材材料料에 에에 에 따른 따른 高高溫溫溫 Alumina Alumina …

001.hwp222000000777 888
Alumina Alumina Alumina Alumina
MatrixMatrixMatrixMatrix
BendingBendingBendingBending

Sintering Sintering Sintering Sintering Characteristics Characteristics Characteristics Characteristics of of of of High High High High Alumina Alumina Alumina Alumina Refractory Refractory Refractory Refractory and and and and Its Its Its Its
Effect Effect Effect Effect on on on on High High High High Temperature Temperature Temperature Temperature Bending Bending Bending Bending for for for for Different Different Different Different Material Material Material Material
Composition.Composition.Composition.Composition.
2007 2007 2007 2007 6 6 6 6


....
2007 2007 2007 2007 6 6 6 6

2007 2007 2007 2007 6 6 6 6

List of tables ··············································································································· iii
List of figures ············································································································· iii
1111 ······························································································ 1
2222
2-1. Alumina-Mullite ····································································· 3
2-2 .
2-2-1. Silica ·································································································· 4
2-2-2. Alumina ···························································································· 9
3 3 3 3
3-1. ····················································································· 18
3-3. Bending ·································································· 20
3-4.
3-4-2. ············································································ 23
- ii -
4 4 4 4 ·························································· 26
5 5 5 5 ················································································ 50
ReferencesReferencesReferencesReferences ························································································· 51
Table 2.1. Chemical Composition of Refractory materials ························· 4
Table 3.1. Raw material for test ······································································· 18
Table 3.2. The mixture ratio of Matrix ·························································· 20
Table 3.3. The mixture ratio of testing specimen
for high temperature bending ···························· 21
List List List List of of of of FiguresFiguresFiguresFigures
Fig. 2.1. The temperature of silica transformation ······································· 6
Fig. 2.2. Hexagonal close-pac structure of α-Alumina ························· 10
Fig. 2.3. Refractoriness with composition of
the Al2O3-SiO2 system ·············································· 13
Fig. 3.1. The test method of high temperature bending ·························· 25
Fig. 4.1. The sintering shrinkage with sintering temperature ··············· 27
Fig. 4.2. The sintering bulk density with sintering temperature ······· 28
Fig. 4.3. Microstructure of raw material(alumina+kaolin Matrix)
with sintering temperature(1450, 2hr) ································ 29
Fig. 4.4. Microstructure of raw material(alumina+kaolin Matrix)
- iv -
Fig. 4.6. Microstructure of raw material(alumina+silica matrix)
Fig. 4.9. Microstructure of raw material(alumina+clay matrix)
Fig. 4.12. Microstructure of raw material(alumina+silica fume matrix)
Fig. 4.15. XRD pattern of testing specimen(alumina+kaolin matrix) ··········· 43
Fig. 4.16. XRD pattern of testing specimen(alumina+silica matrix) ············ 44
Fig. 4.17. XRD pattern of testing specimen(alumina+clay matrix) ············· 45
Fig. 4.18. XRD pattern of testing specimen(alumina+silica fume matrix) ··· 46
Fig. 4.19. The test of high temperature bending with matrix ·············· 47
- v -
ABSTRACT
Sintering Sintering Sintering Sintering Characteristics Characteristics Characteristics Characteristics of of of of Matrix Matrix Matrix Matrix of of of of High High High High Alumina Alumina Alumina Alumina Refractory Refractory Refractory Refractory
and and and and Its Its Its Its Effect Effect Effect Effect on on on on Bending Bending Bending Bending for for for for Different Different Different Different Material Material Material Material Composition.Composition.Composition.Composition.
Bae Ji-su
Department of Advanced Materials Engineering
Graduate School of Chosun University
Theresultstestbyadjustingvariousraw materialsandcompositionconditionsforthe evaluationoftheevaluationofthebendingcharacteristicsofAlumina-mulliterefractories areasthefollows. 1)Wehaveconfirmedthatthesinteringwascarriedoutrelativelywellevenatthe temperatureof1550 andcompositionreactionofMullitewaswellaccomplishedwhen weusedKaolinandClayastheraw materialsofMatrixbutthesinteringtemperature musthavebeenover1650 WhenweusedfinepowderofSilicafume. 2)Matrixspecimenthathasusedsilicaasraw materialwaspoorinsinteringatthe temperaturelessthan1650 andcompositionreactionofMullitewasalsoindicatedas low andMullitecompositionwasnotgeneratedatthetemperatureof1450.Silicafume witerelativelymorefinepowdershowedsimilarfeaturebutthelevelofsinteringand mullitewashigher. 3)Wecouldconfirm throughtheresultsofmeasuringtheBendingcharacteristicsof
- vi -
- 1 -
.

