroniiun with included particles. Although

regular chroaiun is harder at 55" and 50 asd, when enough additive is used

for the effective inclusion of hard particles, there is little difference

in hardness between deposits plated with high or low temperature-current

density conditions.

The effect on the chrotaiusi deposits of all the additives tried was

the sane except for degree. A given amount of cesiu^i salt appeared to

degrade the properties (cause discontinuities, fissures, roughness, low

hardness) of the chronium to a slightly lesser degree than did thallium

for the sazne conditions (Fig. 3^. Lithium salts seened to have the r.ost

deleterious effects on the chromiuai properties of all the additives

tried (Fig. 39), but- by using snaller asounts a suitable deposit having

included particles could be obtained. The effects of other additives

ranged between those of lithiun and thallium.

The ar:ount of particles included in the deposit at a given set of

conditions also affected the properties of the chronium. Included material

-37-
in amounts much over 1% of the weight of the chromium had a deleterious

effect in addition to that of the additive on the hardness, structure,

and probably therefore the wear-resistance. Data obtained from some

deposits with over 1% particles show that for seven deposits with an average of 3.1 wt.% inclusions, the average hardness was 281 KHN^qqo

There were no wear-test results because of discontinuous deposits or

the deposits wore through before completion of the test. Not all

deposits with more than about 1 wt.% of inclusions were soft and

discontinuous, but of those that could not be wear- tested most had

more than 1 wt.% included material. These poor deposits were usually

formed during tests of larger amounts of additive or when the bath

had a high concentration of trivalent chromium. Those deposits having

wear-resistance more than that for hard, bright chromium (about 6 mg

for 10 K abraser cycles) almost always contained between 0.1 and 1.0

wt.% of particles. The average amount of included particles in 22

deposits showing improved wear over standard chromium was 0.39 wt.%.

This could be an indication of the approximate amount of particles to

aim for in practical applications.

It was noted that particles remaining in the bath over a substantial

period of operation were less likely to be incorporated in the deposit

than freshly added particles, so a small amount of fresh particles were

added to the bath before each run. These small additions compensated

for spillage and drag-out losses maintaining the desired concentration.

It was rather disappointing to learn that of the several new types

of particles tried, only one showed any improvement in wear-resistance

over the previously tested B^C. The particle giving improved wear when

incorporated in chromium was the closely related B,C and the improvement

o was only slight. This means that for top wear-resistance diamond powder

must be incorporated in the deposits. The expense of using diamond could

be reduced by using a smaller amount in the bath without seriously affecting

incorporation rates. It is estimated that as little as 10 or even 5

g/l instead of 30 g/1 would be effective in the bath. Since the amount

usually included in the deposit is 1 wt.% or less, the depletion rate

would be minimal. However, in general B^C and even SiC give improved wearresistance when included in deposits and would probably be effective for

most uses

.

-38-
Particles are included most effectively at 45**C or below and at

current densities of 50 and down to 20 asd with the most effective combination for most selections of additives and particles at 45°C and

30 asd. These conditions result in a deposition rate of about 1 mil per

hour and reasonable distribution. If required, higher temperatures and

current densities include some particles up to about 65*C and 60 asd.

Some types of particles seem to be more readily incorporated than

others. This may be related to their ability to become electrically charged.

Shape, size, mass, and adsorption may also have some effect. Fdr example,

nickel coated diamond is more readily incorporated than uncoated diamond

and Sic and CrB^ were incorporated more easily and in larger quantities

over a range of conditions than some other types that may not be as conductive .

Normally the life of a chromium bath is indefinite, requiring only

periodic additions of CrO^ to replace deposit and drag-out losses. The

life test run on the chromium bath containing additives for the including

of particles up to 5100 ampere-hours per liter showed that the only problem

was a build-up of the additive or by-products of the additive in the bath.

When the bath was treated for removal or reduction in . concentration of

these by-products, it behaved normally again. The only exception was a

bath used with lithium nitrate as an additive. It seemed to contribute

to the build-up of Cr-^O^ in the bath and prevent its reduction to CrO^

again. Deposits from a bath thus affected were dull and rough and uniformity of coverage was poor.

It is considered that in a large plating bath the use of the other

additives would not cause any problems as 5100 ampere-hours per liter of

-39-
bath represents a considerable amount of plating in a particle plating

operation.

Further tests of several of the additives used, mainly NH^NO^ and

CeNO^, confirmed previous results indicating that CeNO^ was most effective

for incorporating particles in a chromium deposit with minimal disruption

of the structure and characteristics of the chromium. However, it is

quite ejcpensive and more common materials such as NH^NO^ are inexpensive

and adequate for practical operations. Probably the ultimate combination

according to present results would "he CeNO^ and nickel coated diamond

particles added to a 200 g/1 CrO^, SH^SO^ bath operated at 45*C and 30

asd for the best wear-resistant deposit.

Particles were incorporated on vertical cathodes in cadmium and zinc

deposits from the cyanide baths used without the use of an additive.

However, the use of thallium in the zinc bath enhanced the amount of parti- j

cles included. It was not tried in the cadmium bath. Wear -resistance

| was more than doubled for cadmium deposits containing hard particles. !

Wear-re,sistance for zinc deposits containing hard particles was improved

but only by about 30 to 50%. It is possible that variation of mechanical

arrangement of the electrodes and bath composition could considerably

increase the amount of included material and thus perhaps the wear -resistance

Heating the chromium deposits in air oxidized the exposed copper basis

material extensively but only treatments at 400*0 and above oxidized the

chromium. The reduction in wear-resistance at the higher temperatures was

expected as any softening of the chromium matrix reduces wear qualities

despite the presence of hard particles which were most likely unaffected

by the comparatively low temperatures used.

