RD-A ( : -^

/j TEGHNIGAL LIBRARY

AD "■- ,

'-■■

T' U ' ^

EN-79-03

■

"■• ,

■

VESSEL SYSTEM OF PHOSPHATING

FERROUS ALLOYS UNDER STEAM PRESSURE . !

■ • - ■ T ■ 7 \-r- '' r - - -• ■ ?

■ -

- ! ■ -

by ■

■

- : r "% r _. ■

i .u / ^yr-^^-^r^ ^ -: -~- •> ^ £%

HENRY GRAIN /

J ' ■

- -- ~- ' " T\ _ - 1 , - .. . - S-L,

; - i^ ■■-■ i and - r < *. ' : •- : -'

" ■' "".. : r LINDEN H. WAGNER .."" *- t .^ -' ' v, ' \ " -. ■- . i 1

■■ "-. '■f-\

■ - • .-»■

-rf^' ■

^^~'"'J r

1 ■■ 1

r ;._ •

- 'x ■ :; - - '■■ ". *

■ \

1 . /■■ ■

-f 1,/ —

■■'. AUGUST 1979 / - - , \ ■

■

;. -f. ^_, ■ ■ ";, . .

■

■

■

■

1

1 .

... ,-, i.

■

* '.

J

■

• , r

— —

ENGINEERING DIRECTORATE

i

Approved for public release; distribution unlimited.

' j J.

■

r

:

i - e,' ^.^ ,..

■r "■*

ROCK ISLAND ARSENAL ROCK ISLAND, ILLINOIS 61201

J-. <■■■■

- i '■'; " >

-J i

I -

■

■

• ^ ■

■

\ ■ -- ■

-

■

I.

DISPOSITION INSTRUCTIONS:

, r > ■

.

> •

i - i

Destroy this report when It Is no longer needed. Do not return It to the originator.

DISCLAIMER:

' ■ ■

uiiULMintu:

i

The findings of this report are not to be construed as an official Department of the Army position unless so designated by other authorized documents.

'■ ; '

■

.

.

/ I

\

J

/

.

'> " \

'

1

1

'

.

•> ■

'

■

■

■ ■ '

-

UNCLASSIFIED SECURITY CLASSIFICATION OF THIS PAGE (When Data Entered)

REPORT DOCUMENTATION PAGE READ INSTRUCTIONS BEFORE COMPLETING FORM

I. REPORT NUMBER

EN-79-03

2. GOVT ACCESSION NO. 3. RECIPIENT'S CATALOG NUMBER

4. TITLE (and Subtitle)

A DUAL VESSEL SYSTEM OF PHOSPHATING FERROUS ALLOYS UNDER STEAM PRESSURE

5. TYPE OF REPORT & PERIOD COVERED

Technical Report

6. PERFORMING ORG. REPORT NUMBER

7. AUTHORfa;

Henry Grain and Linden H. Wagner

8. CONTRACT OR GRANT NUMBERfeJ

9. PERFORMING ORGANIZATION NAME AND ADDRESS

CDR, Rock Island Arsenal ATTN: SARRI-ENM Rock Island, IL 61299

10. PROGRAM ELEMENT, PROJECT, TASK AREA & WORK UNIT NUMBERS

AMS Code 3297.16.6785

1 1. CONTROLLING OFFICE NAME AND ADDRESS

CDR, Rock Island Arsenal ATTN: SARRI-ENM , Rock Island, IL 61299

12. REPORT DATE

August 1979 13. NUMBER OF PAGES

21 14. MONITORING AGENCY NAME & ADDRESSff/d/f/orenf from Controlling Olllce) 15. SECURITY CLASS, (of thla report)

UNCLASSIFIED

15a. DECLASSIFI CATION/DOWN GRADING SCHEDULE

IS. DISTRIBUTION STATEMENT (ot thla Report)

Approved for public release, distribution unlimited.

17. DISTRIBUTION STATEMENT (of the abatract entered In Block 20, It dltterent from Report)

18. SUPPLEMENTARY NOTES

19. KEY WORDS (Continue on reverse aide If neceaaary and Identify by block number)

1. Phosphate coatings 4. Corrosion resistance

2. Manganese phosphate 5. Pressure process

3. Heat resistance 20. ABSTRACT fConfftiue MX r«verM al-da if nenevary ami identify by block number)

A dual vessel system of phosphating ferrous alloys under steam pressure was investigated for the application of high temperature corrosion resistant coatings on a continuous production-type basis. In this system, the phos- phating bath can be transferred from one vessel to another using differential steam pressure. Either vessel can be used as a phosphating or holding tank and the bath can be maintained continuously under pressure. Sludge can be removed from the bath during the transfer of solution to the other vessel, and

nn F FORM AN 73 1473 EDITION OF I MOV 65 IS OBSOLETE UNCLASSIFIED

SECURITY CLASSIFICATION OF THIS PAGE (When Data Entered)

UNCLASSIFIED SECURITY CLASSIFICATION OF THIS PAGEOWien Data Entered)

20. ABSTRACT (continued)

the bath can be used continuously on a production-type basis. Four types of manganese enriched baths were used in testing the dual vessel system. Salt spray corrosion testing was divided into two groups: unheated panels and panels heated to '♦SO'F for one hour. Results from the manganese tartrate enriched bath best illustrated the success of pressure phosphating using consecutive produc- tion-type runs in the dual vessel system. For this manganese tartrate bath, 30% of the heated and 8]% of the unheated sets of panels passed a minimum 100-hour salt spray resistance test. Continuous control of free (to less than 3.5 points, and total acid (to above 30 points) values and proper maintenance of the bath with chemical additions after each processing period are needed for reproducible superior heat and corrosion resistant phosphate coatings. A manufacturing level phosphating capacity and the design of a sludge recycling system is recommended for utilization of this process in the application of heavy manganese phosphate coatings to ferrous metal items. (U) (Grain, Henry and Wagner, Linden)

i i UNCLASSIFIED SECURITY CLASSIFICATION OF THIS PAGEfHTien Data Entered;

FOREWORD

The project was carried out under the title "Application of Heat and Corrosion Resistant Phosphate Coatings." This work was authorized as part of the Manufacturing Methods and Technology Program of the U.S. Army Materiel Development and Readiness Command and was administered by the U.S. Army Industrial Base Engineering Activity.

i i i

CONTENTS

Page

DD FORM 1473 Report Documentation Page i

FOREWORD • " <

TABLE OF CONTENTS iv

TABULAR DATA

INTRODUCTION

PROCEDURE

RESULTS AND DISCUSSION

CONCLUSIONS

RECOMMENDATIONS

DISTRIBUTION

15

16

i v

LIST OF TABLES

Table Page

1 Chemical Control of Manganese Phosphate Bath 5 Enriched with Manganese Citrate

2 Physical Properties of Manganese Phosphate Coatings 6 Enriched with Manganese Citrate

3 Chemical Control of Manganese Phosphate Bath 7 Enriched with Manganese Gluconate

k Physical Properties of Manganese Phosphate Coatings 8 Enriched with Manganese Gluconate

