FE-3800-10

Dist. Category UC-90C

MATERIALS RESEARCH FOR CLEAN UTILIZATION OF COAL

QUARTERLY PROGRESS REPORT

October 1 - December 31, 1976

{ J'AwuiiRy)

Samuel J. Schneider

Project Manager

Institute for Materials Research

National Bureau of 3 candards

Washington, D. G. 20234

PREPARED FOR THE UNITED STATES

ENERGY RESEARCH AND DEVELOPMENT ADMINISTRATION

Under Contract No. E(i9-1) -3800

'’Tliij report '^as prepared as an account of work sponsored by the United

Stetes Governnent. Neither the United Scales nor the United

f tatos ERDA, nor any of their employees, nor any of their contractors,

fuocoiit.r. actors, or their employees, makes any warranty, express or

impjied, or assumes any legal liability or I'esponsibility for the

. cr--' crr-T.ile teness , or usefulness of any information, apparatus,

irroduct or process discJ.csed, or represents that its use would not

riap,':. privaceiv ovrned righrs,”
I
TABLE OF CONTENTS

PAGE

I. OBJECTIVE AND SCOPE OF WORK 1

II. SUMMARY OF PROGRESS TO DATE 1

III. DETAILED DESCRIPTION OF TECHNICAL PROGRESS 2

1. Metal Corrosion 2

a. Constant Strain-Rate Test 2

b. Pre-Cracked Fracture Test 18

2. Ceramic Deformation, Fracture and Erosion 22

3. Chemical Degradation 23

a. Reactions and Transformations ....... 23

b. Slag Characterization ...... 24

c. Vaporization and Chemical Transport 20

4. Failure Avoidance Programs 30
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I. OBJECTIVE AND SCOPE OF WORK

Coal Gasification processes require the handling and containment of

corrosive gases and liquids at high temperature and pressures, and also

the handling of flowing coal particles in this environment. These severe environments cause materials failures which inhibit successful and longtime operation of the gasification systems. The project entails investigations oh the wear, corrosion, chemical degradation, fracture, and

deformation processes which lead to the breakdown of metals and ceramics

currently being utilized in pilot plants. Studies will also be carried

out on new candidate materials considered for improved performance.

Special emphasis will be dovoted to the development of test methods,

especially short-time procedures, to evaluate the durability of materials

in the gasification environments. These methods will focus on wear,

impact erosion, stress corrosion, strength, deformation, slow crack

growth and chemical degradation of refractories. A system has been

initiated to abstract and compile all significant operating incidents

from coal cor version plants. This program will provide a central

information center where problems of common interest can be identified

and analyzed to avoid unnecessary failures and lead to the selection of

improved matt-rials for coal cnversion and utilization. Active consultation to ERDA and associated contractors will be provided as reqested.

II. SUMMARY OF PROGRESS TO DATE

The summary of progress is contained in the individual task progress and

plans - Section III.

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III. DETAILED DESCRIPTION OF TECHNICAL PROGRESS

1. Metal Corrosion

a. Constant Strain-Rate Test (G. M. Ugiansky and C. E. Johnson, 312.04)

Progress : The investigation of the cause of embrittlement of type 310

stainless steel at elevated temperatures and at slow strain rates has

continued. Comparisons were made between embrittled specimens and

non-embrittled specimens of 310 SS and other alloys. Microscopic

examination of the cross-sections of 310, 310 S, 347 SS, and Incoloy

800 tested at 540°C (1000°F) in H2 S plus steam or H2 S saturated with

water vapor at room temperature revealed internal intergranular

cracking in 310 SS that was tested at a strain rate of 3.6 X 10“^ s~l

as well as surface cracks progressing into the bulk of the specimen

(Fig. 1); whereas, a 310 SS specimen testec at the faster strain

rate of 1.3 X 10“*+ s“l (in the same environment and at the same temperature) shows a ductile type fracture with no internal or surface

