AOI[3]: Smart Refractory Sensor Systems for

Wireless Monitoring of Temperature, Health,

and Degradation of Slagging Gasifiers
PI Team:
Dr. Debangsu Bhattacharyya a
Mr. Jeffrey Bogan b
Dr. David Graham c
Dr. Vinod Kulathumani c
Dr. Edward M. Sabolsky d
aDepartment

of Chemical Engineering, WVU

bHarbisonWalker International Technology Center
cLane Department of Computer Science and Electrical Engineering, WVU
dDepartment of Mechanical and Aerospace Engineering, WVU

Researcher Team:
Post-doc

Rajalekshmi Pillai

Graduate Students

Qiao Huang

Gunes Yakaboylu

Steven Andryzcik

Priyashraba Misra

Undergraduate Students

Brian Armour

James Meyer

HWI Team

4/27/2016

Margaret Raughley

Joshua Sayre

Acknowledgements:
We would like to thank U.S. Department of Energy (DOE) for
funding the project under contract DE-FE0012383.
Dr. Maria Reidpath, U. S. Department of Energy, is greatly
appreciated for her insight and valuable guidance.
We also would like to acknowledge WVU Shared Facilities.
Thanks to HarbisonWalker International for the technical
staff.
Kindly acknowledge Faculty and staff of West Virginia
University for their support.

4/27/2016

Background- Gasifier Sensing Needs:

Online monitoring sensors of refractory used in coal gasifiers under
extreme conditions including high temperature (>1300oC) and high
pressure (up to 1000 psi) for >20,000 hr.
Erosive and corrosive conditions (due to slag and high pressure, in
addition to various pO2 levels) causes degradation of refractory over
time.
Ability to monitor the integrity of the refractory materials during
gasifier operation would contribute significantly to improving the
overall operational performance and reliability of coal gasifiers.
Temperature
Stress/strain within refractory liner
Spallation events
Refractory liner health
Monitoring interior thermochemical conditions allows for efficient
control of the gasification process.

4/27/2016

Technology Vision:
Item A represents the smart
refractory material.
Item B is an interconnection
(alignment) pin.
Item C is an interconnection brick,
which will permit transfer of the
signal to the exterior wall.
Item D is the sealed electrical
access port to connect to the
signal acquisition/processing units.
Item E is low-power electronics
and wireless communication.

4/27/2016

Program Objectives:
1) Investigate chemical stability, thermomechanical properties, and electrical
properties of refractory ceramic composites at temperatures between 7501450C.
2) Define processes to pattern and embed the conductive ceramic composites
within refractory materials to incorporate temperature and strain/stress
sensors into refractory bricks.
3) Develop methods to interface the electrical sensing outputs from the smart
refractory with an embedded processor and to design a wireless sensor
network to efficiently collect the data at a processing unit for further data
analysis.
4) Develop algorithms for model-based estimation of temperature profile in the
refractory, slag penetration depth, spallation thickness, and resultant health
by using the data from the wireless sensor network.
4/27/2016

Task Assignments:
Task 2: Fabrication and Characterization of
Oxide-Silicide Composites.
Task 3 and Task 4: Sensor Patterning and
Embedding and Static and Dynamic Sensor
Testing.
Task 5: Data Ex-Filtration Using a Wireless
Sensor Network.
Task 6: Model-Based Estimation of Refractory
Degradation/Temperature.
4/27/2016

Task 2:
Fabrication and Characterization of
Oxide-Silicide Composites.
(Sabolsky)

4/27/2016

Task 2.0 Objectives:

Investigate chemical stability, thermomechanical
properties, and electrical properties of refractory
silicide-oxide composites at temperatures between
750-1450C.

4/27/2016

Silicide/Oxide Stability (XRD):

* Prepared via mixed oxide route followed by sintering in Argon atmosphere at 1400-1600C.
Al2O3

