New Developments in Monolithic Products

REFRATECHNIK
New Developments in Monolithic Products
For the Portland Cement Industry
Mark Weidhaas
Senior Sales Manager
Director of Monolithics
Refratechnik North America, Inc.
Content
 Introduction
I t d ti
 Cement Bonded Monolithics
 Mix
Mix--Crete Cement Bonded Monolithics
•
•
AR Mix-Crete
Z-AR Mix-Crete
 Chemically Bonded Monolithics
 Nanobond No-Cement Monolithics
 EZ Dry No-Cement Monolithics
 Conclusions
Consumption of Monolithic Refractory Material
Cement Industry: Areas of Application
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Cement Bonded Monolithics
CALCIUM – ALUMINATE Cement Bonded Monolithics
• REGULAR Cement
CA > 4%
• MEDIUM Cement
2% < CA < 4%
• LOW Cement
1% < CA < 2%
• ULTRA – LOW Cement
CA < 1%
M t i l Cl
Material
Classes
 VIBRATION Castables
 SELF-LEVELING
SELF LEVELING Castables
 PUMPABLE Castables
 DRY GUNNITES
 SHOTCRETES (Wet Gunning)
Mix--Crete Monolithics
Mix
AR MixMix-Crete Monolithics
AR Products - Riser Duct ((after approximately
pp
y 1 yyear))
reaction zone
silicate-rich
ili t i h protective
t ti llayer
unaffected microstructure
Improved Alkali Resistance
AAl2O3
high
alkali cuup test / 1100 °C / K2CO3
formation of
protective layer
87 %
bauxite
60 %
andalusite
40 %
fireclay
coatingrepellent
REFRACLAY 40 JC
25 %
fireclay
low
REFRACLAY 25 JC
SiC
0%
5–10 %
20–30 %
50 %
AR-Mixcrete Concept
p
The Mixcrete Concept: 6 refractory concretes
for the whole kiln line ((static sections of the kiln line))
• modular / flexible installation
• flexible use of standard products
• graduated SiC contents/concepts
• zonally adapted product properties
• standardized product range
• smaller number of products
• simplified storage
• minimized storage times
• reduced warehousing costs
• mixing bag by bag
• easy application
• mixing batches:
3:1 / 1:1 = 100 kgs
2:1
= 75 / 150 kgs
product combination
REFRACLAY 40 LCC+
REFRA-SiC50 AR
REFRAMULLITE60 LCC+
REFRA-SiC
A SiC50
50 AR
REFRAMULLITE63 LCC+
REFRA-SiC50 AR
REFRABAUXITE75 LCC+
REFRA-SiC50 AR
REFRABAUXITE85 LCC+
REFRA-SiC50 AR
ratio
3
2
1
3
2
1
3
2
1
3
2
1
3
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
Al 2O3
[[wt.-%]]
38
36
32
44
42
36
48
45
39
52
48
41
61
56
47
SiC
SiO2
[[wt.-%]] [wt.-%]
45
12
43
17
39
25
36
16
35
20
33
27
36
13
35
17
33
25
27
16
27
20
27
27
17
16
18
20
20
27
Alkali Cupp Test
REFRACLAY 40 LCC + REFRA-SiC 50 AR
RCY 40 LCC
31
3:1
21
2:1
1:1
R-SiC 50 AR
Alkali Cupp Test
REFRAMULLITE 60 LCC + REFRA-SiC 50 AR
RME 60 LCC
31
3:1
21
2:1
1:1
R-SiC 50 AR
Alkali cupp test
REFRAMULLITE 63 LCC + REFRA-SiC 50 AR
RME 63 LCC
31
3:1
21
2:1
1:1
R-SiC 50 AR
Alkali Cupp Test
REFRABAUXITE 75 LCC + REFRA-SiC 50 AR
RBE 75 LCC
31
3:1
21
2:1
1:1
R-SiC 50 AR
Alkali Cup Test REFRABAUXITE 85 LCC + REFRA-SiC 50 AR
RBE 85 LCC
31
3:1
21
2:1
1:1
R-SiC 50 AR
AR-Mixcrete – Clinker Cooler Curbs
REFRABAUXITE 85 LCC + REFRA-SiC 50 AR (1:1)
Cooler Curbs after 6 months
REFRABAUXITE 85 LCC + REFRA-SiC 50 AR (1:1)
Cooler Curbs after 4 months
AR-Mixcrete – Kiln Nose Ring
AR-Mixcrete
nose-ring after 12 months
Z AR MixMix-Crete Monolithics
Z AR-Mixcrete Concept
The Mixcrete concept: 6 refractory concretes
for the whole kiln line (static sections of the kiln line)
• modular / flexible installation