cracks (Fig. 2). Surface cracking of 310 :5S was detected in specimens

up to a maximum strain rate of 7.2 X 10“^ when tested at 540°C

(1000°F) (Fig. 3). The necking which can be seen when Fig. 1 and Fig. 3 are compared shows that the specimen in Fig. 3 is still somewhat ductile

inspite of the surface cracking. At a slower strain rate of 8.4 X 10"^

s“l, the 310 3S (Fig. 4) does not exhibit c\s much internal intergranular

cracking but does reveal larger surface cracks progressing farther into

the bulk of the specimen than in the 310 SS specimen tested at the

higher strain rate of 3.6 X 10~^ s~^ (Fig. 1). Precipitates were seen

in the grain boundaries of all the 310 SS specimens regardless of the

strain rate at which it was tested. Fig. 5 shows a representative

area of grains with grain boundary precipitates in the 310 SS specimens.

Internal intergranular cracking was observed in 310 S stainless steel

but only wher tested at the slow strain rate of 8.4 X 10“7 s~l (Fig. 6).

Precipitates were also present in the graii boundaries in all of the

310 S specimens regardless of the strain rate at which they were tested,

but the precipitates seemed to be more proisounced in the specimen tested

at the slow strain rate of 8.4 X 10“^ s“l 'Fig. 7). In the 310 S, with

a lower carbon content than 310 ^ there is .'ess carbon present to diffuse

to the grain boundaries to form the precipitates; and, therefore, the

formation of the precipitates requires longer times- No internal

cracking was revealed for any of the 347 SJ- specimens over the range

of strain rates tested. No surface cracking was apparent even though

several of the specimens showed tool marks on the surface. On the

347 SS specimen (Fig. 8) run at the slow strain rate of 8.4 X 10“^ s“^,

some of' the tool marks opened up in the necked-down area but were

shallow and blunt. However, all subsequent specimens tested had tool

marks removed by polishing the surface of the reduced area.

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No surface cracking and little, if any, internal Intergranular cracking

could be detected in the Incoloy 800 over the range of strain rates

tested. Only the Incoloy 800 specimen tested at 8.4 X 10~7 (Fig. 9)

showed a slight indication of internal cracking. There did appear to

be some formation of precipitates in the grain boundaries of Incoloy

800 run at strain rates of 7.3 X 10“^ and at 8.4 X 10~^ s“l (Fig. 10).

A determination of the origin of the crack process would help identify

the mechanism of cracking, especially with respect to the influence or lack of same of the environment on cracking. However, a thick

corrosion product layer on the fracture surface of the 310 stainless

steel specimens tested at 540°C (1000°F) in H2

S plus steam or H2S saturated with water vapor at room temperature prevented a detailed

fractographic study of those specimens. However, microscopic examination

of the fracture surface of type 310 SS tested in dry helium, argon, and

vacuum (house vacuum line, 34 Torr, 4500 Pa) at 540°C (1000°F) and at

strain rates == 1 X 10“^ s“^ have revealed evidence of brittle fracture

(intergranular cracks and faceted structure) near the original

surface of the specimen with ductile fracture (dimples) at the center

of the fracture surface and on the shear lip. This indicates that

the origin of the crack is at the metal /environment interface and not

at the center of the specimen — further evidence that the cracking ij

by an environmental mechanism. Fig. 11 shows a representative fracture

surface of a 310 SS specimen tested at 540°C (1000°F) and 1 X 10“6 ^“1.

Fig. 12 is a photomicrograph of the flat area near edge of fracture

surface of Fig. 11. Note the intergranular cracks and faceted structure.

Fig. 13 is a photomicrograph of an area near the center of the fracture

surface of Fig. 11. Note the dimpled structure indicative of ductile

fracture

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To clarify the mechanism of failure, fur :her methods of eliminating

the oxygen and water vapor from the test environment are being applied.

New flanges were made for the test chamb ar to facilitate the test of

310 SS in a somewhat better vacuum (2 X 10”^ Torr, 2.66 Pa) than that

in which tie previously tested specimens were tested (house vacuum).