-40-
At the end of the program a few tests were made in a 200 g/1 CrO^

chromium bath using sodium fluosilicate as a catalyst plus an additive and

hard particles. Efficiency was very low and only a coarse, greenish colored

deposit was obtained which had completely unsatisfactory wear qualities.

There was no time to experiment with other fluoride catalysts or plating

bath combinations.

This program for incorporating hard particles in chromium deposits

has shown that many monovalent cations are effective when added to the

bath in amounts of about 3 g/1 or less over a range of plating conditions

and even on vertical cathodes. Without these additions no particles are

included from the standard chromium bath. However, the additives or the

included particles or both result in the deposition of softer, dull deposits under plating conditions that would normally yield hard bright

deposits. Wear -resistance is improved over bright, hard deposits only

because of the presence of hard particles in the chromium matrix. If

additives and conditions could be found that deposited bright, hard chromium with included hard particles, it is fairly certain that the improvement in wear-resistance would be many times that achieved in this program.

-41-
CONCLUSIONS

The work on this program demonstrated that it was entirely feasible

to include hard particles in chromium deposits with a resultant increase

in wear-resistance. Other particles such as metal powders and dry lubricating material were incorporated in chromium. Hardness and brightness

were diminished when particles were included either because of the presence

of the particles or because of the monovalent cation added to the bath or

both. Inclusions of more than 5 wt.% of particles seriously degraded

all properties of the chromium but even less than 1 wt.% of hard particles

in the deposit was effective in reducing wear. Boron carbide particles

yielded the best wear, with the exception of diamond, of any particle

commercially available with inexpensive silicon carbide a close second.

Bath-life was reasonably good and no impediment is seen to scaling up

the process for practical application on at least a semi-production basis.

Particles were included on horizontal and vertical surfaces as well as on the inside of tubes with suitable internal anodes and with the use of

plating conditions within the normal range for chromium deposition.

-42-
REFERENCES

1. P. Morisset, J, Oswald, C. Draper, R. Pinner, Cliromiurn Plating ,

R. Draper Ltd., Teddington, England (1954).

2. J. Doskar, J. Gabriel, Additives in Hard Chromium Plathing Baths ,

Metal Finishing 65_,(3),(1967).

3. T. Tomaszewski, L. Tomaszewski, H. Brown, Codeposition of

Finely Dispersed Particles with Metals , Plating _56, (11) ,

1234 (1969).

4. L. Spencer, Abrasives and Their Application in Metal Finishing ,

Metal Finishing 6:8, (8) , (1970)
BIBLIOGRAPHY

1. AHILAD, Iqbal, Greco, V.P., and Barranco, J.H.; Reinforcencnt of Nickel

with some High-Strength Filarients (U.S. Army Watervliet Arsenal, New

York), J. Composite Materials I^, 18 (1967).

2. ALEXANDER, J. A. and Stuhrke, W.F.; Effect of Temperature on Mechanical

Properties of Boron—Electrodeposited Nickel Composites (General

Technologies Corp., Alexandria, Va.), Am. Soc. Testing Mats., No. 427,

. 34-52 (1966) (Pub. 1967). ••

.

'

3. ANTLER, M.; Nev Developments in the Surf aces ' Sciences of Electric

• Contacts , Plating 53, (12), 1437 (1966).

4. BAKUL, v., Sagarda, A., and Onap, A.; Characteristics of Diamond-bearins:

Electrodeposits , Mashunostraitel , No. 10, 21-2 (1968).

5. BLACKBURN, L.D., et al . ; Filament >Latrix Interactions in Metal Matrix

Composites , Twelfth Sagamore Arizy Materials Research Conference, Raquette

Lake, New York', August 1965." • ,

6. BOWDEN, F.P., and Tabor, D.; The Friction and Lubrication of Solids , Oxford, Clarendon Press, Vol. 1, 1954; Vol. 2, 1964.

7. BRANDES, E.A. and Goldthorpe, D.; Elec trodeposition of Cermets (Fulmer

Research Institute, Stoke Pages, England) Metallurgia 76 (457), 195-8

(1968) (England). M

8. BR0V7N, H. and Tomaszewski, T.; Occlusion Plating of Fluocarbon Resins , U.S. Patent 3,677,907.

9 . BRO^vNING , M . E .

, e t al . ; Developm:ent of Manufacturing Methods for

Deposition Forming , Progress Report No. 3, Contract AF 33 (615) -1375

Alex. Div.' AMF, October 1964.

10. BRO\\i^ING, 'M.E. , et al,; Deposition Forming Process for Aerospace

Structures , ML-TDR-64-26 (February 1964)

.

11. BURiNEY, J., A Study of the Possib'ility of Reinforcing High-Temperature

Alloys by Addition of Refractory Powders, WADG Tech. Rept. 57-535,

ASTIA Doc. No. 150971 (195S) . 12. BURT, F.'M.; Chro-.ium Diffusion for Corrosion and Abrasion Resistance , Metal Finishing 51.. (^) . 72 (1953).

13. CRATCI^ILEY, D., Experimental Aspects of Fiber-Reinforced Metals , Metallurgical Rev., Vol. 10, No. 37, 1965, p. 79.

14. COOPER, G.A. ; Eloctroformed Composite Materials (Univ. Cambridge, Eng.)

J. Materials" Science 2, 409-414 (1967).
"le CUFF, F.B., Jr.; Compositiion of Dispersed Phases in Refractory Metal

Alloys , (Adv. Metals Res. Corp., Somerville, Mass.)^ OTS AD 277, 152

16, DEAL, B.E.; A Method for Determining Abrasion. Resistance of Thick

Anodic Coatings on Aluminum, Plating 46^, 823 (1959) .