1000-1200 (high temperature materials)
(refractory ceramics) .
SK26 ()
.

, slag,
.

.

.
, , cement, ,
boiler, ,
, ,
.
(refractory brick)
,
(kiln furniture) .

Al2O3-SiO2 . Al2O3-SiO2
- 2 -
(kiln furniture) 1600
alumina-mullite ,
(bending) .
alumina-mullite fused alumina fused mullite
matrix 1~5 calcined alumina kaolin
.
matrix , matrix alumina kaolin
(1~2)

, bending .
, creep alumina-mullite
, matrix
(5)
(6,7)
matrix
, matrix
alumina-mullite bending .
- 3 -
2 2 2 2
2-1. 2-1. 2-1. 2-1. Alumina-MulliteAlumina-MulliteAlumina-MulliteAlumina-Mullite
Al2O3 90% SK 40
Al2O3
45% , Al2O3 99%
. ,
, , , (kiln) .
α- alumina mullite(3Al2O32SiO2)
, .
α- alumina , , ,
. mullite Al2O3-SiO2 2
, α- alumina
, .

(kiln furniture) . 1600
alumina-mullite .

, , , ,
, .
- 4 -
2-2. 2-2. 2-2. 2-2.

mortar
,
, . 2-1
.

silica(SiO2) . silica
, , , ( ; quartz),
( ; quartz sand), ( ; diatomaceous earth)
(Mono-crystal) ( ; rock crystal).
.
silica () , (;
2.64~2.65), cristobalite( 2.32~2.33), tridymite(
- 5 -
1) 1) 1) 1) SilicaSilicaSilicaSilica
silica Si O
. SiO2
, Si
. 4
, silica .
silica
. Fig. 2.1 2()
(sluggish type inversion)
αβ (αβ type inversion) .
Silica quartz(). tridymite, cristobalite
, (high form) β (low form)
α . α-quartz,
α-quartz 573 β-quartz , β-quartz
573 α-quartz . α→β
(inversion)
. Silica α→β quartz
(volume change)
.
870 β-quartz β-tridymite
tridymite
quartz .
quartz
- 6 -
Fig. Fig. Fig. Fig. 2.1. 2.1. 2.1. 2.1. The The The The temperature temperature temperature temperature of of of of silica silica silica silica transformationtransformationtransformationtransformation
- 7 -
tridymite . 1470
cristobalite
. β
-tridymite β-cristobalite quartz
α→β α-tridymite α-cristobalite
.
(silica stone) (, SiO2)
. ,
. α-quartz
silica ,
, .
, ,
, Fe-Si , .

900~1000 (;calcination)

() .
2% CaO
. Fe2O3 CaO
(SiO2) cristobalite
tridymite . , ,
.

- 8 -
.
, , ,
99.99% SiO ,
,
.
.
3) 3) 3) 3) (quartz (quartz (quartz (quartz sand)sand)sand)sand)
.
()

() ()
,
. .
.
.