Upon completion of the test at == 1 X 10~ ’ s“^, the surface of the specimen was oxidized, and the same brittle type fracture occurred with

secondary surface cracks. There was apparently enough oxygen and/or

water vapor present to cause cracking.

-Another test was run on 310 SS. This time a reducing environment

(H2 ) was used. It was thought that the reducing atmosphere of H2 would

prevent or limit the effect of oxygen. The H2 was handled in the

following manner: the H2 gas was passed through a liquid N2 trap,

through copper turnings at 565°C (1050"F), through another liquid

N2 trap, through the test chamber at a low positive pressure, through

-another liquid N7 trap, and through a H2 O bubbler that was vented

directed to the exhaust system. This test run was made at 540°C

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(1000**F) at a strain rate of 8.4 X 10“^ s""^. Some blue oxide was still

present on the specimen after the test, but the amount of oxide was

the least that has been seen for any tests in any environment. The

fracture was still of the brittle type with some secondary cracking.

The reduction in area (23.3%) was higher for this specimen, tested in

than for other 310 SS specimens tested in other environments

(17-19%) with the exception of one 310 SS specimen tested at 540°C

(1000°F) at a strain rate of 8.4 X 10“^ s~^ in ultra pure He (25%).

Testing of the alloys has been started at a strain rate of 1 X 10“^ s~^

in H2

S saturated with water vapor at room temperature at 540°C (1000°F).

Gas mixtures of CO, CO 2 , H2

» and CH^ have been prepared and analyzed

but have not been shipped since they will be used to calibrate flowmeters that have been ordered. The gasfs and flow meters are scheduled

to be delivered in two weeks.

Plans ; Complete tests of types 310, 310 S, 347 stainless steel and

Incoloy 800 at the very low strain rate of 1 X 10“^ s“l in H2 S saturated

with water vapor at room temperature at 540°C (1000°F), while continuing

the search for the cause of failure in the 310 SS.

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growth rate as a function of or the stress-intensity threshold level

below which crack growth rate does not occur can be readily determined.

For this configuration of specimen, the stress intensity (K^) is then

given in terms of the crack length (a) , the specimen height (H), the

specimen arm displacement due to the wedge (V) and the modulus of the

specimen (E) as follows: (ref. 1)

^ ^ ^ 3.46 -I- 2.38 (H/a)

^ ^

/h 7.97 (|)^ + 16.48 (|) + 11.32

n rl

This equation shows that the stress-intensity (K^) , is relatively

insensitive to crack length (a) for a/H values greater than about 3, so that accurate values of are determined without requiring extremely

accurate crack 1 ingth (a), measurements.

For use at eleva'.ed temperature, the above equation for stress-intensity,

K^, must take in;o account the following effects:

1)

Decrease in elastic modulus, E, with increase in temperature.

2) Increase in arm displacement, V, due to thermal expansion.

3) Increase in affective crack length, due to increase in plastic

zone size caused by the decrease in the yield strength of the

specimen witli increase in temperature.

4)

Decrease in ":he measurement capacity (maximum stress- intensity that can be measured) for a given size specimen due to decrease in the

yield strength of the specimen material.

The equation for stress- intensity given above was modified to take into

account these ef.'ects. For a wedge-loaded, doi ble cantilever beam

specimen loaded vt room temperature to a stress-intensity level designated

(Kj)^, the change in stress-intensity when the temperature is increased to

some value T is vK_)„, where the ratio (K_)_/(K_) is: IT 1 T I o

OCi>T

where:

- modulus of elasticity of specimen at temperature T.

E^ — modulus of elasticity of specimen at room temperature.

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V - arm displacement at room temperature,

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where a^ and are the crack length and specimen height at temperature T a

f (•g“) is the same function for crack length, a^, and specimen height, H

at room temperature.