17, DIVECHA, A. P.; Preparation of Fiber-Metal Composites by Electrodeposition , U.S. 3,498,890, tlarch*3, 1970.

DUPERKELL, G.; Method of Chromium Plating and Treating Steel Airplane

. Propeller Blades , U.S. 2,462,615.

19. FLOWER, Frank A.; The CEM Process , Progress Report, Thomp'son Products,

Inc., Cleveland, Ohio (Wash. Office, 744 Jackson PI., N.W., Washington,

D.C. 20004, Me 8-5046), July 15, 1958.

20. FLUKMANN, W.; Wear-resistance of Gold Alloy Electrodeposits , Plating 56 , 12, 1351 (1969) . 21. GEISLER, A.H.j Phase Transformation in Solids , (John Wiley and Sons, Inc.,

New York, N.Y., 1951), p. 387.

22. GILLAI-I, E. , McVie, K.M., and Phillips, M. ; The Structure of Nickel

Electrodeposited with Alumina Particles (Cass. Coll., London), J. Inst.

Metals, Bull. Met. Rev. 94_, 6, 228-9 (1966).

23. GORSUCH, P.D.; Mechanical Properties of Internally Oxidized Binary Silver

Alloys , Doctorate Thesis, Rensselaer Polytech. Inst., Troy, N.Y. (June 1956)

24. GRANT, N.; Strengthening of Metals , Ed. 0. Peckner (Reinhold Pub. Corp.,

1964), Ch. 5.'

'25. GRAZEN, A.E.; Method for Electroforming and Coating , U.S. 3,061,525,

October 30, 1962.

26. GRECO, V.P. and Baldauf, W.; Electrodeposition of Ni-Al ^Q^; Ni-TiO ^ and

Cr-TiO ^ Dispersion Hardened Alloys , Plating 55, 3 (1968) . 27. GRECO, V.P., Wallace, W.A^, and Cesaro, J.N.L.; Bond Strength Characteristics -of. Electrodeposited Nickel on Boron and Silicon Carbide Filaments

(Reinforced Composites) , Plating 56, 3 (1969)

28. GRIFFIN, J.; Experimental Chromium Deposits as Affected by a Variety of

Possible Catalysts , Plating 53,, 2 (1966).

29. IMMARTINO, N.R.; Graphite Fibers Forge Ahead , Chemical Engineering 79,

(3), 30 (1972).

30. JUN, O.K., and Shaffer, P.T.B. Advanced Ceramic Systems , The Carborundum

Company, Dept. Navy Contract No. 0017-71-C-4410, Nov, 1971.

31. KELLY, A,; S'trong Solids (Clarendon,- Oxford, 1966), p. 159.

KELLY, A., and Davis, L.; The Principles of Fiber Reinforced Metals , Metallurgical Rev., Vol. 10, No. 37, 1965, p. 79.
32. KELLY, A. and Tyson, W.; High Strength Metals, (John Wiley and Sons, Inc., |

New York, N.Y., 1965), p. 578, I

\

' * *

1 33. KILGORE, C.R.; Engineered Composite Coatinris , Products Finishing, May 1 1963, p. 3A. 1'

34^ KRAGELSKII, I.V.; Friction and Wear , Butterworths , Washington, 1965.

35. NEWMAN, D.R.; Practical Aspects of Plating Mi Incorporating; Inorganic

Particles , IMF (Inst. Met. Fin.) Symp. 1966, 4-6. 1

36^ Occlusion Plating , U.S. Pat. 3,4'98,890, March 3, 1970.

37, ODEKERSEN; Co-Deposited Non-conducting Materials in Nickel-Chroiriium

Electrodeposits, Elec. & Metal Fin. 17, (1), 2-11 (1964).

38, OROWAN, E.; Synposium on Internal Stress in Metals , Rept. Progr. Phys.

12, 214 (1948-49). •

39, OTA, Jiro, Ishikawa, Tsuyoshi, and.Kosakai, Kaoru, Plating of an

Indium-tin Alloy , Kinzoku Hyomen Gijutsu 16_ (6), 246-50 (1965) (Japan).

40, RABINOWICZ, E.; Friction and Wear of Materials , John Wiley and Sons,

Inc., New York, 1965.

41, ROBERTS, A.G.; Improved irSS Abrasive Jet Method for Measuring Abrasion

Resistance of Coatings , ASTM Bulletin, No. 244, February 1960, p. 48.

42, ROBERTS, A.G.", Grouse, W.A. , and Pizer, R.S.; Abrasive Jet Method for

Measuring Abrasion Resistance of Organic Coatings , ASTM Bulletin, No. 208,

September 1955, p. 36.

43, RUBINSTEIN, Marv; Some Tips on Electroforming . Metal Finishing 54, C^)

58 (1956).,

44, RUML, v.; Nickel Coatings vith the Addition of Silicon Carbide , Metalloberflache 23, (2), 35-36 (1969).

45, SAIFULLIN, R.S., and Dryazgova; Lgad Plating and Nickel Plating from

Electrolytes Containing Dispersed Particles , Tr. Kazan. Khim.-Tekhnol. Inst.

Cmeni, S.M. Kirova No. _34, 160-5 (1965) (Russ.).

46, SAUTER, F.K.; Electrodeposition of Dispersion-Hardened Nickel-Al^O^ Alloys , J. Electrochem. Soc. 110 , 557 (1963); Tech. Rpt. WVT-RR-6204, AD 275956

(February 1962) . 47, SAUTER, F.K.; Electrodeposition of Dispersion-Strcnghtened Gold-Al^O^ Alloys , Tech. Rpt. WVT-RR-6321, AD 435622 (December 1963), OTS.