Y2O3

ZrO2

Cr2O3

MoSi2

MoSi2, Al2O3, Mo5Si3,

SiO2

MoSi2, Y2O3, SiO2,

Y5Mo2O12, Mo3Si, Mo3O

MoSi2, ZrO2, Mo5Si3

MoSi2, Cr2O3,
Cr3Mo, SiO2

WSi2

WSi2, Al2O3, W5Si3

WSi2, Y2SiO5, WO2, SiO2

WSi2, ZrO2, W5Si3

WSi2, Cr2O3, SiO2, W3O

ZrSi2

ZrSi2, Al2O3, ZrO2, SiO2

ZrSi2, Y2O3, Y2Si2O7, SiO2

ZrSi2, ZrO2, SiO2

ZrSi2, Cr2O3, ZrSiO4,

Cr3O, SiO2

TaSi2

TaSi2, Al2O3, Ta5Si3,

Ta3Si, SiO2

TaSi2, Y2SiO5, Ta2O5,

Y10Ta4O25

TaSi2, ZrO2, Ta5Si3, SiO2

TaSi2, Cr2O3, CrTaO4,

Ta2O5, TaO2

NbSi2

NbSi2, Al2O3, Nb5Si3

NbSi2, Y2O3, Y2SiO5,

Nb5Si3, SiO2

NbSi2, ZrO2, Nb5Si3, SiO2

NbSi2, Cr2O3, Nb5Si3,

CrNbO4, CrNbSi, SiO2

TiSi2

TiSi2, Al2O3, Ti5Si3, SiO2

TiSi2, Y2O3, Y2Si2O7,

TiO2, SiO2

TiSi2, ZrO2, TiO2, SiO2

(Cr0.88Ti0.12)2O3,
Cr3Si, SiO2

CrSi2

CrSi2, Al2O3, Cr5Si3

CrSi2, Y2O3, Y2SiO5

CrSi2, ZrO2

CrSi2, Cr2O3, Cr3Si, SiO2

Metal silicides show high stability in Al2O3 and ZrO2 matrix only with formation of different type
of silicides (Mo5Si3, W5Si3, Ta5Si3, Nb5Si3, Cr5Si3) and SiO2 (highlighted).
They partially react with Y2O3 and Cr2O3 to form undesired secondary phases.
4/27/2016

10

Silicide/Oxide Microstructure (SEM):

(60-40) vol% MoSi2-Al2O3

(60-40) vol% MoSi2-Y2O3

20 m

(60-40) vol% WSi2-Al2O3

10 m

(60-40) vol% WSi2-Y2O3

(60-40) vol% MoSi2-ZrO2

3 m

(60-40) vol% WSi2-ZrO2

20 m

Secondary Phase
10 m

1 m
4/27/2016

Chemically etched in 1:1:1 HCl:HNO3:H2O

11

3 m

Silicide/Oxide Properties:
CTE (100-1000C)

4-point DC Conductivity (100-1000C)

4

10

12.0

MoSi2-Al2O3 composites

10.0
9.5
9.0
8.5

30

40

50

60

70

10

10

10

80

(75-25) vol% MoSi2-ZrO2

10

~ 9.65x10-6K-1
20

Volume Percentage of MoSi2

MoSi2-based composites
100 200 300 400 500 600 700 800 900 1000

10

WSi2-Al2O3 composites

10

10

10

(60-40) vol% TiSi2-Al2O3

Silicide/Al2O3 composites
0

100 200 300 400 500 600 700 800 900 1000

MoSi2-Al2O3

at ~ 1000C
(S/cm)

WSi2-Al2O3
MoSi2-coarseAl2O3

Conductivity (S/cm)

-6 -1
Alpha (10 K )

11.0
10.5
10.0
9.5
9.0
8.5

~ 9.41x10-6K-1

8.0
7.5

(60-40) vol% TaSi2-Al2O3

10

Temperature (C)

Temperature (C)

12.0
11.5

(60-40) vol% WSi2-Al2O3

Conductivity (S/cm)

10.5

7.5

(60-40) vol% MoSi2-Al2O3

(60-40) vol% MoSi2-ZrO2

11.0

8.0

(60-40) vol% MoSi2-Al2O3

Conductivity (S/cm)

-6 -1
Alpha (10 K )

11.5

10

(20-80) vol% MoSi2-Al2O3

20

30

40

50

60

70

Volume Percentage of WSi2 (%)

80

10

TaSi2-Al2O3

TiSi2-Al2O3
MoSi2-ZrO2
WSi2-ZrO2
CrSi2-Cr2O3

10

10

60/40 vol%

MoSi2-Al2O3

43.6

WSi2-Al2O3

26.7

WSi2-ZrO2

20.7

MoSi2-c.Al2O3

20.5

100 200 300 400 500 600 700 800 900 1000

Temperature (C)

Key Parameters: (1) metal silicide type and fraction, (2) mixedness or level of homogeneity, (3)
relative density, and (4) particle size of the metal silicide and refractory oxide.
4/27/2016