5 Chemical Control of Manganese Phosphate Bath 9 Enriched with Manganese Tartrate

6 Physical Properties of Phosphate Coatings 10 Enriched with Manganese Tartrate

7 Chemical Control of Manganese Phosphate Bath 11 Enriched with Manganese Dihydrogen Phosphate

8 Physical Properties of Manganese Phosphate Coatings 12 Enriched with Manganese Dihydrogen Phosphate

INTRODUCTION

Manganese phosphate coatings are conventionally applied to ferrous articles by immersion in a phosphating bath operated at 200oF - 210oF. These coatings are required by Specification MIL-P-16232 to withstand a 1-1/2 hour salt spray test (ASTM B117).1 The coatings are applied to military small arms weapon components when low reflectivity and corro- sion resistance are desired. They also serve as a base for the supple- mentary application of lubricant for increased corrosion protection. At low temperatures, phosphate coatings retain their protective proper- ties; however, at temperatures above 230oF, they deteriorate and show a large reduction in corrosion resistance.

Recently, a new and improved manganese phosphate coating has been developed in this Laboratory. The new method of phosphating produces superior corrosion resistant coatings capable of withstanding tempera- tures up to i»50oF. The coating can also withstand the 5% salt spray test for more than five-hundred hours. This represents at least a hundred-fold increase in corrosion protection over that of conventional manganese phosphate coatings. The new method of phosphating requires bath temperatures above 2150F using steam pressures in excess of 1 psig and additions to the bath of either manganese citrate, manganese tar- trate, or manganese gluconate. A previous report2 on phosphating using steam pressure, describes a batch processing procedure. The report on the dual vessel system describes the continuous production of superior manganese phosphate coatings on a pilot line.

PROCEDURE

The apparatus for producing superior phosphate coatings consists of dual vessels shown in Figure 1. This system has the following capabilities

a. The phosphating bath can be transferred from one vessel to another under differential steam pressure.

1Annual Book of ASTM Standards, American Society for Testing and Materials, Vol. 7, 66, 1970.

2Wagner, Linden H., "The Application of Heat and Corrosion Resistant Phosphate Coatings Under Steam Pressure," Rodman Laboratory Technical Report R-TR-71»-012, March 197i».

10

a: Q-

en LLI

Q- 00 O

O

00

<

EC

C3

b. Either vessel can be used as a phosphating or holding tank.

c. The bath can be maintained continuously under pressure.

d. Sludge can be removed from the bath during the transfer of solution to the other vessel.

e. The bath can be used continuously on a production basis.

The vessels are joined together by a two-pipe system. An upper 1/2 inch pipe connecting the vessels near the top is used to purge the system and equalize the steam pressure. The lower 1-1/2 inch pipe has two valves which can be operated manually to control the flow of the solution between the vessels under pressure. This pipe joins the stainless steel inner processing chambers. A steam gauge and a sight glass are attached to the system for monitoring pressure and liquid level. The liquid level can thus be observed during the transfer of the solution. A steam regulating valve is used to control the flow of steam to the inlet line connected at the base of the vessels. Steam traps at the base of the vessels control

the flow of condensate.

The stainless steel liner in each vessel has a capacity of 8.0 gallons (30 liters). Each of the containers and the phosphating solution are heated with steam. The processing-procedure was as follows: Steel panels (SAE 1020, 2 x 3 x 1/16 inches) were blasted with #80 steel grit. They were then suspended on a rack and placed in the phosphating bath at 170oF to l80oF. A constantan-copper thermocouple was inserted into the bath and connected externally to a potentiometer. The lid was bolted in place, and the steam turned on. Air was purged from the vessel, and the purging valve was closed. Steam pressure from 1 to 1-1/2 pounds per square inch gauge (psig) was used to raise the temperature of the bath to 212° - 2130F. Steam pressure was then maintained at 1 psig so that the temperature of the bath remains constant. The time of processing was continued for an additional 15 minutes. The bath was then transferred to the other vessel under a slight differential in steam pressure. Pressure on the phosphating vessel was released and the lid was removed. The coated panels were placed in the rinse tank. Recycling of the bath was accomplished by increasing the steam pressure of the holding vessel there- by forcing the bath to return to the processing vessel.

For chemical analyses, free acid and total acid determinations were done on 10-mi11i1iter samples of the bath. These determinations were done by titration with sodium hydroxide (NaOH) to a phenolphthalein end- point for free acid and a combination methylorange-xylene cyanole for the total acid. Values are listed in points (mi 1111iters) of 0.1N NaOH to reach the endpoint for a 10 mi Hi liter sample.

To control the free acid content of the bath, manganese carbonate (MnCOa) was added. This addition was usually necessary after each run since the free acid value would rise after processing. The addition of manganese dihydrogen phosphate [Mn (HzPOit^l , served as a replenisher for the loss of manganese and phosphate as coating and sludge during processing.

Four sets of evaluations were conducted on the dual vessel line using different chemical additives. These included: manganese citrate, manganese gluconate, manganese tartrate additions and no manganese-

organic compound addition.

The coating weight of panels, an important value for assessing coat- ing quality, was determined by weighing the panel with the coating and subtracting the weight of the panel with the coating removed by stripping. Stripping was accomplished by immersion of the panel for 15 minutes in chromic acid solution heated to l80oF.

Salt spray testing was used to determine corrosion resistance. The testing was done according to ASTM (Bll?). Visual examination of the panels labeled the coatings a corrosion failure if three or more rust spots appeared. For comparative purposes, an arbitrary standard of 100 hours salt spray resistance was selected to denote a successful protec- tive coating. Salt spray testing was divided into two groups: unheated panels and panels heated to kS0°F for one hour. Heating was done in an oven at atmospheric conditions.

RESULTS AND DISCUSSION

Presented are the results of consecutive phosphating operations used to test the production-type dual-chamber pressure phosphating apparatus. Tables 1 through 8 display the phosphating results and analyses for each of the four types of baths. Specifically, Tables 1, 3, 5 and 7 show the chemical analyses (free acid and total acid bath content before process- ing), and chemical additives (additions of manganese dihydrogen phos- phate, manganese carbonate, and manganese-organic compound to the conven- tional bath). Tables 2, ^t, 6 and 8 show the physical characteristics of the coating. They display the weight of the phosphate coating in milli- grams per square foot and the salt spray corrosion resistance in hours for both heated and unheated panels.