48, SAUTER, F.; The Electrodeposition of Dispersion Coatings and Oxide Stabilized

Alloys, Metall. JL8, (6), 596-600 (1964)
SAUTTER, F. and Chen, E.; Surface and Interfacial Enar^^y of Gold and Golcl-

. Al^O^, Trans. AI!-IE (1966). • • •

"

50. SHAVER, R., Withers, J., Proc. 10th Meeting of Refr. Comp. Vrc. Gp.,

Atlanta, USA (1965).

51. SMITH, C.R.; Electrodeposited Disperslcn-Hardencd Alloys---Kev to rligh -

Temperature Strength in Clad Pieces , (An evaluation of Corj::ercial

Applications), OTS-US, Dept. Cocinerce, PB 181,502; J. Metals 15_, (10),

^. 740-1 (1963).

52. SMITH, D.W. and P.D. Groves, A Study of the Mechanisns of Cer-et Electrcdeposition . Trans. Inst. Metl. Fin. 50, (1972).

•

• • • 53. SPIRO, P.; Diar.ond Bending by Electrof orning; and Elec tro-la tint , Industrial

Diamond Rev. 2S, No. 337, 533-538 (Dec. 1968).

54. SPIRO, P.; Electrof orr.ing—A Corr.prehens ive Survey of Theory, Practice ar.d

Cormercial Applications , (Robert Draper Ltd, 1968) .

55. STA-RCK, J.R., et al . ; Developrient of a Substitute or Inprove-.ent of

ChromiuTTi Electrodepcsits , Tech. Rpt. ;/53-271, Wright Air Dev. Cent.,

Contr. AF 33 (616)-234, PJ)0 No . 611-11.

55. SUTTON, W.H., et al . ; Inves tieation of Bonding in Oxide-Fiber (VThisker) - Reinforced Metals, Final Report, A2-IPvA Cr 65-01/4, July 1, 1964-July 31,

1965, DDC AD 630,359.

57. SUTTON, W.H., Chorne, J., Mehan, R.L., and Sauer, E.; Development of

Composite Structural Materials for High Tenperature Applications , Bureau

of Naval Weapons Contr. NOw-56-0176-c, February 1965, AD 466,957.

58. ' SUTTON, W.; Fiber Conoosite Materials , ASM, Symp. (1965).

59. SUTTON, W., Feingold, E.; Role of Interf acially Activfe Metals on the'

Apparent Adherence of Nickel to Sapphire , G.E. Tech. Info. Series

R65SD39, August 1965.

60. SYAURUKAITE, L., Khotyanovich, S.I., and Parfenov, V.; Electrolvtic

Coatings Produced by Simultaneous' Deposition of Silver and Finely

Dispersed Particles , Mater. Respub. Konf. Electrokhim. Litov, SSPv, Sth,

Vilnyus 1966, 97-102 ' (Russ)

.

61. TABOR, D-. ; The Wear Properties of Hard. Chroniua , Galvanatechnik 53 , (3), 114-21 (1962).

62. TOMASZEWSKI, T.W., Clauss, R.J., and Brown, H.; Satin Nickel bv CoDeposition of Finely Dispersed Solids , AES Technical Proceedings, 1963,

pp. 169-174.
63. TSVIKI, ^:asayasu and Ueno, Yasusada, Kel^^et Copper-lead Alloys from

Brush-like Copper Elec trodeposits

.

I. ElcVtirodeposition of Brush-like

Copper from Copper Cyanide Baths and the Preparation of Kelnet Alloys , Gifu Daigaku Kogakubu Kenkyu Hokoku No. 17_, 4A-52 (1967) (Japan).

64. TSUIKI, Masayasu, Ueno, Yasusada, and Suzuki, Takau; Kelinet Copper-lead

Alloys fro::i Brush-like Copper Electrodcposits , II. Electrodeposition of

Brush-like Cooper from Sulfate Baths , Gifu Daigaku Kogakubu Kenkyu

Hokoku No. 12, 53-62 (1967) (Japan). ' •

65. VAKIIIDOV, R.S., Markicheva, D.V., Pankova, S.M., and Kir'yyakov, G.Z.,

Electrolytic Deposition of Nickel-Phosphorus Alloys at Various Ter.peratures, Tr. Inst. Khim. Nauk, Akad. Nauk Kaz. SSR L5, 45-53 (1967) (Russ.).

66. VESELY, K., and Masarik, V.; Electrolytic Deposition of Satin Nickel

Coatines, Korose Ochrana Mater. 9_, 77-80 (1965) (Czech).

67. VEST, C.E., and Bazzarre, D.F.; Co-deposited Nickel-Molvbdenun Disulfide ,, A Self-Replenishing, Solid Film Lubrica^.t , Ilet. Fin. 65, (11), 52-53 (1967)

68. VISWANATHAN, M-. ; Occlusion Plating to form N'ickel Cermets , Metal Finishing

2i» 1 (1973) . . 69. WELL30R.N, Bonding Diamonds to >fetal Bases , U.S. Patent 3,465,416,

'

September 9, 1969. . •

' •

70. WILLIAMS, R.V.; Electrodeposited Composite Coatings , Electroplating

and Metal Finishing 19, 92-96 (1966)

.

71. WITHERS, J.C.; " Electroplated Cermet Coatings for Oxidation Protection

of Substrates in Excess of 2000°F , AMF, Jan. 1961, WADD Tech-, Rpt. 60-

718. Cont. AF 33 (616)-6807 .

•

72. WITHERS, J.C.; Reinforced Metal Composites , Prepared for 7th Meeting

O-f the Refractory Composites Working Group, Palo Alto, Calif. 12-14

March .1963. . .