.
.
, ,
.
, ,
, , , ,
. ,
,
- 9 -
(aluminum oxide; Al2O3)
alumina . (corundum ;
) ,
, α-, β- .
1) 1) 1) 1) AluminaAluminaAluminaAlumina
alumina 101.96 3.965, 2080
8×10 -6
(25~1,000). alumina
bauxite Bayer , ,
, , , , ,
, , .
alumina ,
300 α-
. β-
γ- .
alumina α- Al2O corundum
M2O3(M: metal)
Fig. 2.2 . (hexagonal close-packed
structure) ABAB 3 6
.
- 10 -
Fig. Fig. Fig. Fig. 2. 2. 2. 2. 2. 2. 2. 2. Hexagonal Hexagonal Hexagonal Hexagonal close-packed close-packed close-packed close-packed structure structure structure structure of of of of αααα- - - - AluminaAluminaAluminaAlumina
alumina bauxite, (), (
) . alumina
bauxite Al2O H2O(diaspore boehmite)
Al2O 3H2O(gibbsite bayerite) Al2O xH2O
- 11 -
, SiO2, Fe2O3, TiO2, CaO, MgO, Cr2O3
.

, , .
Bayer.
bauxite , autoclave (NaOH)
(NaAlO2) .
SiO2, Fe2O3, TiO2 (; red mud)
.
, gibbsite
. Al(OH)3
50% H2O
. 2 ,
1200~1300 (calcination). Al2O
(Al2O3) .
alumina .
,
.
1, 0.1
.
- 12 -
,
.

(abnormal grain growth) ,
.
.

, .
,
.

.
.
65% Al2O3-SiO2
, Fig. 2.3 .
SiO2 (), Al2O3 ()
, SiO2 92~93%
, Al2O3 55% .
Al2O3 50% ,
, ,
.
- 13 -
.
mullite Al2O3-SiO2 mullite
.
5) 5) 5) 5) (clay)(clay)(clay)(clay)
(fine particle)
(wet State) (plasticity)
- 14 -
(sintering) .
, , (flux) (glass
phase) 3 ,
.
,
,
.
kaolinite ·dickite ·halloysite (kaolinite ; Al2O3
2SiO2 2H2O) , montmorillonite ·bentonite ·
(montmorillonite ; Al2Si4O10 (OH)2 nH2O) illite
sericite (illite ; K,H3O)Al2(Si,Al)4O10(H2O,OH)2)
,
. Si-O Al-O
.

.
.
- 15 -
kaolin , , ,
.
kaolin halloysite
.
kaolin , kaolin
. kaolin
, kaolin
(refractoriness) () kaolin kaolin
chamotte .
kaolin ( differential
thermal analysis, DTA) 600 , 98
0 .
600 OH
() , kaolin Al2O3
2SiO2 meta-kaolin .
980 meta-kaolin mullite γ-alumina
γ-alumina alumina SiO2
spinel .
spinel , mullite cristobalite .
kaolinite .
kaolinite () .
K2O Al2O3 6SiO2 + 2H2O + CO2 =
Al2O3 2SiO2 2H2O(kaolinite)+ 4SiO2 + K2CO3
kaolin 500~600
- 16 -
.
1000~1100 1200~1300
6) 6) 6) 6) MulliteMulliteMulliteMullite
mullite . .2.4
Al2O3-SiO2 . mullite
Al2O3 . mullite alumina
1840 .
3Al2O3-2SiO2 2
mullite(3Al2O3 2SiO2) kaolin
, glass alumina ,
. glass
mullite , creep Al2O3
SiC ,
. 1840 , ,
kiln furniture .
alumina ,
. mullite