12

Long-Term Stability of the Composites:

Thermal Stability (1400C)

Grain Growth Kinetics (1400-1600C)

MoSi2-Al2O3 composite
30000
27000

(60-40) vol% MoSi2-coarseAl2O3

(60-40) vol% MoSi2-ZrO2

12

18000

10

24 hrs

15000
12000

9000

3000
0

20

30

40

50

60

2 ()

70

: MoSi2 : ZrO2 : Mo5Si3

48 hrs

27000
24000
21000

24 hrs

18000
15000

12000

9000

6000
3000

20

30

Sintered

40

4/27/2016

50

60

2 ()

70

Precursor
MoSi2 Powder

90

MoSi2-ZrO2 composite
30000

80

80

Sintered

After annealing

Intensity (a.u.)

(60-40) vol% MoSi2-Al2O3

14

21000

6000

Intensity (a.u.)

18
16

48 hrs

24000

Pure MoSi2

MoSi2 Grain Size (m)

: MoSi2 : Al2O3 : Mo5Si3

20

90

Pure MoSi2

After Sintering
(1600C - 2h)

After Annealing
(1400C - 24h)

MoSi2-Al2O3

5 m

1 m

Silicide/Al2O3 and silicide/ZrO2 composites are highly

stable at 1400C (up to 48 hrs).
Refractory oxides successfully retard the grain growth.
13

Task 2 Conclusions and Future Work:

Metal silicides show high stability in Al2O3 and ZrO2 matrix
(with occasional formation of sub-silicides).
Electrical conductivity of composites characterized with
various silicide content consistent performance transferred
to sensor design and fabrication task.

Future Work:

Alternative materials and designs (layered structure) will

be investigated to prevent the reaction between
silicide/oxide composites and Cr2O3.
Process parameters will be optimized by correlating the
degree of distribution (D index) with the physical
properties of the composites (conductivity) at high
temperatures.
4/27/2016

14

Task 3: Sensor Patterning and

Embedding.(Sabolsky/HWI)
Task 4: Static and Dynamic Sensor Testing
of Smart Refractory Specimens.
(Sabolsky/HWI)

*US Provisional Patent Number 61/941,159

4/27/2016

15

Task 3 Objectives:
To develop methods for patterning technology the ceramic
composites within the refractory matrix.

Task 4 Objectives:
To test the electrical performance of the smart refractory
brick (with embedded thermocouple or thermistor sensors).
To investigate corrosion/erosion kinetics in static and
dynamic tests on smaller prototype and full-size smart cups
and bricks (at WVU and HWI).
To implement and test methods for data collection on initial
prototypes.

4/27/2016

16

Smart Refractory Fabrication:

General Smart Refractory Processing Method
Examples of Sensor Preforms

4/27/2016

17

Thermoelectric Voltage (mV)

High-Temperature Thermocouple
Performance:
WSi2// TaSi2

32

MoSi2// WSi2
MoSi2// NbSi2

24

MoSi2// TiSi3

16

9
8
0
0

400

800

1200

1600

Temperature (C)

Various thermocouple
compositions studied
at 1500 C

90 vol% silicide and 10 vol% oxide

The thermocouple with composition MoSi2 //TiSi2 exhibited 34 mV at 1400 C

4/27/2016

18

Long Thermocouple Preforms:

1st cycle

2nd cycle
10

1500

1350 C
8.3 mV

Temperature (C)

1200

1350 C

8.43 mV
5h

9
8

10 h

1050

900

6
5

750

600

450

300

150

Thermoelectric Voltage (mV)

1350

-1
0

12 15 18 21 24 27 30 33 36 39 42 45 48 51 54 57 60 63 66

Time (hours)

Long Thermocouple: [75-25] Vol% MoSi2-Al2O3//[75-25] Vol% WSi2-Al2O3

laminated between alumina substrates and sintered at 1500 C, 2h in argon
and tested isothermally at 1350 C for 2 cycles in argon atmosphere
Temp. C

Experiment

Hold Time, h

EMF, mV

1350

Cycle # 1

8.3

1350

Cycle # 2

10

8.43

4/27/2016

19

TC: [75-25] Vol% MoSi2Al2O3// WSi2-Al2O3

Smart Refractory Microstructure:

Sensor embedded
Cr2O3 refractory
brick

Monoliths of sensors were fabricated via tape casting, laminated and sintered
at 1500 C. These laminates were embedded in the Cr2O3 brick while slip
casting and co-sintered at 1500 C in Argon atmosphere.
4/27/2016

20

Embedded Thermocouple: Smart Chromia Brick

Sensor preform embedded
HWI high-chromia
formulation.