The first series of tests were conducted with manganese citrate ad- ditions to the bath. These tests were done in two separate cycles of three and four consecutive phosphating runs (Table 1). Salt spray re- sults presented in Table 2 show only 1^^ of the heated and 23% of the unheated sets of panels passing the 100-hour minimum salt spray corrosion test.

2

-a XI <

O I c

o a. :r

CM ro J- I — ^ oj CN

o tn UJ E

01 00 UJ ai en

s O o o (_> CTVCM tn c fmm

s (U > S

o o o o o o CM CM CM

vO

o o vO CM

O O O O CM P^\

en

a oo LU < h- h-

Q- T3

i a: O o < vD crv-a- O co o ro cr\ n ■ • • • • • • •

Q- 2 — r^ f* LA <T>— O O co

Ul 00 Ul 4-1

c

4-1 o

ro ro ro ro ro ro ro ro

1 1 ^

0) "O

LL ^ o o > < _i

^— CM ro ro — O CM CM OO to <u • • • • • • •

o

H

c QJ ro-a- -a- ro-a- ro-T ro <

Li. z o LU o O

—1 g 5 Ol UJ T3 C >

z: C — IT} (/)

< QQ < LU 3:

M C 0) (U (U (U 3 ^^ — CM ro — CM ro J-

<J

o o QC

> O >•

o Q-

< of

to LU

<

<

3 Q LU

O

^—^ XI in (U i- ■M 3 <n J-J- JT o a)

-C c =3

in 4J in (U 1- U.

o > O (0 un i_ -a- a

00 -o CM PJ CM

■u ■M m

(D V GO i:

-3- O O CM CM CM

-a- -a- O CM CM

l^)

CM

< o o

Q-

o

CO

< C3

u. o oo

0. o a.

< o

oo

^^ 4-1 o o

it-

en CU c t-

MM (D 4-1 3 nj cr O U1 o

u n- 0) o Q

4-> in -C E Ol ro

i_ '<u en 3 —

^— ■—

3

0O LTV P^ -T LA0O r^ ^r vD -a- -a- ovo -a- oo en 0~> (J^vO unco cr> — CM IXWD CM j- urvvo -a- LA

(3> -o C c < n? in

in c (1) 0) 0) 3 PM

U o: o "o O > > u o o Q-

C3

LU > <

— .— CM ro

CO

(U

>- o

CM ro-a-

TABLE 3

CHEMICAL CONTROL OF MANGANESE PHOSPHATE BATH ENRICHED WITH MANGANESE GLUCONATE

Cycle and Analyses (points)

Processing Run Free Acid Total Acid

Cycle A

2 3.'. 3.8

31.0 30.1

3 "1.7 3.5

28.5 27.1

5 6 2.2

38.0 26.2

7 8

3.5 3.3

30.3 27.1

Cycle B

1 M 3^.7

2 3.3 30.1

3 3.8 it.3

31.7 30.8

5 6

3.6 3.5

IS.* 33.2

Cycle C

1 2

2.9 3.3

25.3 26.3

3 2.8 23.U 23.S

5 6

J.'t 3.0

28.8 27.9

7 8

2.2 2.2

2l|.6 26.0

AVERAGE 3.'t 29.6

Add i tIves (Grams)

Mn^POiJit MnCOa Mn-gluconate

100

llOO 200

200 200

200

200 200

200 '♦20

210

120

150 180

210 210

210

I6'(

100

350

350 100

300

200 100

200 150

150

120

150 180

210 210

210

I^O

10 10

10 11

II 12

12 13

10 11

II 12

13 1ft

10 11

12 12

12 13

yk 15

12

TABLE k

PHYSICAL PROPERTIES OF MANGANESE PHOSPHATE COATINGS ENRICHED WITH MANGANESE GLUCONATE

IZllsT^ Wei3ht 0f Coat^ Sa.t Spray TestS fa^

— (milligrams per square foot) Heated (^"F)

Cycle A

1 2

3

5 6

7 8

Cycle B 1 2

3

5 6

Cycle C

5359 '•378

5876 11(69

7886 9288

93'i7

81(12 6509

103711 6676 ^B

Unheated

100 100 5 3

775 150 1 3

775 768 775 720

775 720 6289 672 'j%

ItH lkk '•32 6953 7'.'i 71,/,

7't'i 7kk

7it|t 7it't 7i|ii

J fS I S'89 24 q ^ 1272

5 1659 6 71(66

i I

5 I

1 | 600 )oo

6,76 ] 5

AVERAGE 6117

TABLE 5

CHEMICAL CONTROL OF MANGANESE PHOSPHATE BATH ENRICHED WITH MANGANESE TARTRATE

Processing Run

9

Analyses (points NaOH)

Free Acid Total Acid

1 3.2 32.3 2 k.k 31.7

3 it.l 32.1 k 2.7 29.8

5 y* 31.7 6 2.1. 30.6

7 3.5 29.J 8 2.8 21..8

2 6 26.6 5 2.8 25.9

11 2.6 27.3 12 2.6 29.1.

13 2.8 27.2 |l, 2.6 21.1

15 3.1 26.9 16 3.1. 26.2

17 3.3 25.8 ,8 2.6 29.0

19 3.1. 25.9 20 2.7 23.8

21

MnCHzPOu): MnCOs

160 260

Mn-tartrate

100 200

10 11

200 200

200 11 12

200 100

200 100

13 14

200 200

200 200

15 16

200 200

200 200

17 18

200 210

200 200

18 19

21.0 300

200 19 20

210 60 180

21 22

210 21.0 90

22 23

- 60 23 21.

21. 2.7 22.1.

AVERAGE 3.0 27.6 152 ■'•O .8

TABLE 6

PHYSICAL PROPERTIES OF PHOSPHATE COATINGS ENRICHED WITH MANGANESE TARTRATE

Weight of Coating Salt Spray Tests (hours) Processing a ■

Run (Hilligrams per square foot)

1 8107 2 l\\09

3 601(9 k Sk37

5 7537 6 8640

7 TtJS 8 7417

9 9825 10 11030

11 8252 12 9309

13 7380 14 6582

15 5935 16 7268

17 7735 18 10360

19 6970 20 9314

21 5182 168 72

AVERAGE 7808

Heated (450°F) Unheated

840 30

840 24

6 840

6 336

840 336

336 336

840 840

30 840

840 840

840 840

840 840

120 840

840 840

100 840

840 840

100 120

840 840

840 840

100 840

408 840

10

CQ <

a. CO O X

CD O

a > x

< C3

3

z LU

< 00

10 E TO 1_ Dl

T3 XI <

T3 C

o Q. E O a o c m u o I c

(U a) 0) 0) 0) 0) OJ 0) cu <u c c c c c c c c c c o o o o o o o o o o c c c c c c c c c c

o o O O o o o o O O ^D vD ro (ricr» CM (SJ vD vD LTVOO O

o a. x

m LTV CM -a- vo in o o o o ro <r» LTV o o OA *— CM c^

< X Q.

o X

00

< z <

o

o o

<

o

O

in (U in >- TO c <

LTVLTv CMO r^-d" J-ro JTLA

cvi csj CM CM CM CM

OO vO CM CM CM CM CM CM

CM

O-J- OOn-* OvO -^--3- LAO

cn c in in c <D 3 O a: O L.