mullite .
mullite , ,
- 17 -
sagger, satter, , ,
.
,

Fig. Fig. Fig. Fig. 2. 2. 2. 2. 4. 4. 4. 4. Phase Phase Phase Phase diagram diagram diagram diagram for for for for the the the the AlAlAlAl2222OOOO3333-SiO-SiO-SiO-SiO2222 systemsystemsystemsystem
- 18 -
3 3 3 3
3-1. 3-1. 3-1. 3-1.
(matrix) Table 3.1
.
Table Table Table Table 3.1. 3.1. 3.1. 3.1. Raw Raw Raw Raw material material material material for for for for testtesttesttest
Al2O3 SiO2 Fe2O3 TiO2 CaO MgO K2O Na2O Ig.
loss
calcined
alumina
daihan
ceramic 2.5 99.6 0.04 0.04 0 0.06 0.05 0 0.2 0
kaolin duckyou
mesh 36 49 0.31 0.09 0.07 0.02 0.01 0.04 14.4
silica duckyou
mesh 0.5 99.2 0.02 0.01 0.01 0 0 0.1 0
clay kibushi 325
mesh 35.1 45.98 1.06 0.83 0.23 0.21 0.41 0.13 15.32
silica
fume
saint-
gobain 0.5 0.13 97.6 0.3 0.03 0.01 0 0 0
ZrO2
1.9
fused
alumina
daihan
ceramic
1-0.5
0.5-0.2
0.2-0
fused
mullite
daihan
ceramic 0.2-0 76.5 23.37 0.03 0.01 0.01 0 0 0.1 0
- 19 -
matrix mullite
Al2O3 72%, SiO2 28% ,
( ; Ignition loss) .
matrix 1 500g
30wt% (, ; Sanopco Co. No. 5468)0.6% 5
. mullite matrix slip
200×200×50mm
.
matrix 100mesh
matrix .
3-2. 3-2. 3-2. 3-2. Matrix Matrix Matrix Matrix
matrix table 3.2 . 4
silica(SiO2) matrix 3%
mold(140×25×5mm) 50Mpa
.
70 12
1450, 1550, 1650 2
.
- 20 -
Table Table Table Table 3.2. 3.2. 3.2. 3.2. The The The The mixture mixture mixture mixture ratio ratio ratio ratio of of of of Matrix Matrix Matrix Matrix

silica fume 0 0 0 28%
* M-K : matrix-kaolin, M-S : matrix-silica, M-C : matrix-clay, M-F : matrix-silica fume
3-3. 3-3. 3-3. 3-3. Bending Bending Bending Bending
matrix matrix alumina-mullite
bending matrix alumina, mullite
Table 3.3
. poly-vinyl
alcohol (PVA ; , P-05A 0.3%) 20%
.
, 120 Mpa.
(70) 12
1650 2 .
- 21 -
Table Table Table Table 3.3. 3.3. 3.3. 3.3. The The The The mixture mixture mixture mixture ratio ratio ratio ratio of of of of testing testing testing testing specimen specimen specimen specimen
for for for for high high high high temperature temperature temperature temperature bendingbendingbendingbending

Matrix
( Alumina + Kaolin)
- 22 -
3-4. 3-4. 3-4. 3-4.
3-4-1. 3-4-1. 3-4-1. 3-4-1.

.

.
(bulk specific gravity),
(apparent specific gravity) .
.
W1 :
W2 : 3

W3 :

(Sa) = (W1 - W2 )/ W1 ( )
(Sb) = (W3 - W2 )/ W1 ( )

- 23 -
.
3-4-2. 3-4-2. 3-4-2. 3-4-2.

. , ,
, , slag,
, spalling
.
12~30%, 70~80% .
.

.
(Pa, %)=(W3 - W2) /(W3 - W1) × 100

.
p .

.
- 24 -

.
3-4-3. 3-4-3. 3-4-3. 3-4-3. (Softening (Softening (Softening (Softening under under under under load) load) load) load)

(
) ,
.

.
(kiln furniture)
( ) .

.

.
kiln furniture
bending .
1) Bending
.
1600 .
alumina-mullite bending
Fig. 3.1 500g 1600 10hr,
20hr, 30hr height gauge bending .
:140*25*10mm:140*25*10mm:140*25*10mm:140*25*10mm
:100mm:100mm:100mm:100mm
::::
500gram500gram500gram500gram