•

73. WITHERS, J.C, and'Abrams, E.F.; Electroforming of Composites , Plating

55, (6) 605-11 (1968),

74. WITHERS, J.C; Electroplating Cermets , Products Finishing (August 1962).

75. WORN, D.K., and Marton, S.E.; Properties of Nickel Containing a Dispersed Phase of Thoria, (Mond. Ni Co., Birmingham, Eng.), Pwdr.

Met. Proc. Intern. Conf ., New York, 1960, 309-41.
Supplemental Publications1. Method of Producing a Wear-Resisting Surface on a Metal Element,

U.S. 2,999,798, Sept. 12, 1961 (Daimler-Benz Aktiengesollschaf t , Ger.).

2. Nickel-Al^O^ Alloys (dispersions), Watervliet Arsenal, Research and

Engineering Division, Watervliet, N.Y. OTS Report No. AD 275956, 75c,

U.S. Department of Commerce, Washington, D.C. 20025.

3. Codeposition of Inert Non-metallic Particles or Compounds with Metals

(Ni, Cu, Cd, Ag) , including SiC, Al^O^Wc and TrO^, Platecraft of

American, Inc., Buffalo, N;Y., U.S.A.

4. The Budding Technology of Submicron Metal and Oxide Powders (Feb. 1963),

OTS Report No. AD 181475, U.S. Department of Commerce, Washington, D.C.

5. Wear Resistance Surfaces, Financial Times, Jan. 17, 1964, p. 13; Copper

Abstracts 1964, No. 62, p. 8, Addition of carbide particles to plating

solvents

.

6. Dispersion Strengthened Alloys Become Commercial, J. of Metals,

561 (August' 1962) .

' ' • .

7. A Dispersion Strengthened Nickel Alloy, Metal Progress, 88-91

(December 1962)

.

8. New Technique Yields High-Strength Metals, Chem. & Engr. Nev7s,

40-41 (July 2, 1962)

.
LIST OF ILLUSTRATIONS

Figure 1 - FigurS^ 2 & 3 - Sigure 4 -

5 -

6 -

7 -

8 -

9 -

10 -

11 -

12 -

. 13 - - 14 - Figures 15 Si 17

Figure 16 -

" 18 - Figures 19 & 20

Figure 21 - Figures 22-26 -

Figure 27 -

28 -

" 29 -

" 30 - •

" 31 -

32 -

" 33 - Figures 34 & 35

Figure 36 -

" 37 -

" 38 -

" 39 - Figures 40 &. 41

Figure 42 -

Experimental Plating Bath Sketch

Cr Deposition on Cu Disc Showing Abraser Track

Deposit Cross-Section without Inclusion

Cross-Section of Bornhauser Deposit

Graph of SiC Inclusion in Cr

Uncoated Diamond Particles

Graph of Diamond Particles in Cr vs. TINO^

Graph of Current Density vs. Particles in Cr

SEM of Diamond in Cr

Types of Diamond Particles vs. Amount Included

Cross-Section of Cr With and Without Inclusions

Effect of Current Density on Hardness and Wear of Cr

Inclusions vs. TINO^ Content of Bath

Cross-Sections of Cr with SiC Particles

Inclusions vs. Particle Concentration in Bath

Included SiC vs. Wear-Loss '

. . Cross-Sections Showing Results of Method of T1N0„ Addition

, 1 3

Effect of Method of TINO^ Addition on Inclusions of Particles

Summary of Inclusions, Wear-Loss and Hardness of Cr Deposited

at Various Conditions

Effect of TINO^ Concentration on Wear and Hardness

Temperature-Current Density Conditions for Good Wear Resistance

Wear vs. TINO^ Concentration for Cr with Low Wear-Loss

Summary of Tests with New Particles

Summary of Performance of New Types of Additives

SEM Photos of B.C and B,C Hard Particles

4 6

Cross-Sections of Cr Comparing Effects of TINO^ and CeNO^

Effect of Bath Additives on Cr Structure

Included Particles in Cr Plated on Vertical Surface

Bath Aging Effect on Wear of Cr Deposits

Bath-Life vs. Wear-Loss of Cr Deposits

Performance of Various Cr Bath Additives

Effect of Bath Additives at Similar Conditions

Inclusions vs. Wear in Cd Deposits
Figure 43 - Summary of Inclusions in Various "Cd Deposits

" 44 - Summary of V.'ear-Loss of Cd with Included Particles

" 45 - Cd and Zn Deposits Containing B^C Particles

Figs. 46, 47, 49 - Inclusions vs. Wear-Loss for Zn

Figure 48 - Summary of V/ear-Loss of Zn Deposits

" 50 - Summary of Inclusions in Zn Using TINO^

" 51 - Cr Deposits with Inclusions on Inside of Tube

" 52 - Heat-Treated Cr Deposits v/ith Inclusions

Pv

Kin LH-ihj

STJKRlR

+

PVC GCVhxi

Cr03 SOL^. u^ytL

^SPLCIMLN DISC

IKSHU'XIGN

FIGURE 1. Plating arrangement for making deposits on a 3 3/4 inch

circular horizontal cathode. Underside of cathode is

insulated from plating current as is the cathode

supporting rod.

FIGURE 2. Experimental chromium deposit 5 mils thick on 3 3/4 inch

horizontal copper cathode disc showing wear track of

Tabor Abraser wheels. Center area not plated. Wear

resistance of deposit determined by weight loss.

FIGURE 3. Off-center Abraser wheels mark specimen surface ac

nearly right angles. Deposit contains 0.43 wt.% of

codeposited nickel coated diamond particles.

Original 330X.

1 V - »

.V'

/

*

FIGURE 4. Cross-section of deposit that appeared to have inclusion

of Ti02 but gave no positive analytical test for Ti.