UJ

a: LU

<

— CM CA-3" LAVO i—co cr\ o

11

i a. o

z LU

o a >-

LU

UJ z

3:

3

a: z

^—, T3 w 0) l_ -u VO O LTVOO ooo CO o o -a- 3 •D CO O -a- o o o -a- vo o 0) m — — -a- r— CM CM

-C c

in ■I-J ^ 0 l-

u. > 0 nj O s_ LTV Q. -a-

CO oo-a- oo -a- o o o o o o XI O vO JT VO -3--3- -a- -3- -a- -a-

+-I (U 4-1

-a- ts CM CM oo oo oo oo oo TO TO

oo (U

00 O0 CD

< < O o

Q-

O

to LU z

o CO

I- CC LU Q- O

<

OO >-

^^ 4-1 O O

u- Dl 0) C 1_

TO +-> 3 TO cr o tn o

\~ u- 0) O a

4-> in ^ E

CT1 TO • — U <U C71 3

^— '— 3

I^Cl —\0 LACM -a-vO rrvO COUA voro o^ir^ r^cv-\ OOCM CM— in-a- <r\<T\ o-a- o^o r^.oo ir\oo vo so r-»oo vo oo

oo CM

en c in in c 0) 3 o cc o t-

Q-

C!3

LU

— CM c^-g- LTVVO r>.0O CT> O

12

The second series of tests used manganese gluconate additions. These tests were conducted in three separate cycles of 8, 6 and 8 pro- cessing runs (Table 3). Salt spray results given in Table k show 53% of the heated and 6h% of the unheated sets of panels passing a 100-hour minimum salt spray test.

The third series of tests were conducted with manganese tartrate additions to the bath. in this test 21 consecutive runs were performed on the same bath (Table 5). Salt spray results in Table 6 show 30% of

the heated and 81^ of the unheated sets of panels passing the minimum 100-hour salt spray test.

Finally, testing was conducted without any manganese-organic com- pound addition to the bath. Only manganese dihydrogen phosphate for bath replenishment and manganese carbonate for free acid control were used (Table 7). For this bath, ten consecutive runs were conducted. Salt spray results of Table 8 show 70% of the heated and 30% of the unheated sets of panels passing a 100-hour minimum salt spray test.

The manganese citrate phosphating results were the poorest. Low salt spray corrosion resistance can probably be attributed to high ini- tial free acid and insufficient additions of manganese compounds. The average initial free acid content of this bath was 3.8 points. This is higher than the 3./t, 3.0 and 1.2 point averages of the other baths. A high free acid bath content will produce a thinner phosphate coating, and consequently this coating will provide less protection against corro- sion. Also, the amount of manganese citrate added to the bath is small when compared to the amount of manganese organic compound added to the manganese gluconate and tartrate baths. Initially for this project, small quantities of the manganese-organic compound were added to the phosphating bath. This was the case for the Mn-citrate bath. Later, for the Mn-gluconate and Mn-tartrate baths, larger amounts were added to improve the coatings and obtain better corrosion resistance. The amount of manganese dihydrogen phosphate added is also lower than the amount added to the other baths. This lower bath concentration of Mn(H2P0it)2 results in thin coatings of inferior corrosion resistance. This combination of high free acid and low manganese compound content yields coatings for this bath that are unable to meet a 100-hour minimum salt spray test.

Results from the manganese gluconate bath varied. Cycles A and B produced good coatings, while Cycle C yielded poor coatings. A plau- sible explanation for the poor corrosion resistance of the coatings pro- duced from Cycle C is the low initial total acid content. This low value of total acid means insufficient manganese dihydrogen phosphate in the bath. Thus thin coatings with poor corrosion resistance are pro- duced. The minimum value of initial total acid should be at least 30 points for reproducibly good coatings.

13

The results from the tartrate bath are the best for illustrating the success of•pressure phosphating using consecutive runs in the dual vessel system. The bath produced the greatest percentage of sets of panels passing a minimum 100 hours in the salt spray. Additionally, 76% of the heated and kj>% of the unheated sets of panels exceed 800 hours of salt spray testing. A total of 21 consecutiye processing periods demonstrated the success of production-type pressure phosphating.

The bath without any manganese-organic compound addition was also successful. Larger additions of manganese dihydrogen phosphate were substituted for the Mn-organic compound additions. The consecutive num- ber of runs could have' been extended; however, ten consecutive runs were

■considered sufficient to illustrate the success of the bath and procedure. I

These series of tests conducted on the dual vessel phosphating system show that successful production-type pressure phosphating is possible. Limitations for the process exist with the large amount of precipitate deposited after processing. A sludge recovery unit for con- verting the precipitate to the useful form of manganese dihydrogen phosphate would most likely need to be installed for the system to be production feasible. As shown by the results, careful control of the bath is also needed to produce good quality coatings. Initial free and total acid must be carefully controlled. The bath must also be maintained with chemical additions after every processing period to replenish the depleted bath. With proper maintenance of the bath, the reproducibi1ity of pressure phosphate coatings having superior heat and corrosion resis- tance should be easily obtained.

CONCLUSIONS

1. Manganese phosphate coatings of high quality can be applied con- secutively under carefully controlled conditions on ferrous metal items processed in an enriched bath under low steam pressure.

2. A phosphating bath operated continuously under constant pressure requires frequent replenishment and acid control to function properly. To operate the bath efficiently, automated methods are needed to maintain the bath with a total acid value exceeding 30 points and a free acid value less than 3-5 points.

3. The success of pressure phosphating in the dual vessel system is shown by the salt spray corrosion results of the manganese tartrate bath This bath had 21 consecutive processing periods and yielded 90^ of the heated and 81% of the unheated sets of panels passing the minimum lOO-hour

salt spray test. Additionally, 76% of the heated and kit of the unheated sets of panels surpassed 800 hours of salt spray testing.

\k

w

RECOMMENDATIONS

It is recommended that:

1. The method of phosphating ferrous metal items in a bath enriched with manganese compound additives (particularly, manganese tartrate and excess manganese dihydrogen phosphate) and processed under steam pressure be utilized for the application of heavy manganese phosphate coatings.