::::
1600160016001600
Fig. Fig. Fig. Fig. 3.1. 3.1. 3.1. 3.1. The The The The test test test test method method method method of of of of high high high high temperature temperature temperature temperature bendingbendingbendingbending
- 26 -
4 4 4 4
matrix
(bulk density) Fig. 6 Fig. 7
.
Fig. 4.1 clay 1650
9.7% , kaolin,
silica fume, silica .
clay, kaolin 1450 OH
,
.
silica , silica
fume 1550 1650
. silica
fume silica 1550
.
Fig. 4.2 bulk density silica fume
silica 1650
.
1650 silica fume
.
- 27 -
Fig. Fig. Fig. Fig. 4.1. 4.1. 4.1. 4.1. The The The The sintering sintering sintering sintering shrinkage shrinkage shrinkage shrinkage with with with with sintering sintering sintering sintering temperaturetemperaturetemperaturetemperature
- 28 -
M-K : matrix-kaolin, M-S : matrix-silica, M-C : matrix-clay, M-F : matrix-silica fume
Fig. Fig. Fig. Fig. 4.2. 4.2. 4.2. 4.2. The The The The sintering sintering sintering sintering bulk bulk bulk bulk density density density density with with with with sintering sintering sintering sintering temperaturetemperaturetemperaturetemperature
- 29 -
Fig. Fig. Fig. Fig. 4.3. 4.3. 4.3. 4.3. Microstructure Microstructure Microstructure Microstructure of of of of raw raw raw raw material(Alumina material(Alumina material(Alumina material(Alumina + + + + Kaolin Kaolin Kaolin Kaolin Matrix) Matrix) Matrix) Matrix)
with with with with sintering sintering sintering sintering temperature temperature temperature temperature (1450(1450(1450(1450, , , , 2hr)2hr)2hr)2hr)
- 30 -
Fig. Fig. Fig. Fig. 4.4. 4.4. 4.4. 4.4. Microstructure Microstructure Microstructure Microstructure of of of of raw raw raw raw material(Alumina+Kaolin material(Alumina+Kaolin material(Alumina+Kaolin material(Alumina+Kaolin Matrix) Matrix) Matrix) Matrix)
with with with with sintering sintering sintering sintering temperature(1550temperature(1550temperature(1550temperature(1550, , , , 2hr)2hr)2hr)2hr)
- 31 -
Fig. Fig. Fig. Fig. 4.5. 4.5. 4.5. 4.5. Microstructure Microstructure Microstructure Microstructure of of of of raw raw raw raw material(alumina+kaolin material(alumina+kaolin material(alumina+kaolin material(alumina+kaolin matrix) matrix) matrix) matrix)
- 32 -
Fig. Fig. Fig. Fig. 4.6. 4.6. 4.6. 4.6. Microstructure Microstructure Microstructure Microstructure of of of of raw raw raw raw material(alumina+silica material(alumina+silica material(alumina+silica material(alumina+silica matrix) matrix) matrix) matrix)
- 33 -
- 34 -
- 35 -
Fig. Fig. Fig. Fig. 4.9. 4.9. 4.9. 4.9. Microstructure Microstructure Microstructure Microstructure of of of of raw raw raw raw material(alumina+clay material(alumina+clay material(alumina+clay material(alumina+clay matrix) matrix) matrix) matrix)
- 36 -
- 37 -
- 38 -
Fig. Fig. Fig. Fig. 4.12. 4.12. 4.12. 4.12. Microstructure Microstructure Microstructure Microstructure of of of of raw raw raw raw material(alumina+silica material(alumina+silica material(alumina+silica material(alumina+silica fume fume fume fume matrix) matrix) matrix) matrix)
- 39 -
- 40 -
- 41 -
Fig. 4.3 ~ Fig. 4.13 matrix
.
Fig. 4.3 ~ Fig. 4.5 kaolin 1450
, kaolin 2
mullite . 1550 mullite
, .
1650 .
Fig. 4.6 ~ Fig. 4.8 silica 1450 kaolin
mullite . 1550
.
Fig. 4.9 ~ Fig. 4.11 clay kaolin
.
Fig. 4.12 ~ Fig. 4.14 silica fume 1450, 1500
. , 165
0
.
1450, 1550
.
1650 5 ,
.
.
mullite , 1550 () mullite
. 1650 ,
.
silica silica fume 1550
- 42 -
mullite , 1650 ,
. Fig. 4.2
1650 kaolin clay
.
- 43 -