Dark areas are probably oxides of chromium or small

voids in the chromium. Original 550X.

FIGURE 5. Cross-section of deposit plated at bO'/UO asd from the

Bornhauser bath plus 20 g/1 SiC. Deposit contained

10 wt.% SiC but hardness was only 243 KHN200 wear

loss an excessive 7+ grams. Original 350X.

T1N03 - g/1

C

*•

H o 3- o ID

P-c3 ni-( 3 o H'

u> rt

li

(U C: D rr

ro

03 o o o3 D n

3" ro

01 3 c ft

cn

i-i rrH" o O

3" 3

i-( O <: 3 ro H- 11 c CO 3 c

CO cr

&> rt 3

3" o M c • 3

rtO

I-" 05rt H-

(T> 3o

I-' 0> c

rt CO ON o o CO O

H"

0) 3 3

CL rt3* J> ro O

CL

m ro CO •oo

CO

tl HH- rr

rr CO 3-

N3

i-n o O3

(N

rr

I-' 3-

ro H- CD O rt

CU3

O.

03f1

FIGURE 7. A scanning electron microscope (SEM) photograph of

6-10 \im uncoated diamond particles. Original lOOOX.

T1N03 - g/1

00 ^ o oo 3 < n

TO

m 1—

1-5 c

CO (0 c Hn Oa o 03 cn u> 3o O c 3

sr

D

If rr

n o If 3 O 1 H- c C rr 3 f cr f-»

c» o

rr• 3

o.HH-' 0>

09 3

nO

fij 3

Q. O.

03rt

•t ON rt- O H- o fi O y-* fO

0> cn 3

O. )-»• 3

4> o O c

03 a.

cn ro a. a. I

Current Density - asd c

(0O o c o l-{ "I

ft)

M rr O fD o D

COHrr<

rt (D

i-f fD cnc w cn o

1-1 rt D_

S" fD c H> • en O

y-' C 1—1 n CD 3

H1-1 o 1—

O3 cn H- o S Hi o 3 3

cn Cr

(a

a

rt 3 3

3* o m 3 Of( OJ 1 rt

<«

<. 03 rt a^ ft o rt o H- n O

s: fD

03 rtor /~\ c^ Ln 1 OQ o

H' c3 H —

MZo 3

Cu

(D D. O n cnHrt

cn

i-h tio3

rt3-

(D

cnrt

033

CL

03

>-{ Cu
i
FIGURE 10. SEM photograph of deeply etched, nodular chromium

surface containing imbedded diamond particles.

Original 265X.

c

n:

a. H

o

O 'VO

(p cn o M rr i-pi o O CL

l-i 3 H- o 03 CB 3

O

cr 3

03 o CL

rr IfH- "O N 03 O i-J M 3 rr C rr Hcn C3 o M h-' Ui fD O cn OO 03n- c

h-" 3- cn O ro H O- CL

t— ro S O

(- rr

• 05rt

fDDro 0)rf 03<

ro oo 03

ro 3 033

O

c o 3

1 rr 0^O O

0>

It)

CO ro Q. 03n

H- zr 3

rt

rr3"a

ro

cn Hrr 3

0) n

3 t-" Cu c

03 a-

>-< ro

1—

1

3

n O

c CO

cnO

3

cnH-3

n

i-i

1 1-' K

rr

0^

N3

3

CU

&06

Figure 12 A & B. Cross-sections of similar chromium deposits

with (607) and without (606) the addition of

5 g/1 of thallium to the bath. Chromium plated

from 200 g/1 Cr03 standard bath at bC/AO asd.

607 contains 1.5 wt.% diamond powder.

Original 350X.

TO i C • Wear Loss - mg

O (-n .

U) fDo

rf

ft o

"O o

I—" c C I-! CO 1^

fj 1—' D

rr

(JO

t-^ en ^ rt OCO o O c ? •-! fD H* >-< n- C» Cl3 Q

CO 3

C/^ H1—1 ca rr1 3 C

&3

O • ?^

fD

rt)

O t3 O O

Q} tn rt HfD rT

D. 3

H- to OJ CL 3 fD O

CL 3

cn

O rr S CO CL 3

rt) CL

i-( CU

Co a.

rr

tsj Ln OOo n TO1— i

T1N03 - g/1

OQC

to CO o zr o m

1-'

H- ^ S3 no o

rt a- m

rr rro

l-h c c- 1—( 3

rr

O

M ZT

C

OQ < COHh-' n O3

5CC CO XT CO H-3

s: H- — o O M i-( O "O 1 -r £u K O r-{ rr rr • (U p- 3 n

ro

O H-3

CO a.

cn o

H- CO O Hrr •a cn H "O

rr

M H- OJ O rr M ro (D Q.

CO HCJ 3

rr

CO Oi rr Ui OJ o 3 O CL

to 3 CL o

01

cnCL
I
Particles in Cr-wt.%

Ui (-• Ui

i

Wear Loss - mg

> CXJ N) O

I

I

FIGURE 19. Cross-section showing distortion of deposit by the

addition of 5 g/1 TINO3. Plating had started

before addition was made. Deposit contained 1.7 wt.%

diamond powder. Original 350X.

FIGURE 20. Cross-section of deposit made with 1 g/1 TINO3 added

in increments, one-half first then two additions of

one-fourth at equal time intervals. Deposit made in

200 g/1 Cr03 bath plus 18 g/1 of 15 ym nickel coated

diamond powder at 55''/50 asd and contained 0.18 wt.%

diamond. Original 350X.