2. A sludge recycling system be designed for the pressure phosphating system so that the precipitate can be converted to the useful form of

Mn(H2P0j2.

3. The small 30 liter production-type dual vessel system should be scaled-up to manufacturing level capacity.

15

DISTRIBUTION

A. Department of Defense

Defense Documentation Center ATTN: TIPDR Cameron Station Alexandria, VA 22311*

B. Department of the Army

Commander US Army Materiel Development and Readiness Command

ATTN: ORCMT 5001 Eisenhower Avenue Alexandria, VA 22333

Commander US Army Materiel Development and Readiness Command Scientific and Technical Information Team^ - Europe ATTN: DRXST-STL, Dr. Richard B. Griffin APO New York 09710

Commander US Army Armament Materiel Readiness Command ATTN: DRSAR-RDP

DRSAR-SC DRSAR-QAE DRSAR-IRW

Rock Island, IL 61299

Commander US Army Armament Research & Development Command ATTN: DRDAR-PMP, Mr. Donald J. Fischer Dover, NJ 07801

Oi rector US Army Materials and Mechanics Research Center ATTN: DRXMR-M Watertown, MA 02172

Commander US Army Maintenance Management Center ATTN: ORXMD-A Lexington, KY 40507

Commander US Army Electronics Research and Development Command ATTN: DRSEL-PA-E Fort Monmouth, NJ 07703

16

Cop i e;

12

DISTRIBUTION

Copies

Commander US Army Missile Research and Development Command ATTN: DRDMI Redstone Arsenal, AL 35809 I

Commander US Army Tank-Automotive Materiel Readiness Command ATTN: DRSTA-Q Warren, Ml k8030 ]

Commander US Army Tank-Automotive Research and Development Command ATTN: DRDAR-UL 1

ORDTA-RKA 1 Warren, Ml k8030

Commander US Army Aviation Research and Development Command ATTN: DRDAV-EXT I P.O. Box 209 St. Louis, MO 63166

Commander US Army Troop Support and Aviation Materiel Readiness Command ATTN: DRSTS-PLE 1 ^300 Goodfellow Blvd. St. Louis, MO 63120

Commander Ballistic Research Laboratories ATTN: DRXBR-X ] Aberdeen Proving Ground, MD 21005

Commander Harry Diamond Laboratories ATTN: DRXD0-RCD ] 2800 Powder Mill Road Adelphi , MD 20783

Commander New Cumberland Army Depot ATTN: SDSNC-QA I New Cumberland, PA 17070

Commander Pueblo Army Depot Activity ATTN: DRXPU Pueblo, CO 81001 '

17

DISTRIBUTION

Copies

Commander Red River Army Depot ATTN: SDSRR-QA Texarkana, TX 75501

Commander Sacramento Army Depot ATTN: SOSSA-QA Sacramento, CA 95813

Commander Seneca Army Depot ATTN: SDSSE-R Romulus, NY l^SM

Commander Sharpe Army Depot ATTN: SDSSH-QE Lathrop, CA 95330

Commander Sierra Army Depot ATTN: SDSS1-0QA Herlong, CA 96113

Commander Tobyhanna Army Depot ATTN: SOSTO-Q Tobyhanna, PA 18^66

D i rector- US Army Industrial Base Engineering Activity ATTN: DRXIB-MT Rock Island Arsenal Rock Island, 1L 61299

D i rector USDARCOM Intern Training Center ATTN: SDSRR-QA Red River Army Depot Texarkana, TX 75501

Commander US Army Tropic Test Center ATTN: STETC-TD Drawer Sk2 Fort Clayton, Canal Zone

18

DISTRIBUTION

Cop ies

Cornmander Anniston Army Depot ATTN: SOSAN-QA Anniston, AL 36202

Conimander Corpus Christ! Army Depot ATTN: SDSCC-MEE Mail Stop 55 Corpus Christi, TX 78AI9

Commander Fort Wingate Army Depot Activity ATTN: DRXFW Gallup, m 87301

Commander Letterkenny Army Depot ATTN: SDSLE Chambersburg, PA 17201

Commander Lexington-Blue Grass Army Depot Activity ATTN: SOSLX Lexington, KY ^0507

Commander Tooele Army Depot ATTN: SOSTE-QA Tooele, UT 8407^

Commander Holston Army Ammunition Plant ATTN: SARHO Kingsport, TN 37660

Commander Indiana Army Ammunition Plant ATTN: SARIN Charleston, IN ^7111

Commander Iowa Army Ammunition Plant ATTN: SARI0 Middletown, IA 52601

19

DISTRIBUTION

Commander Joliet Army Ammunition Plant ATTN: SARJO Joliet, IL bOklh

Commander Lone Star Army Ammunition Plant

ATTN: SARLS Texarkana, TX 75501

Commander Louisiana Army Ammunition Plant

ATTN: SARLA P.O. Box 30058 Shreveport, LA 71161

Commander Milan Army Ammunition Plant ATTN: SARMI Milan, TN 38358

Commander Radford Army Ammunition Plant

ATTN: SARRA Radford, VA Zk]k]

Commander Riverbank Army Ammunition Plant

ATTN: SARRB Riverbank, CA 95367

Commander Scranton Army Ammunition Plant

ATTN: SARSC Scranton, PA 18501

Commander Twin Cities Army Ammunition Plant ATTN: SARTC New Brighton, MN 55112

Commander Volunteer Army Ammunition Plant ATTN: SARVO-T P.O. Box 6008 Chattanooga, TN 37^01

Cop les

20

DISTRIBUTION

Copies

C. Department of the Navy

Commander US Navy Materiel Industrial Resources Office ATTN: Code OAA, CPT L. C. Oictmar I

Code 227 ' Philadelphia, PA 19112

0. Department of the Air Force

Commander Air Force Materials Laboratory ATTN: LTM 1 Wright-Patterson AFB, OH ^33

21

DISTRIBUTION LIST UPDATE

FOR YOUR CONVENIENCE

Government regulations require the maintenance of uHJJJ:**]* distribution lists for technical reports. This fo™J* P™1*** for your convenience to indicate necessary changes or corrections.

If a change in our mailing lists should be made, Plea*? check the appropriate boxes below. For changes or c?r^f 1o^:/^d°lJed address exacts as it appeared on the mailing label. Fold on dotted lines, tape or staple the lower edge together, and mail.