It is desirable for temperature to have as small an effect as possible on the stress- intensity . That is, for the ratio to be approximately 1 over

a wide range of temperature. To achieve this, the effect of temperature

on each of the terms in the above equation was investigated to select

values than minimize the effect of temperature on the ratio ^T. The effect

Ko

of temperature on crack length, a, and specimen height, H, is relatively

small and since for a/H ratios greater .than about 3, the stress intensity

K is relatively unsensitive to a/H, the ratio

reduced to

:

is approximately 1.0. Therefore the above equation is

^ - ^T

where:

V

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w s [h (1 + a )(T - T )] - [h (1 + a )(T - T^)]

height of wedge at loading point

height of slot in specimen

coefficient of thermal expansion of wedge

coefficient of thermal expansion of specimen

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For a given test material the choice of wedge size and material is chosen

so that as nearly as possible the thermal expansion of the wedge

compensates for the decrease in modulus of elasticity of the test specimen

with temperature.

Plans

:

The analysis of the effect of thermal expansion, change in modulus

of elasticity with temperature and change in plastic zone size with

temperature will be completed. For each of the specific materials of

interest for use at high temperature, the elastic stress- intensity factor

will be calculated for temperatures up to 2000°F and the maximum stressintensity for use of linear elastic fracture mechanics will be established.

Reference:

1. B. F. Brown, Stress-Corrosion Cracking in High Strength Steels and

in Titanium and Aluminum Alloys, Naval Research Laboratory, 1972

Chap . 2

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2. Ceramic Deformation, Fracture and Erosion (E. R. Fuller, S. M. Wiederhorn,

C. R. Robbins and D. E. Roberts,

313.05)

Progress : The main effort of the past quarter has been the design and

construction of new test equipment. In addition, the mechanical properties

and mineral composition of two laboratory mixtures of castable refractories

(high and low alumina calcium-aluminate castables) have been studied

after elevated temperature-pressure exposure, and the erosive behavior

of a phosphate-bonded refractory has been examined.

A great deal of progress has been made on tfe construction of the apparatus

for mechanical properties testing in simulated coal gasification environ

ments. The outer pressure shell for this apparatus has been constructed.

A Radiographic inspection of the original g..rth welds revealed two flaws

which have been repaired. The design of tht; interior of the apparatus

has been completed, detailed mechanical drawings have been prepared, and

the components are presently being constructed in the NBS Machine Shop.

A base, which will support the pressure vessel, has been designed and is

also being constructed. The base will provide explosion protection, and

ventilation for the pressure vessel. Other systems and components (such

as: temperature controllers, refractory insulation, a pressure-balance

controller, and a chain hoist) have been orcered and most have arrived.

The equipment for particle erosion has been enclosed and connected to an exhaust system. The enclosure will satisfy the NBS Safety Office rules on dust/particle hazards and will permit injection of additional gaseous

components into the stream of eroding particles. In addition, a ventilation system for exhausting explosive and/ot noxious gases from the three

pressure vessel systems and the gas tank storage rack has been designed.

A spark-proof ind corrosion resistant exhaus t fan for^this system has

been ordered, and received, and will be ins railed shortl'y.

High-temperature exposure experiments were :.nitiated in a pressure

vessel recently purchased by NBS. The unit, has been plagued with a number of minor problems (pressure leaks, a faulty temperature controller,

a faulty water pump, and a defective pressui e gauge isolation system)

which have slowed the collection of data. Most of these problems have

now been overcome and specimens of both a high alumina ('v-95%) and a low

alumina (v56%) , calcium-aluminate refractory castable have been exposed

to steam at 1000 psig (7.0 MPa) at temperatures running from 310°C

(590°F) to 910"C (1670°F) . After exposure the following properties have

been examined: flexural and compressive strengths at two rates of

loading; erosive wear by particle impingement; porosity; mineral phases;

and microstrue tural morphology. Results are still preliminary at this

time.

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Plang ; Construetion will continue on the apparatus for mechanical properties testing In simulated coal gasification environments. Completion

of the main portions of this apparatus and ’’check-out" of the heat zone

is anticipated in the next quarter. Construction of the ventilation

system should begin and be substantially completed in the next quarter.