Fig. Fig. Fig. Fig. 4.15. 4.15. 4.15. 4.15. XRD XRD XRD XRD pattern pattern pattern pattern of of of of testing testing testing testing specimen(alumina+kaolin specimen(alumina+kaolin specimen(alumina+kaolin specimen(alumina+kaolin matrix)matrix)matrix)matrix)
- 44 -
Fig. Fig. Fig. Fig. 4.16. 4.16. 4.16. 4.16. XRD XRD XRD XRD pattern pattern pattern pattern of of of of testing testing testing testing specimen(alumina+silica specimen(alumina+silica specimen(alumina+silica specimen(alumina+silica matrix)matrix)matrix)matrix)
- 45 -
Fig. Fig. Fig. Fig. 4.17. 4.17. 4.17. 4.17. XRD XRD XRD XRD pattern pattern pattern pattern of of of of testing testing testing testing specimen(alumina+clay specimen(alumina+clay specimen(alumina+clay specimen(alumina+clay matrix)matrix)matrix)matrix)
- 46 -
Fig. Fig. Fig. Fig. 4.18. 4.18. 4.18. 4.18. XRD XRD XRD XRD pattern pattern pattern pattern of of of of testing testing testing testing specimenspecimenspecimenspecimen
(alumina (alumina (alumina (alumina + + + + silica silica silica silica fume fume fume fume matrix)matrix)matrix)matrix)
- 47 -
M-K : matrix-kaolin, M-S : matrix-silica, M-C : matrix-clay, M-F : matrix-silica fume
Fig. Fig. Fig. Fig. 4.19. 4.19. 4.19. 4.19. The The The The test test test test of of of of high high high high temperature temperature temperature temperature bending bending bending bending with with with with matrixmatrixmatrixmatrix
- 48 -
martix mullite
XRD Fig. 4.15 Fig. 4.18 . 1450
kaolin clay mullite
, kaolin clay
mullite . kaolin clay
mullite
. silica silica fume
1450 mullite ,
silica tridymite .
1550 mullite peak intensity
, silica silica fume tridymite peak
, 1650 mullite peak
intensity alumina .
kaolin clay 1550 XRD
. silica silica fume
1650 mullite
, kaolin clay 1650
1550 mullite .
1650 alumina peak
alumina mullite
.
Fig. 4.19 matrix alumina, mullite
alumina-mullite 1600
500g 10, 20, 30
- 49 -
bending .
clay bending
matrix mullite, alumina
.
Silica bending
. bending
.
- 50 -
5 5 5 5
alumina-mullite bending
matrix bending
matrix bending .
.
1) matrix kaolin clay 1550
mullite , silica
silica fume 1650
.
, silica fume
, mullite .
3) matrix alumina-mullite
bending silica bending
,
bending .
- 51 -
ReferencesReferencesReferencesReferences
and ", J. Am. Ceram. Soc., 42(7) 311-324(1959).
2. Comeforo, Fisher and Bradley, " Mullitization of Kaolinite", J. Am.
Ceram. Soc., 31(9) 254-259(1948).
3. S. Kanzaki and H. Tabata, " Sintering and Mechamical properties of
Stoichiometric Mullite", J. Am. Ceram. Soc., 68(1) C6-C7(1985)
4. S. H. Risbud and J. A. Pask, “ Mullite Crystallization from
SiO2-Al2O3 Melts", J. Am. Ceram. Soc., 61 (1-2) 63-67(1978)
5. P. Lessing, R. Gordon and K. Mazdiyasni, " Creep of Polycrystalline
Mullite ", J. Am. Ceram. Soc., 58(3-4), 149(1975)
6. I.A. Aksay and J.A. Pask, "Stable and Metastable Equilibria in the
System SiO2-Al2O3", J. Am. Ceram. Soc., 58(11-12) 507-512
(1975).
7. A. P. S Rana, O. Aiko and J. A. Pask, “ Sintering of
Alpha-Alumina/Quartz and Alpha-Alumina/Cristobalite Related to
Mullite Formation", Ceram. Int., 8, 151-153(1982)
- 52 -

10012031
: : :Bae Ji Su
664-6 103-202
E-MAIL : [email protected]
Bending
: Sintering characteristics of matrix of high
alumina refractory and its effect on bending for
different material composition.

.
- -
1. DB
, ,
2. .
, .
3. , , .
4. 5 , 3
.
5.
1 .
6.

7.
.
2007 6

1
2-1. Alumina-Mullite
3-4.
3-4-1.
5

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材材料料에 에에 에 따른 따른 高高溫溫溫 Alumina Alumina …