[~i RenoM Maw rra« List J Oiangs or Ooeroct MUTBM

OOMENTS

Date: Signature:

Technical Raport #

SARRI Form 900-643 (One-Time) (I Feb 75)

— to u. O — o

ID O > Q

«M CM

< TJ

ui rg

< X >- a. i- oo c o 0 X X

_ ^ ma:

- J^ z -J 00 UJ

#i u < 4) Wl

"O c

<n _I < cC

y ii- u

O — e 4-

°

D> E 4) C 0) </> U O)

— 4J tn « c *-> Ui <0 JZ .x •—

■M — c .c (D ■!-»

in ^ 3 ^:

c — O <fl .- ID ^

> in M

Q. O

E

rn 4-1 u m nj tn to JI ifl l_ Q. L a, a) o >- 4-

c 4- o

^ 01 > O 4-'

4) C -Q -M JZ

'! I-Jl 1.1 4» 111 V- (U ■ O 3 f0 O U 4)

air-- F « -n tz H_ m V ■w < • ■M 3 H L, m -o T» in in u D.-Q « >. in +J ir m

m • w flj m c 3 o r-^ f 1 c

1 -TV a u: O 0) en CM fl> +J =1 JQ r-. rr» tA j;: t n

M 01 -C L. C z <a fl) <» u- +J a a) m UJ -a > +J o r (A -C U

0 in o n 4J w o n o u tg i. 0 n. c <!> O </) T fl) m ril

Q-Z: ■a 4-> m in r r r o <U < 3 o 0 w ■M >

_ _ ui a:

CO (/> >- O0

V 7" _i O0 LU

—1 CU LU

rr oo s:

—1 < al

i ^ ■Z> LU

h- u Q Q

DIP-.

< •

c a) in i-

4-» 1/1 V „ ■ >- > 4J r u o 01 ra U 3 u 0) UJ 4J 4) -a

w» c -a +J o a C -C c e c 3 4J (0 4J E at n u ■fl W C l- 3 — r—

— — "+- tn o in 41 in oi c_ n .i:

in i- a. o c

1 0 tn 4) E i — (DM- ig 1 Ul -Q ^ U

O C 4-1 < u 4) (Q w < U & k

O >- 4-1 ^ O 4-1 (Q

I 4) — 4J C JO 4-i i- o c 3 — C 4)

OJ u a D

"- O ai 4-1 v- c c **- .- o ■

is

Ul t/l

10 "O -C M- Q. O -W — E i- nj -o a) Q_ja

M> tfl s e 4J

i tn ni Z 1) 0) 4) LU "O > 4-1

O m 4-1 o — L. ra u O i>i

4) <

ui en c x: 3 c — en o •- w

— 3 -M 3 . ^ C flj

•— JT k M- +J Q. 4) O C in JT

| O O +J c o J: o '

, O Q. c — to a)

J-J 4) fO C -C o U O 4-1 4-1

ai ui c en

— fl

> Q nj a

eg (_> > Q

i

< X >- Q- U 00 C o a> X X

S ui

^ 13

>- on V Z —I O0 LU

LU —

a: TD to E K C

4)

-TTT D) a (1) c B U cr

l in

ui V) a >■ a. rj OJ »- 3 '> a. a Q} iij 4J 4) -a ^ rg ■M o CT C JI

m 4) c -C c 3 4-» -C (0 ^J 1 a (D

tn 4^ in r- L. T -i Q 6 u *- in 4)

a. L. 0 tfl 4) L u- s -a 0) O B u 1) i_ 0 L. 3

T1 M u n O C E r ^- o 01 o in 4> E en 4-1 1-

Di in -Q in

L fl a (u o >- -M — 01 > O 4J

CM C ^ — 4> C -Q ^ Q. t- O

cn^-^ u- nj 4-i *-» nj

tD C C ' 4) — O 4-* 4J O " m tg

s: -o — a 4) nj tn c

— o — 4-1 x: tg c Q. 4-» 4) C

O X (0 U U fl

Cftf^ F 4) 4> ■n .tz M- ffl 4) (1 0 4-1 < • 4-1 3 (0 ■TJ TI n tn tn Q. -Q fl) >. en 4-1 a in c

r^ . M 4> T. c 3 0) o r^

i en n 0"> CM -| 4J n r r- ro tn H r i- 01 4-1

in 01 c r 4) 4) '-4- 4-J 11 m 01 n

Lil T3 > 4J f> r r 11 O tn 4-1

r 11 r r (0 o r>. r J n) 01 in

as ■o TI 4-* tn -J < r r r < 3 u O 4-1 4J > to

2

4-* tn 4) -C -^ — tO >. > 4J c I-

4J <g 4) r X

■'■' ^

in 4-1 I- -O >.J3 3 m c \~ 3 — '-

3 O O i- — y- tn C' in 4> — Q. u O — 4) i- <+- 4) X) 4) O 4J

•— U 4) l_ * OJ <4- -O CL c C E

4) e CT1 4-» 0 m 4)

o — ■ 4- in -Q tn

4-1 — p tn CD 4-1 L 4J 03 tn tg 4)

• 01 ^ tn 1. a i- x: TJ > a. o: CL 4) 0 >- 4-1 — 0.(0 0

— in > O 4-»

4>c:-Q4-»-cnj»-0

to i_ (n — xi ^-^ O 5 nj o o 4)

4- oi E c z UJ air-. F a) a -n -C 4- 01 ■ n c UJ 3 vO ".) L. CL O 4-1 — 4) u n

-J < * 4-t 3 tn x) "D a ; J </) 00 vO V) vt Q.-Q 0) m >- co >. in i-> CT in e ni i/> UI r^ . V) ei in cn c 3 a TJ

JZ ■i c — ! a_ i a\ a ir. O — tn dJ

en <N 4) J 4-1 3 JS -C co (A r^ ro e i to +J

-a; i 03 JZ l- B m L- < 03 Z 4) 4) 4) M- 4-1 Q. <U 01 n 4> in

co UI u > 4-t

ui o C

n ui .C o *J

U it L-

4-1 CJ <g

is O t/j 3 '/l ^2: -'J (1)

O h- o flj < c 03 c JZ o a) c < 3 O O 4-1

m t- *» I 0 .- in ^ 0) c 0 — t. > IA (0 • u 4-> o -a i- n 0) — <U Ul 4-» > »*- .- c o. w 3 T3 O </) v (n Q (S M "•1 o v J: 9) JO o lA W U 3 > *-> ■M (0 U) 1- >.— £ 10 3 <A c t- M .C 1(1 ^20 — i*- u a o o ow3 ■ J V (0 o O 4J — o -Cl O) -C 3 C ^ 4J (OH- U

C 0) J-l ■a *« a — -a o. a i- -a — c W "O "O c (0 <u « w a -a 0) CO W — T3 15 O CSi j= w 41 -C ._ O (0 o O 0) u 4-» *-> -a M 10 -M OJ— O .- *J o (0 c 4) — (0 C *J 4-1 t- <4- C (0 I- ^ 10 4) — <0 c c 4J « O -C ^ N m «l O u- in "O >-*-- — to — en