Long TC embedded Chromia Refractory Brick

Sensor embedded below

opening to insert slag
composition for corrosion
testing.
Thin Embedded TC Sensor

Interfaced Smart Brick

Testing Smart Refractory Brick

4/27/2016

21

Embedded Thermistor: Smart Chromia Brick

4.0

1350 C

Resistance ( )

3.5
3.0
2.5
2.0
1.5
1.0
-10

30

70

110

150

190

230

270

Time (Hours)

Performance of thermistor [60-40] vol% MoSi2-Al2O3

Thermistor embedded smart brick in the

testing furnace

The temperature sensor (thermistor) with composition (60-40) vol%

MoSi2-Al2O3 embedded within the Cr2O3 refractory exhibited stable
behavior for more than 250 hours at 1350 C in argon atmosphere.
4/27/2016

22

Static and Dynamic Corrosion Tests:

(Currently On-going)
(a)

Sintered sensor preform

Lignite Coal

(b)

(c)

Brick loaded with coal

Biscuit fired coal samples

Various steps involved in the testing of smart refractory brick embedded

with [90-10] MoSi2-Al2O3 thermistor and tested at 1350 C , 2h in Argon
Lignite Coal Slag 44.3SiO2-5.26Fe2O3-17.5CaO-6.64MgO
4/27/2016

23

Current Issue: Brick Interconnection

Ag wire leads

Smart brick
K-Type Thermocouple

Loss of electrical connection to bricks during testing.

Metal lead delamination due to wetting limitations.
Phase oxide formation in locations that are not embedded causing
drift in response.
Efforts are focusing on better understanding the issue and
developing the proper ceramic and/or metal connections.
4/27/2016

24

Task 3 and 4 Conclusions and Future Work:

All-ceramic thermocouple and thermistor preforms were
fabricated and successfully tested.
Smart high-chromia bricks were fabricated in collaboration
with HWI (both thermistors and thermocouples), and currently
going under test.

Future Work:
Optimize method to interconnect to embedded sensors (in
order to stabilize sensor signal and sensor long-term response).
Investigate the corrosion/erosion kinetics of sensor embedded
refractory bricks in static and dynamic mode with slag.
Scale-up all sensor preforms and smart refractory brick for
FULL-TECHNOLOGY DEMO IN TASK 7.
4/27/2016

25

Task 5:
Data Ex-Filtration Using a Wireless
Sensor Network.
(Graham/Kulathumani)

4/27/2016

26

Task 5 Objectives:
To develop methods to interface the electrical
sensing outputs from the smart refractory with an
embedded processor
To design a wireless sensor network to efficiently
collect the data at a processing unit for further data
analysis
Energy
Harvester

Sensor

4/27/2016

Interface
Circuit

WSN
Mote

27

Radio

Base
Station

Electronics interfacing Approach:

Aim: To reliably collect data from the sensors embedded within
the smart bricks and interface them to wireless sensor nodes for
communication
Approach:
(i) Iterative approach to sensor interface circuitry in parallel with
the sensor development
a)
b)

Initial sensor interface circuitry using off-the-shelf circuitry

Move to integrated circuits for lower-power and more compact
solutions

(ii) Investigate energy harvesting using thermoelectric devices to

help power the sensor motes and interface circuitry

4/27/2016

28

Custom Integrated Circuit:

2

3
5

1. Cold-Junction Compensator
2. Thermocouple Amplifier
3. Capacitive Sensor
4. Thermocouple Amplifier V2
5. Wheat-Stone Bridge
Bridge Circuit Temperature vs Actual Temperature
120

Resistance-Based Sensor

110

Within 2% accuracy

100

Temperature(C)

90
80
70
60
50
40

Measured
Ideal

30
20
20

4/27/2016

29

30

40

50

60
70
80
Temperature(C)

90

100

110

120

Circuits for Thermocouple-Based Sensors:

Compensates for measurement

error at thermocouple cold
junction
Adds offset to thermocouple
input to allow for the correct
temperature measurement
Greatly improves accuracy over
a large range of temperature
values

TC Amplifier with CJC Offset

Percent Error vs Temperature

5

1500

4
3

1
Error(%)

Temperature(C)