Exposure studies will continue with gaseous compositions (molar percent)

of 70% water and 30% carbon dioxide and of 30% water and 70% carbon

dioxide at 1000 psig total pressure. Upon completion of the ventilation

system^ mixtures with carbon monoxide will be considered. Work to

characterize the erosion behavior of three basic castable compositions

(a 95% alumina » a 56% alumina and a phosphate bonded refractory) as a function of temperature, particle velocity and impingement angle will be

completed, and studies on the effect of particle size on erosion rate

will be started.

3 » Chemical Degradation

a. Reactions and Transformations (F, Mauer and C. R. Robbins, 313.06)

Progress : During this quarter work ©a the design and construction of

apparatus for x-ray examination of refractory castables under simulated

gasification conditions was continued. While the pressure vessel was under construction in the NBS Instrument Shops, design of the x-ray

goniometer (for mounting and aligning the pressure vessel on the x-ray

apparatus) was completed and construction was begun. The pressure

vessel and goniometer are expected to be completed by about January 15,

1977 .

All of the components for the gas manifold have been purchased. Gases

will be introduced through a gauge block that includes a needle valve,

pressure gauge and rupture disc. Water will be introduced separately

from a 40 ml cylinder pressurized with ISI^ gas. A second 40 ml cylinder

has been included in the systm so that- a saaple of the atmosphere can be withdrawn for analysis.

Additional samples have been obtained for us i in preparing standard x- ray patterns by the energy dispersive diffraction method. A calculator

program has been w^ritten which can be used to convert d-spacings and

Intensities from a conventional powder diffraction pattern to channel

number and counts (peak and background) for the energy dispersive diffrac

tlon pattern. This program is being used in the Interpretation of the

patterns being .prepared for use as working standards.

Plans : Construction of major components is expected to be completed

during January so that the systm can fee assembled during February and

used for calibration runs. In situ x-ray diffraction measurements

(subtask 3a-3) are expected to begin by April 1, 1977, as proposed in

our original work statement.

23
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b. Slag Characterization (W.S. Brower, J.L. Waring, 313.03 and

D.H. Blackburn, 313.02)

Progress ; The viscosities of synthetic slags (one modeled after Montana

Rosebud Coal Ash analyses and the other modeled after Pittsburgh Seam

Coal Ash) have been measured at ambient pressure over the temperature

range of 1300°C to 1600°C (Figure la and lb) . The compositions are given

in Table 1.

Table 1. Slag Compositions

Rosebud Pittsburgh Seam

SlOj 42.10 wt% S102 49.0

A1203 19.50 AlO 26.0

7.11 19.0

CaO 24.48 CaO 3.5

Na20 0.21 Na20 0.6

K

2

O 0.10 K

2

O 1.2

MgO 5.50 MgO 0.7

TiO^ 0.90

The gear motor for crucible rotation has^ been received and the torsion

wire suspensions have been calibrated wi-.h two fluids of known viscosity

using two different "drag cup geometries' (Figure 2)

.

Preliminar} tests have been run in an autoclave operating at 30 psig

steam pressure using a platinum strip heater with a radiating area

of 15 squai e inches to evaluate the effe.’.t of steam pressure on the

heater tern] erature at a constant power level. A 20% reduction in

temperatur« was observed from ambient pressure to 30 psig (Figure 3)

at 800°C.

Plans ; While the pressure vessel cons traction is being completed a series of synthetic slags xv^ith systematir;ally varying composition will

be formulated and the viscosities measured is a function of temperature

and compared to viscosity data obtained Jrom predictive equations. In

the next quarter the vessel construction should be complete. .

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24
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temperature.

Rosebud

Type

Coal

Ash

o

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00

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25

TEMl^ERATURE
L5!finnjuT
Figure

lb.

Viscosity

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vs

temperature.

Pittsburgh

Seam

Type

Coal

Ash

t

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{sas-pod ®'^Sox) AJLisoDSIA

26

TEMPERATURE

(“C)

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ANGULAR

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Temperature

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heater

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pressure.

n

Do aaaivHadioi.