— o 3 W QJ n o E i- -C »- c OJ t/l o C 4-1 i_ w 5 o a— « (A 0 IA 3 <0 CL X — </) «J w 4> >-^r t- D M -a u u O 3 (0 c i- -C c a) J: O flJ o o +J o 4-1 «0 -C Q. Q. U O a> o -i-i ui a « — 4-» 3 o c <U >.JC «0--^— w — H- 4) flj >«"0 J3 4-» 4-t in tn 3 4) 4-1 E IQ a) *J «) > -a tu

1- -M x: C »4- i- c J: — 4) 4) f M- a. ID o o 3 — W J3 — -a ex. O in « to O O flJ — c tfl

JC -Q V 0* JO Q.X) O at 4} o m 4-i O O 1 3

<U — in -a 3 CA O LA <U T3 — E a. Q. (0 — a) 13 o • .c o L. o

3 U 4) >.trt 0) j; 0 * — ro 4~» i. +J c u u jr a 4-i a} m

(0 — a *-• E c u- « U t- V (D 3 ID O U

>» 4-1 3 (0 E W in in to U t_ t)

in Oi c u c nj fU 01 OJ 01 o 4-J

JD m a. *J o 0) ! 0) > XJ OJ n

Q. OJ Ul C ■ >• 4-1 a) c ■ ID E Ul i u <D 10 3 CT>

C XJ JC n C o c c ai fTJ

0) n 1 ci E jr E

u J-I ij w 3 QJ fD X) en in JZ -C *-!= O B Q. i-i Q, -w u 3 in Q. ■M 0 O L-

in c x: O ro QJ o> L- CLU.

4-1 M- C o I o C 3 Ul U

-M 3 >^ in T3 0 3 in

IA 4) 4-> Lft QJ in

o o c C <4- (0 fl» E C T3 4) 4) < 4J -u C 4t

— to .

4J

4) C — >*-

O T3 O »- o o a —

10 en a

in c (A ■u — o ^) IA X

'— (A Q. {9 4)

.C 3 in C 4) U. >.

-o O 4) 3 4-1 C ID — 4) 4-i x: C c o 3 O

0) u en — -o PM 3 a

■— o. IA (0

m 4)

M- 4-1

p c u (TJ

w Q. i-l u in i: -c u (A *? '0 QJ 11 8 L- u -a o —

ttl« « „ O c 0 _ L. > in tt 4) 4J o -o »- <0 4) — 4) in 4-1 > «*- — CO. 4-1 J -o O tn 4) in O ^ V) 10 i . o 4) J= <u A 0 m in in u D > *-» 4-» tO IA i- >.—

JT (D 3 m E 1- W £ in 4-i 3 O — **- QJ o o O — 4-1 g 1 J! « 10 0 o 4J .— o o -Q O* -C 3 c *-^ *J 10 M-

C 4) 4-J •o** ID 13 Q. O i- "O — c 4J ■a -o C (0 « 4) W O -O 4) GO in •- "O 10 O C JC in 4> .c u « O U 0) 1. 4-t *J T3 IA <o *> OJ — 0 .- w O *0 c 4) (0 C 4-1 4J U M. L. C (0 i- — 10 4) — (0 C C W 10 o -C 4-1 N in 0) O Li- in ■o >. 4-1 — (0 — ai

— O 3 (A 4) ID O E t- .c _ c 4) (A O — C 4J l_ 4-1 a) O Q.— (A O LA — 3 10 Q. JZ — IA 4J 4-1 4) 1-J- — L, 4) M ■X3 O 1-0 3 c u .!" c 4) -C 3 ffl 0 O +> 4) 4-1 (0 -C a a i- O, U 4-1 IA OL 4) ■IJ 3 a C 4) ^X ID (A — H- 4> ffl >.T3 J3 4-1 4-> m (A X 4) 4-1 E (0 0) 1 4J 4) > T3 ID

t. *J J: C M- i_ c sz — 4) Q> X 4- a. (o 4-I O O 3 — 4J x — -o Q. 0 (A 4) ID O o to in

x: JQ ■W ** -C a-o U en QJ o IA U o o 3 C £ -C 4) — IA -a 3 en o irt a> •O — E a a (o — 4) -o O • -C 2^8 >•(/» 4) X O " CA 4-1 4) « CO i- J: Q. 4-1 4J m

(0 — a. +J ■ c »*- 4) O u 4» U . Q. U ID (0 o »- (0 c 3 E C 4) -Q -C H- lA ID O 3 T3 1) > 4-1 4) 1- 3 — en

U. +J C .- a) c u o c c <A (0 4) ■l-l 4-1 <A C ^ii ID > 4J 3 (0 B IA to E

■ in m ro .u u <o c •O 4J IA — 1- ■4) 4-«

lit l- ID Z to (U < IA

-a >* ^ ._ ^- fl) 4J 4J IA 4) C L. c nj -a a c 4) (A 1 (D IA (0 (0 O 4-1 e i-i — 4) •

-Q lA CL 4-t Q in —• *0 c m ai£ 4) 4) in E o> c

4J > T3 4) en ui ID 4) 4) c — <+- Q., 4> (A C 4> o. 4) l- O >.— 4J 4) — c 1- 4) (D Vi o 4-i tg <D C in fo in 14- Q. (0 >. c 1 3 4) ID 3 en o -ei o u O c -a -C D> c « u- u O O 4) O C C en ID c; O CL — L.

— 4) 3 ID c E 10 1_ v ID 4-t .C E .ex — -a (U 4-i 4) O O 4-1 4-J tn O tz a. nj en 3 "10 (0 — M- u to X T3

■a cn w -c x: JC 0 4J Ol 0.-3 a. 0 C Q. 4-1 Q. U C tA tz tn — tx U .- D IA m 0 4) — O (A ID Q. 4-1 Q E 0 »- 4-> O 3 w x

IA l- O -C O 4) w a «i 0) ID 4) Ol t- CLU. IA in to 4) JZ

4-1 l*- 3 > U 4-1 M- 4-1

O c § in 4) "O O o c o l_ . 4 3 .—. L. (0 c

•— 4-1 4-« 3 E 4-1 C in a. 4-1 c > — m 4) 10 in en — -a o 3 tf) 4J 4) 4-1 c x: — — in E in 4) 4-* in OJ in £ C — O in in ol 4) 3 in c 4) »- >■ c o o ID 4J 4) 4> 4-1 O 3 - a: Q. IA 3 (_) Q. 4) u -a o —