2
1000

0
-1

500

-2
-3
Measured
Ideal

500

1000
Temperature(C)

4/27/2016

30

-4
1500

-5
700

800

900

1000
1100
1200
Temperature(C)

1300

1400

1500

Circuits for Energy Harvesting:

Start-up Sequence

Leverages COTS-based DC/DC converter

circuit (LTC3108)
Start-up Sequence shows the output of
Thermoelectric Generator, LDO Regulator,
Storage Buffer, and VOUT.
The Mote Experiment was done using a
TelosB. The results shown are 10 minutes
into the test. Once a minute, the TelosB
turned on and was powered by the energy
harvesting system for a 5 second radio
transmission.
VOUT System Output
Storage Buffer Energy Storage Output
LDO Regulator Internal Regulator Output
TEG Thermoelectric Generator Output
4/27/2016

31

Mote Experiment: Testing Results

Wireless sensor network overview:

Sensor
1
Sensor
2

Data In
Command
Out

Base Station
Desktop/Laptop

Sensor
3
Master
Mote

Sensor
4

Collect refractory sensor data over wireless medium

(data ex-filtration)
Enable remote configuration of parameters
(over-the-air programming)
4/27/2016

32

Assembled complete signal chain:

Smart bricks with embedded sensors were interfaced with

a wireless mote yielding a complete signal chain
comprising
the smart brick,
resistance measurement / amplifier circuit,
and wireless data transmission.
4/27/2016

33

Verified wireless signal chain performance:

5

LabView Full Run

x 10

LabView Half Run

200
Resistance( )

Resistance( )

3
2
1
0
0

10

15
Time(h)
WSN Full Run

20

150
100
50
0

25

6
8
Time(h)
WSN Half Run

10

12

10

12

200
Resistance( )

Output(V)

3
2
1
0
0

10

15
Time(h)

20

150
100
50
0

25

6
Time(h)

Wireless Sensor Network (WSN) data collected from smart

bricks by measuring voltage from ICs [bottom figure]
Resistance measured directly on Labview by connecting an
ADC probe [top figure]
Figures show similar trend, thus verifying correctness of
the wireless network based data collection
4/27/2016

34

Results on increasing scale of network:

Tested ability of sensor network protocol to handle larger

network sizes
Evaluated sizes from 40-200 using a ns-3, a network
simulator
Customized collection tree protocol to periodic data
collection scenario
100% data reliability
Latency and message size grow linearly with network size
4/27/2016

35

Task 5 Conclusions and Future Work:

The end to end signal chain for data collection system has been
implemented and tested using actual smart brick prototypes
Sensors are interfaced with microcontroller + radio (motes)
Data collection protocol has been implemented
Visualization and sensor control interfaces have been
implemented
Scalability of network protocol was evaluated
Refinements to interface circuits to suit updated sensors
Model based data reduction techniques are being explored
This can help reduce data rate without compromising with
information required for analyzing system characteristics.
4/27/2016

36

Task 6.0:
Model-Based Estimation of
Temperature Profile and Extent of
Refractory Degradation.
(Bhattacharyya, Huang)

4/27/2016

37

Task 6 Objectives:
To develop algorithms for model-based estimation of
temperature profile in the refractory, slag
penetration depth, spallation thickness, and
resultant health by using the data from the wireless
sensor network

4/27/2016

38

Motivation:
Typical correlation based approaches are inadequate
Stiff temperature gradient along the refractory
resulting in a large temperature change along the
sensor length
Change in thermal and electrical properties over time
due to slag penetration

4/27/2016

39

Property Models:
In order to build the model of smart refractory , several
temperature-dependent property models for refractory
or sensor material are needed:
The electrical resistivity model for refractory*

Specific heat
Emissivity
Thermal conductivity
Electrical conductivity
Thermal expansion
Dielectric constant
Youngs modulus
Poissons ratio

*Hensler J R, Henry E C. Electrical Resistance of Some Refractory Oxides and Their Mixtures in the
Temperature Range 600 to 1500 C[J]. Journal of the American Ceramic Society, 1953, 36(3): 76-83
4/27/2016

40

Property Models for Composite:

The properties of refractory will change as the slag
penetrates into the wall. These models can be used
to predict the effective properties of a special kind of
composite(slag and the refractory).
Specific heat
Thermal conductivity
Dielectric constant

4/27/2016

41

Thermal Model of a Gasifier Wall:

2-D heat conduct equation was used:
1

4/27/2016

42

Slag Penetration Model:

Velocity of capillary flow through the horizontal pores (Washburn, 1921)
Corrected by porosity and tortuosity of the refractory pore system.
(Williford et al., 2008)

Velocity of slag penetration

decreases quickly
Temperature gradient
Williford, R. E.; Johnson, K. I.; Sundaram, S. K.; Pilli, S. Effective diffusivity and spalling models
for slagging coal gasifiers. J. Am. Ceram. Soc. 2008b, 91, 4016-4022.
4/27/2016

43

Sensor Models:
Resistive
circuit
sensor

Five different types of sensors:

Thermistor or
thermocouple

Interdigital capacitor (IDC)

Strain gauge
Resistive circuit
Thermistor

Strain
gauge

thermocouple

4/27/2016

44

Interdigital
capacitor

Interdigital Capacitor (IDC) Sensor Model:

Sensitivity to slag penetration
Composite property
model
Slag can only fill the
pores

5.00E-12

Capacitance (F)

4.80E-12

4.60E-12

0 vol% slag
5 vol% slag
10 vol% slag

4.40E-12

15 vol% slag
20 vol% slag

4.20E-12

4.00E-12
0

0.005

0.01

0.015

0.02

Distance (m)

* Igreja R, Dias C J. Analytical evaluation of the interdigital electrodes capacitance for a

multi-layered structure[J]. Sensors and Actuators A: Physical, 2004, 112(2): 291-301.

4/27/2016

45

Estimation:
Methods:
Traditional Kalman Filter (TKF)
Linear process model
Computationally cheap
Less accuracy for highly nonlinear process
Extended Kalman Filter (EKF)
Nonlinear process linearized at every time step
Computationally costlier than TKF
Higher accuracy than TKF for nonlinear process
Unscented Kalman Filter (UKF)
Nonlinear process
Computationally expensive
Superior accuracy

4/27/2016

58

46

Filter Algorithm:
Differential Algebraic Equations System
Nonlinear differential algebraic equations (DAE) system:
,

Developed approach for handling the DAE System:

Linearized process model:

Augmented form:

4/27/2016

59

47

Estimation of Temperature Using EKF:

Assume five IDC sensors are embedded
diagonally in the refractory brick.

Estimation of capacitance
Temperature Estimation for Different
Extent of Slag Penetration are completed

4/27/2016

48

Estimations of Temperature Using UKF:

Assuming five IDC

sensors are embedded
diagonally in the
refractory brick

4/27/2016

61

Estimations of Extent of Slag Penetration

Using UKF:
Temperature is assumed
to be under the normal
operating conditions

4/27/2016

50

Task 6 Conclusions and Future Work:

Nonlinear filtering algorithms have been developed
to estimate temperature and the extent of slag
penetration. The filters have been tested by using the
data from the model of gasifier wall.
Future work will focus on validation and testing of
developed models and filtering algorithms using
experimental data.

4/27/2016

51

Products:
1. Edward M. Sabolsky, R. Chockalingam, K. Sabolsky, G. A. Yakaboylu, O. Ozmena, B. Armour,
A. Teter, D. Bhattacharyya , David Graham , Vinod Kulathumani, Close Timothy and Marc
Palmisiano, Refractory Ceramic Sensors for Process and Health Monitoring of Slagging
Gasifiers, 227th ECS Meeting- Chicago, Illinois, USA, May 28th, (2015).
2. Edward M. Sabolsky , R. Chockalingam, K. Sabolsky, G. A. Yakaboylu, O. Ozmen, B. Armour,
A. Teter, D. Bhattacharyya, David Graham, Vinod Kulathumani, Close Timothy and Marc
Palmisiano, Conductive Ceramic Composites Used to Fabricate Embedded Sensors for
Monitoring the Temperature and Health of Refractory Brick in Slagging Gasifiers, XIVth
International Conference European Ceramic Society- Toledo, Espana 24th June, 2015
3. R. C. Pillai, E. Sabolsky, K. Sabolsky, G. Yakaboylu, B. Armour, J. Mayer, J. Bogan, M.
Raughley and J. Sayre Performance of high temperature ceramic-ceramic thermocouples
embedded within chromia refractory bricks to monitor the health and stability of industrial
gasifiers Materials Science and technology MS&T2015, Oct 4-8, 2015, Greater Columbus
Conventional Center, Columbus, Ohio, USA.
4. G. Yakaboylu, R. C. Pillai, B. Armour, K. Sabolsky, E. Sabolsky,Development of Refractory
Oxide/Metal Silicide Composites for High Temperature Harsh-Environment Sensor
Applications,Materials Science and technology MS&T2015, Oct 4-8, 2015, Greater Columbus
Conventional Center, Columbus, Ohio, USA.
5. G.A. Yakaboylu, R. C. Pillai, B. Armour, K. Sabolsky and E. M. Sabolsky, Conductive
Ceramic Composites for Fabricating High Temperature and Harsh Environment Sensors:
Thermal Processing, Stability and Properties, International Conference and Exposition on
Advanced Ceramics and Composites, January 24-29, 2016, Daytona Beach, Florida, USA.