Inclusions - wt .%

cn si;

CO 1-^ O CP3 O

O riO

CD CD o rr

1-* rr w

Co Ml

CL. O

C- 1—

1 1. /— rr Q*

w t J

1—3 3 ^ rt

I w

Z3 6 cn 3

rrw

rt 3

O C

^^ 3

oj cr

(—' fD o

o o

3 i-n O rt) 3 »a

rr c

i-{ ca D (—

rrO 3

3 CL O

i-Ti ,r>c

(-> TO h-"
1

.urt

It tl

• n

HOm

»5

n

't :c

3

I

;e

18 (

! c Or

: a

It

(I!
o

U) o

CO CO

00

CD CO 00 00 oo 00

ho

00 00o 00

nC o f-t o

rr

a PT' Q. -a ! I 

n \ yO

rT

0)

H

cn Z J c Tl H' Q O n rr

rr C^ < Oo O 3

ro 4> X O 1 cnO

i-n Q.

H- 03 O rl n

1— o I—" c o

-a

rr o a

en 00

H

O "f/l • rr o

O- o 3

CD c i-l r; CC: 3 O rr rD Q CO O- (/: rr O

CO

rr

a

C

n_ c

rr i-( o O P-c

rro cr

I-! c rr ro rr ao i>

!t o 03 o

H- o

rr c c C/J

"O

r-1 h-

rr

O rr h- rt) C c 73

tfi

cr 1

rr 7]

r. o r rr

iJ

O 3

rr Q. n &)

rj < CL

cr

tj 3 J>O

rr o

rti ft7) 30

c. rr

'/J I-'

-+

03 1 CT»- • U7 : o , o

... I-, ' it - • T"!

'"

?o

•ft

!.::. • _ 00

7r i oO 3o

=1oc

cno3

rr^9

.1-

N3 oI

COoo

C3N O

ONO o
1
H-c

(13 N5

U)

H s: Zo l-t U)

I-' 03 0

!3 CO a. CO

I-' H- 1 La H

00 tDH"

h-" P»H* ^ 0

*-*

rr0 0 rr

X- 0) 0

CLd

(0

CO 0 CO0

rr Ml

Ca a. w m

H- 0

CO CL HH- rr

CO

COrt Ml a

CL 03

COrf

013

cu

03M

Q.0

(W

l-» n0

<y

03rr=r

"Oc

CO

ON o o

00 o—I o

C^

OO

O

03o

COCOI 3

a:

o>M

CL

ro

COCOI ?^ M

N3 h-" o o oO hO o o o

00 OJ o o ooooo

N3oo : O; o - I — I1--

U3

r -H— -t--

--4:-::,

r

o!

]}]:n—4- • 1 -- I

-Uv, j• -,o 1 OJ o w

rt 3O

(-> c

COO

CO oI TO

COO

-Po
•r

V


>Ti

1-1-

ftl NJUl

cap.

(-{ C- o

g M

o Cfl p. p.

J3 Q f>^ fD p. 1^

lU 01

J—

S3 o

f-* iJ

(i

U* w

pfLnLn (-^

>-*-

Ln (X) cn

CO 0)

CO o

G. Hi

>« CL

ra fD

>;o O

fD CO

pf

cn

53W Hi O g

cnrr ^ a:3

Cf. fD

>-( M- a. D

Q. ro

(-^ o

n o

3Jrr 0T3

fti Q- o

o

3:

CO H

z

o

4> CO O

4:> 4>

4>- 4> C

U)

t-i Z fD U) O C/5 CO • rr

O

o

o

o

00

I

• •

•

-• —

o

COo

o

1 -

O

o

-tQ-

"^-f--^ -t-

!o::

iW <3o— -l>^-

- I h ! r

;io-;

! ica

4-: —

033o

3

a3

O

I rt

..J —-4 -

w w

Ul n n cno-T

LnO

Ln

Ui Ul

<^ , N3 J> UJ O O O O



Figure 27. Effect of Tl concentration on wear and hardness at 40°/20 asd.

No particles added to bath.

C

OO

Wear Loss - mg

H o

n>3 o

fD

O (-i rr 03rt o

OJ

C

f-< U)

(-' fD1 o a n

to c

•o ^^ o o 1^

CO fD H' o

rt rt u OfD

—

tu cn rt HO

ro rt

4:-

cu Hi Ul

rt o

rt 0

a.

ro fD m •a j:>

fD o

cn

H ^— o H» fD -O o rt 0 0 cn •a

D> • H- s: 4>« rt o

H- rt o O3 0 cn CjqO

:r

O 4>

Ui

a*

€ C3N s: fD 0

(D 0>

C3n Ui

ri U1 o (B rr CO Ln H- 0 CO

03 rt

fJrr

(I> o

t-« fD Hcn 3

rt 03 H-O fD

fD Q rt C

03 U3

03

cn 00

W 0*- 0

0. H-3

•0M03rtH-3

OQ0*

03rth.
I
Wear Loss - mg

C o s:

rr fD

53 i-i I—" <

ro

ID COc o cn cn H

rt 1—'

CO oo

03

O

rt • CL HiO

03 t-{ ft CL

rt (t) cr 'a

(0 o

(0 (0

(0 Hrt O W O

O P SI to

a. H- H- rt 1 rt p" o s;

CO 03n

03M

a. o

CO

si CO

03 CT*

I-i fD

t-' o o

p' s;

I-I ON

03o 3

rt era fD •

I-i HCDrtH- 03 O rt

CO ft) (X

(D ua s: C H03 rt M P" M^ C>3 O

03oo CO c*- • oP

03

oo oroooooiNj—'coro—'O—'O—'O

cn o

O -F=« -P» ro CO ro

viD CO —' ro CO —I -p» ro ro o ro cn CO

-pi O ^ CO —• CO UD ^ —

'

E

fDO

r+

ro

tor+Q.

fD T3O

CO

-J. rt

u>

r+3

fO

fD

to acu.