: i- > in . O — 4) ' 3 -O O : • O > in (A u 3 > -C (0 3 (A

4-13 0 ) f0 -C 4> ) -Q cn X > C 4) 4J ' J "3 — C

4) 4-1 O "O j J= m O . ) U 4) 1. 4-1

— 4-1 O (0

O ~0 L ID • 4) 4-1 4-i > M- IA Q <0 4) X

1 4-1 (Q lA L. >..•

Q. 4-1

— -a a. a 1- 4-» -a -o c (0

c c n- u e « £■

U 4) O U- (A — O 3

IZ 4> (A O — 4J IA O Lrt — 10 4> i~ -3" — 2 C U

ID O O 4-i 4) O) U 4-1 IA

■C C 4) 4J 10 >.T3 -Q

E (D 4) ■O I- 4-1 J= C M- Q. 10 4-1 (0 O (A 41 f0

-E -Q

— 0) — IA "3 QJ CL fD — QJ IA >.l/> 4) JT IA 4J CO 4) (0 — > u • a »-

3 E C U O V "3 4) 4> U. 4-1 C

m 4) C 4J 9 nj

(0 O >» 4J — ro O E i_ -i-i Q)

. c u; o 4-1 Ol— o 10 C 4-1 4J fl* — (0 X -M N IA

10 — Ol >- X — C o a— —

— IA 4-1 •" ■ L.4)iA-3OL-b3l0

4-1 (0 X t — *J : to—- — • (A IA 3

CLQ.l-.iJ 3 O IA — H> 4)

4-1 ID > "O (0 !-•*- w C.C— 4) 0)^ O o 3— +jja — -3 a

4-1 d* O o 3 tr\

Q. 4-1 to

4) J3

o tn 4) "o — o ■ JZ O L. — m 4-1 t- 3

Q.4-1 E C H- 4) O 3 10 O 1- 10 EX U- - 4J 4) 1. 3 •

4J 10 — 4) 4) <

: m 4) c t. i 10 IA (0 to

Q in Q. w ) 4) ■> 4) > "3 4)

a. 4) IA

I -3 O C 4) ' lU 4J .- QJ

<A^-^ 10 I IA E 1 10 4)

tt in cn-C 31 C C — M- .- — 0

C IA f0 IA 4- a.

c -o x en O C C 1

— V 3 (D I

<o >. t 3 6 O ( O O 4» •■

I (0 — I : x .c I Q. 4J

a. 4-i o E IA t- p .

n} QJ en u 4-1 H-

c p 1 O C 3 IA

-- u tJ 1 >■ — — -a o 3 IA 4J 4J lA 3 IA C 4> 0 3 — a:

o to o 3

4) — IA (A (0

4) 4-1 4) O a to ot-

.c -3 — ot a 3 a. c <A — a

— P tA (0 IA X in a 10 4>

3 '-» *- ID 3 E 4-1 C (A

(D — *J 4) 4-1 C

-C C — ■ C p O

3 u a O lA IA IA ID 4) 41 4) 4) U -O O •

4) — IA — 41 C P — t- > IA 4) • 41 4.1 p -3 t- (0 a — 41 IA 4-* > 4- — C Q. 4-i 3-3 0 tnUiApfOiAfO U

4J J= 4) -Q P in 2 • 0 (A in U 3 >+j+jf0inL.>..-

JT 10 3 (A C 1- 4J ^ M 4-13 0 — U-41PPO— *J3

(0 O O 4-1 . - O O 5 10 -CO) J5 31 X 3 C--' +J (0 »♦- 1-

c4)4-i-3d*io — -3aoi- -0 — c — 4J "3 T3 C <0 4>

QJ CO IA — -3 10 O C H, 4) 4-1 p "3 -C in QJ X — O (0 c O 4) 1. 4-1 4-1 -3 (A 10 -M 3»— P — 4-1 O 10 C 4> — 10 C 4J 4J U 4- t- C<0L.— (04)— f0 C C 4-1 — 10 0 x: 4-1 N (A tu O U- in -3 >. -W — (0 — Ol

— O 3 IA4II0OEU.C— c c 4-> u 4^ 9 p a— — 4) IA O —

IA O IA — 3100. X:— IA4-14J 41 U-7 —

4) 4-1(0X0.0.1-0 c u (0 0 O -M cn 0 4.-J -n O. V — 4-13 p C 41 >--C ro^-v— (A — 4- « 10 >.-3 -Q +J 4-1 in 01 3 ai 4-1 E (0 41 1 4-1 41 > "3 (0

I- 4J .C CU-1-CJC— 4)41X M- a. 10 4-1 p p 3 --MX — -3a O IA 41 10 — P O ro — cm

J= X *-> <**> JZ O-X O 3)41 p (A 4-" OOI 3 C i X 41 — (A "3 3a\otn 41-3 — E a. CLIO— (U-O O ■ -C O L- O >.t/i V JZ 0 -^ m 4i L. n 0 4) 4-1 CO C x: au 41 IA

10 — a.4-iEcM-4}OI-4) L- • a. u 10 3 (0 P t- 10 c 3 E c O 3 "3 41

4} X E X 4- in 10 S — *J 4) 1- 3 — 3»

U- 4-1 c — 4) C O P C C IA 10 41 >• 4J

4-14-1— lACM-lDEgt 3(aEiAro E 5 E

• in in 10 O 1- 4) C -3 *J

IA — 1- 414-110— 414)<iA>k (At- 4-1-3 >- > • 41 4J

IA 41 C l- §5-SS.E| .""3 10 IA (0 10 XI IA a 4-1

41 41 > "3 41 DllAf04) 41C — *. CL V IA c4}aiuk.i-.-— 0 >.— 4-1 4) — C u 0 rg 4-> O *J 10 rtJ C

1 3 4) 10 C "3 J= Ol

in 10 m 14- o. ro >. c

0 C C OlQCpa— U4J c E ro u 4) ro » a.— '01U4-1410

— 41 3 ffl w _c E O 4-1 ■M m P C a 10 .Ol- 3 ••41 IO— t4-L.io X-3 —

■0 .Ol IA J3 XXP4-1 cn CL 3 a p C a4J 014-1 ClAClA— a l_ ._ 3 O. 4J 0 E

W, in 0 0) — O m ID O 1- *-" O 3 W £

IA u 3 xp4> — inaioai (0 41 Ol C a.u- IA tn ro 4) . £

4J H- 3 > U 4-1 M- 4-1

§ = ?« 2 .■SS^SS0c — 4-1 4-1 3E^CinCL*JC'-

IA 23 ID — 4-1 w en >• — -■303 iA4J4l4Jcx: — — in

41IAXC— OIAIAIA 01 41 4-1 m 3 IA C 41 L->>CPOI04)4141 P 3 — QC atA30Q.411--3 0<