28

PSIG

c. Vaporization and Chemical Transport (J. Hastie and D. Bonnell,

313.01)

Progress ; Quantitative vapor transport data have been obtained for

molten Na2 S 04 in an argon environment using our prototype platinum tube

reactor. A wide range of pressures (0.15 to 0.6 atm) and temperatures

(1390 K to 1650 K) were used to test reactor performance and attainment

of thermodynamic equilibrium. The major vapor transport reaction in

this system was determined as

Na2 S 04 (£) = 2Na + SO 2 + O2 and by monitoring mass spectrometrically the partial pressures of Na,

O2 values for the apparent reaction equilibrium constant could

be determined, i.e.,

Kp = (pNa)2(pS02)(p02)

Also, from the so-called second law dependence of Kp on temperature, a value for th’ reaction enthalpy was determined as AHr (1520 K) = 283±13

kcal mol“^. This result is in agreement with the literature value of

287 kcal mol'*^ (JANAF Thermochemical Tables) . Similarly the absolute

values of Kp agree within experimental error with the literature values

based on thermodynamic equilibria. Such agreement provides good evidence

that the liquid Na 2 S 04 vaporization process in an equilibrium one and

that our reac.tor design and sampling conditions are not distrubing the

reaction. These data also establish the lower sensitivity limit for the

technique as 1 ppm per mole of carrier gas.

Plans ; Thoo^h the present reactor design has performed satisfactorily

thus far we intend to decrease the cone angle of the skimmer for aerodynamic reasons. This should allow for imj roved sensitivity at higher

gas pressures . Following construction of this new skimmer we will test

the system W3 th NaCl by monitoring the well known vapor equilibrium:

2NaCl = (NaCl)

2

Once the modified reactor has been shown to perform satisfactorily for

the relatively simple test systems, the inert argon atmosphere will be

replaced by reactive gases, H2 O, H2 , SO2 , etc., common to coal gasification reacttrs. Measurements of vapor composition as a function of

temperature, pressure, and composition w^ill then be made.

29
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4 Failure Avoidance Programs (J. H. Smith, 312.01)

Progress : Approximately 50 additional reports of operating discrepancies

and component failures in coal conversion pilot plants were received in

the Failure Prevention Information Center during the current quarter.

Additional information on the performance of materials in coal conversion

process equipment was received from technical papers presented at the

8th Synthetic Pipeline Gas Symposium and on the properties of high

temperature alloys from papers presented at the Electrochemical

Society meeting.

All information on operating discrepancies, component failures, and

materials performance have been classified and evaluated for technical

completeness and accuracy. Detailed technical abstracts of this

information have been entered into the comput prized data base management

system for ease of future retrieval and data dissemination. An update

of the frequency of failure modes which analyses the information in

this system is shown in Table 1.

Information was disseminated by supplying abstracts of Information

included in the data base on a weekly basis to Battelle - Columbus for

use in preparation of the Materials and Components Newsletter and to

other users as requested. In addition, requests for specific, detailed

information were supplied to approximately 15 organizations in response

to direct inquiries to the Failure Prevention Information Center.

Beginning with the December 1, 1976 edition of the Materials and Components

Newsletter, descriptions of operating discrepancies and component failures

are referred to by NBS information item number for convenience in

referring to specific failure problems.

The format was developed for two separate types of reports to be used

for efficiently disseminating information from the Failure Prevention

Information Cenrer. A draft of the first abstract report on information

about the use o.' 316 stainless steel has been completed.

A draft of a de ailed summary report on erosion in coal conversion

process equipment has been completed.

Plans : The information collecting phase of this task will continue as more information is received on a continuing oasis from the pilot plants.

Visits to operating pilot plants and failure analysis laboratories are planned to significantly augment the information collection activities

and to get additional information on operatin^j discrepancies and

component failures.

The information evaluation phase of this task will include development of

additional programs for use with the data base system. In addition, the

information classification scheme will be revised and improved.

30
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