-s

fD

O

<->• c

=5

fD

-so

to3

to roo

ro

c+ o OJ o

4^ -5 cn o.

o 13

(X> CO to O CO

1 0)

CO 3: o.

NJO o O

o

o

to

I

r-l- 5«

O

I to

O

ocucr o o oI 00

a.

CO —

o o

3

too

cno

ro CO O too o

M

CO OO o <r; o -'• :3 \

O fD --

CJ

I'D to

o o o o o o o o o o C_) <—

' o CPi CO

CO —

1

CD ro CD

tn CO <J^ —'. CO o cn O

O o o

—

1

CO to 00 en to 3

O

c

o*

I

zz

Oi

I CO 3=>

CD O

IN3 tn cn cn —

>

O

I t\3

roo

ro

cn -t. cn

cn

cn COo O

COo

cnO

CO ro —I —I ro o

in

2> O CL

O) U2 CL

<

Figure 32. Deposits made under similar conditions using 1 g/1 CeNO^

(top) and 1 g/1 TINO^. Note the lesser distortion (large

dark areas, roughness and fissures) of the chromium structures by the CeNO^ for roughly similar amounts of included

material

.
1 i II 5
Figure 33. Comparison of effect on structure of 5 g/1 LiNO^ (top), about 4 g/1 NH^NO^

(center), and 5 g/1 TlNO^. Wear for the deposits would be less than for standard

chromium! Appreciable inclusions were contained in all, but were loosely held in

the discontinuities rather than firmly anchored in the chromium matrix.
I
Figure 34. Comparison of structure of deposits at 1 g/1 (top) and

1/2 g/1 NaNO^ additive In plating bath. Roughly the same amount of Sic particles (0.3-0.4 wt.%) were Included In

each deposit. Some of the larger dark areas In the top

photo are considered to be discontinuities In the chromium

rather than Inclusions.

Figure 35. Chromium plated on a vertical surface with included

silicon carbide (0.45 wt.Z) from a bath containing

2 g/1 CeNO^. For comparison to a roughly equivalent

horizontal deposit , see top photo in Figure 7.
1J 1
Figure 36. SEM photos of B4C (top) and B^C hard

particles at about 1600X.
I
to

<De

3

T3

•H

g3 O

M to

nJ 1—

(

o

to

+-> M

•H 03

t/5 O& CQ

f—

1

<+-( o O

a to o

-oc c

o

to

•M o

o

t-i

'4-1 rH GOC•H to

to

nJ fco •H P

•H

oa g3 +J

-c; o

o

CO

60 •H

to CN

18-



to

<N

M

to o

i-Hto oo

CM

•H

(D . to (fl rH O -H > 4J •H ^

»^ +J oJ rH •H

p3O 3 <1) O fii •H 'J) >O -H3 ao

J-i O

0)3

ta

•ri oCM

00 \0 CO

-20-

Figure 40. Comparison of effect of bath additives

under similar plating conditions.

-21-





Temp. = 24^C

C = Current density in asd

Inside ting = g/1 particles in bath

Radii = Inclusions 0-3 wt. %

I 1

Figure 43. Amount of inclusions in cadmium deposits.

Temp. = 34°C

C = Current density in asd

Inside ring = g/1 particles in bath

Radii = Wear loss . t^Q

.

Figure 44. Wear-loss of cadmium deposits with included particles.

Figure 45. Cadmium (top) and zinc deposits containing B^C particles plated from cyanide baths at 24"'C/1 and 3 asd

respectively. No etch.
ll
00

to o

r—

4

o

P • r—

N

•H U 1—

1

o O CN

1—

t

•H -P X

M

O P

•P 4-1 oj

>—

o -a ^ -H o I c

•H fn oi

t/J 3 (D O

t—

1

3

O oj CO

•rH 3 C

'y) -H

to ?-« O (U T) > <D I—

1

P

< -H

p: to o o

•H

r-Hoc

b1

\0

D

00

•H

Pi:4

O

\0

o o

(Sai) ssox j:b3M

-28-

19.6

CO

3

o

•Hp

•H

10 4J •H

(/» O

Oh

t—

s

(D . r—

1

1 o o

I—

1

•H X Nj ^_)

o\« O X +J M-l -P

O 0) o 1 -H •H 5h C

(rt 3 O X 1—1 5 O

O

V) c3

1—4 3

CO S

^1 o

CQ > ^

c

o

•H

in

I—

I

o

S3-

0)

o oCM

(Sui) ssox JBOM

-29-

Figure 48. Wear-loss of zinc deposits with included particles.

CO

00

\0

(U •p

l-l p

•Ho

0} • -a to o

O --H

/—

\

1—

i

1 I/) e o O -H

I—1 t/i X

(U o 3

p

3 m

P P

tn

oi X

o > +-» •H

VI O XI

•H (U •H

t—

(

•H Oj CJ

If) o

ca O oJ •H

VI C

3 -H

I—

1

o

1—

(U3

CO

•H

O o

CM

(Slu) ssox j:HaM

-31-

TiN03

Temp. = 24°C B4C - 30 g/1

C = Current density in asd

Inside ring = g/1 TINO3 or TICI

Radii = amt. inclusions •'^0 %

Figure 50. Inclusions in zinc deposits using thallium.

Figure 51. Chromium deposit on inside of stainless steel tube 3/8 inch ID

X 20 inches long. Chromium deposited at 45°C/30 asd in tube in

vertical position from bath containing 3 g/1 11 \'03 and 30 g/

1

B4C. Cross-sections taken from top, center, and bottom of tube

Hard particles resist polishing and leave "tails" of raised Cr.

No etch.
A