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Products:
6. R.C. Pillai, G.A. Yakaboylu, K. Sabolsky and E. M. Sabolsky,J. Bogan, J. Sayre,
Composite Ceramic Thermocouples for Harsh-Environment Temperature
Measurements, International Conference and Exposition on Advanced Ceramics and
Composites, January 24-29, 2016, Daytona Beach, Florida, USA.
7. E. M. Sabolsky, R. C. Pillai, K. Sabolsky, G. A. Yakaboylu, B. Armour, A. Teter, M.
Palmisiano and T. Close, Refractory Ceramic Sensors for Process and Health
Monitoring of Slagging Gasifiers, ECS Trans., Vol 66(37) pp 43-53 (2015).
8. B. Rumberg, D. Graham, S. Clites, B. Kelly, M. Navidi, A. Diello, V. Kulathumani,
RAMP: Accelerating Wireless Sensor Design with a Reconfigurable Analog/MixedSignal Platform, Proceedings of the ACM/IEEE Conference on Information
Processing in Sensor Networks (ISPN15), pp. 47-58, Seattle, WA, April 13-16, 2015.

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53

Appendix:

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54

Thermocouple Microstructures:
Microstructure of ceramic-ceramic thermocouples sintered at 1500 C in argon

The SEM micrographs clearly shows that the thermocouples are fully dense and hence
improves the conductivity

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55

Image Analysis for Distribution (SEM):

Proposed Method: Determination of coefficient of variation as a measure of the degree of
distribution (D index) by measuring distances between all neighboring silicide grains.
,
,
,

1.0

(60-40) vol% WSi2-Y2O3

0.9

(60-40) vol% MoSi2-Al2O3

0.8
0.7

D index

0.6
0.5
0.4
0.3
0.2
0.1

5 m

Original image
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0.0

Binary image
56

8 10 12 14 16 18 20 22 24 26 28 30 32

Number of lines analyzed

Silicide Thermocouples:
Seebeck coefficients

Thermoelectric Voltage
T1

T2

T2

T1

E AB = A (T ) dT + B (T ) dT

Absolute Thermoelectric Voltage (mV)

Silicide Couples
30
25
20

(Mo or W)-Ti
(Mo or W)- Ta

15
10

Mo-W

5
0
0

500

1000

Temperature Difference (C)

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S500 (V/C)
Reference
-3.0
T. Nonomura (2011)
-0.3
T. Nonomura (2011)
14
Kenneth Kreider (1995)
20.8
Kenneth Kreider (1995)
-3.3
Kenneth Kreider (1995)

The emf generated between hot junction

J1 and cold junction J2 in material A

35
Mo-Ti
W-Ti
Mo-Ta
W-Ta
Mo-W

Material
MoSi2
WSi2
TaSi2
TiSi2
Pt

1500

B-Type = 8.96 mV at 1400 C

(Mo or W)- Ti silicide couples
~ 30-34 mV at 1400 C
Mo-W silicide (most
oxidation resistant) resulting
only~ 4mV at 1400 C
CrSi2- based couples would
perform nicely ( = 200
V/K) but melts at 1470 C

Embedded Thermocouple Preform:

Composite
Powders

Dispersant
(Solvents and Dispersants)

Ultrasonic mixing
Tape casted, laminated
and laser cut alumina
green substrates

Screen printing
Curing at 50 C

Sintering at 1500 C for 2 h. in Ar. atmosphere

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58

Organic Binder Vehicle

Ceramic Thermocouple Performance:

(High-temperature measurements)
Thermoelectric Voltage (mV)

25
20

WSi2 // TaSi2
WSi2 // MoSi2

15

MoSi2 // ZrSi2
WSi2 // ZrSi2

10

NbSi2 // MoSi2
TiSi2 // WSi2

5
0
0

200

400

600

800

1000

Difference in Temperature (C)

Preforms and laminated forms of ceramic

thermocouples heated at 1500 C and
performance is evaluated at 1000 C.

1.
2.
3.
4.
5.
6.

TiSi2// WSi2 exhibited 20 mV at 800 C

(Type B= 3.15 mV at 800C)
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59

[90-10]WSi2-Al2O3//[90-10]TaSi2-Al2O3
[90-10WSi2-Al2O3//[90-10] MoSi2-Al2O3
[90-10]MoSi2-Al2O3//[90-10] ZrSi2-Al2O3
[90-10]WSi2-Al2O3// [90-10] ZrSi2-Al2O3
[90-10]NbSi2-Al2O3//[90-10] MoSi2-Al2O3
[90-10] TiSi2-Al2O3//[90-10] WSi2-Al2O3

Thermocouple Microstructures:
[90-10] WSi2-Al2O3

Intensity (A.U.)

[90-10] TiSi2-Al2O3

[90-10] TaSi2-Al2O3

[90-10] NbSi2-Al2O3

Al O MoSi
2

20

[90-10] MoSi2-Al2O3

40

60
80
100
Angle 2 (Deg)

120

X-ray analysis of various ceramic-ceramic thermocouples sintered at 1500 C in Ar

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60

Ceramic Testing Stress/Strain Sensors:

Introduce 10% oxygen flow into furnace during burnout of imbedded
sensors to eliminate carbon deposits
Texture substrates in the gripper area to prevent slipping during testing
Amend sensor design to increase Gauge Factor
Evaluate temperature effects on strain sensor
Initiate compressive testing of ceramic strain sensors

V3
V4
V5
V6
V7

(mm)
40
40
40
40
40

(mm)
1.0
0.5
0.5
0.2
0.2

(mm)
1.0
1.0
0.5
1.0
0.5

A Sensor length
B Spacing between legs
C Leg width
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Design: V3
61

40.00 mm

0.50 mm
0.50 mm

55.00 mm

40.00 mm

55.00 mm

Design ID

1.00 mm
1.00 mm

Design: V5

Embedded Thermocouples Performance:

Thermoelectric Voltage (mV)

8
38-114-11 Therm o Couple
[90-10] vol% M oSi2 -Al2 O 3 //TaSi2 -Al2 O 3

Pt lead

4
Thermocouple

TC embedded Cr2O3 refractory

brick

0
0

300

600

900

1200

Temperature ( C)

[90-10] vol% MoSi2-Al2O3 // TaSi2-Al2O3

Thermocouple was embedded within the Cr2O3 refractory and was

tested from room temperature to 1200 C in argon atmosphere.
Demonstrated half of predicted voltage, indicating some reaction
or change in junction circuit.
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62

Thermistor Preforms:

MoSi2-Al2O3 based small thermistors

Addition of MoSi2 decreased the resistance of MoSi2-Al2O3 composite thermistors

[50-50] MoSi2-Al2O3 exhibited 786.50 and [90-10] MoSi2-Al2O3 exhibited 10.76
resistance at 1100 C respectively

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63

Static Cup Corrosion Study of Smart Brick:

WSN Data

Lab View Data

1200 C
1100 C

900

1h

25

5h

1h

20
15

600

10

300

0
4

14

280

900

210

Sensor hits the slag

140

300

70

Resistance, k

Temperature, C

1200

0
10

15

1
Data Rail Out Points

20

25

10

12

14

16

18

20

43-11 Brick#10:[60-40]MoSi2-Al2O3 Slag Test - WSN

350

Time, h

1500

43-11 Brick#10:[60-40]MoSi2-Al2O3Run 1 - WSN

19

Time, h

43-11 Brick #10:[60-40] MoSi2-Al2O3 Sensor2: Slag Test

600

Volts(ADC\Resistance)

1200

Volts(ADC\Resistance)

1350 C

Resistance, k

Temperature, C

43-11 Brick # 10: [60-40] MoSi2-Al2O3 Empty Run1

30
1500

3.5
3
2.5
2
1.5
1
0.5
0

Data Rail Out Points

Sensor hits the slag

30

Time, h

8 10 12 14 16 18 20 22 24

Time, h

The analytical test results (Lab View) of Brick #10: [60-40] MoSi2-Al2O3 brick were correlated
with wireless data up to 1350 C isothermal hold and thereafter the data showed deviations.
This may be due to oxidation.
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