• flexible use of standard products
• graduated SiC contents/concepts
• zonally adapted product properties
• standardized product range
• smaller number of products
• simplified storage
• minimized storage times
• reduced warehousing costs
• mixing bag by bag
• easy application
• mixing batches:
1:1 = 100 kgs
product combination
ratio
Al 2O3
[wt.-%]
SiC
SiO2
ZrO2
[wt.-%] [wt.-%] [wt.-%]
REFRACLAY40
LAY 40 LCC+
C+
REFRAZIRCON Z AR
1
1
45
37
5
9
REFRAMULLITE60 LCC+
REFRAZIRCON Z AR
1
1
49
30
7
9
REFRAMULLITE63 LCC+
REFRAZIRCON Z AR
1
1
52
31
5
9
REFRABAUXITE75 LCC+
REFRAZIRCON Z AR
1
1
53
25
7
9
REFRABAUXITE85 LCC+
REFRAZIRCON Z AR
1
1
60
18
7
9
Z AR-Mixcrete: REFRACLAY 40 LCC + REFRAZIRCON Z AR
RCY 40 LCC
1:1
RZN Z AR
Z AR-Mixcrete: REFRAMULLITE 60 LCC + REFRAZIRCON Z AR
RME 60 LCC
1:1
RZN Z AR
Z AR-Mixcrete: REFRAMULLITE 63 LCC + REFRAZIRCON Z AR
RME 63 LCC
1:1
RZN Z AR
Chemically Bonded Monolithics
Chemically Bonded Monolithics
 Phosphate Bonded
 Alumino – Orthophosphate (AlPO4) Bond
• Heat
H SSetting T > 500 °C (930
( °F)
 Plastics
 Ramming Mixes
 2 Component Castables / Dry Gunning Mixes
 NANOBOND (Sol-Gel) System
y
 EASY DRY Bond System
NANOBOND Monolithics
NANOBOND Content
 Introduction
 Performance Characteristics
•
•
•
•
Storage, curing and drying
CCS, CMOR, PLC
Sticking properties
Acid resistance
 Product Groups
•
•
•
•
VIBRATION CASTABLE
SELF LEVELING CASTABLE (P
SELF-LEVELING
(Pumpable)
bl )
DRY GUNITE
SHOTCRETE (Pumpable)
Introduction
Nanobond name derived from the chemical Liquid Binder No.1
• Aqueous colloid dispersion / suspensions of amorphous SiO2
• Uncured spherical particles 5 – 75 nm
• Solutions
Sl
withh ddifferent
ff
particlel size, particlel ddistribution
b
andd solid
l d phase
h content  different
d ff
reactivity
Introduction
Sol-gel reaction / polymerization
• SSystem
t contains
t i one or more componentst  cause
gelling and hardening
• Gelification: colloidal Silica  3- dimensional
network  Si-O-Si bonds  water solvent
• Formation of Si-O-Si binding system
• thermal drying
• changing the pH value
• addition of ion soluble salts
•  Sol-Gel-Bond
Sol Gel Bond
Performance characteristics
Storage, curing and drying
• 2 or 3 componentt packaging
k i (d
(dry & wet)t)  storage
t
up to
t 24 months
th (CA < 12 months)
th )
• Short & controllable curing / hardening time  no exothermic reaction !
• CA takes longer to form complete CAH-phases
• Less sensitive to ambient installation temperatures than CA bonded materials
• Liquid component water content is not part of bonding chemical reactions
• CA bonded systems can trap water in C-A-hydrate phases
• NB  easy water evaporation <150°C / 302°F
• NB Dry out schedules with heating rates up to 100°C / hr (212°F / hr)
• CA: 3 to max. 50°C
° / hr
• Easy water evaporation helps avoid explosive steam spalling during hot repair or initial heat up
Performance characteristics
Initial heat-up of a 250 mm thick lining
22 Hour Savings
Performance Characteristics
>100°C
>100 C
Nanobond
Hydraulic bond (CA)
Performance characteristics
CCS, CMOR, PLC
ccs [N/mm²]
cold crushing strength
cold modulusof
modulus of rupture
110
800
1000
1200
1400
1500
temperature [°C]
15
REFRAJETCAST Nanobond F-60 AR/R
REFRAJETCAST LCF-60 AR/R
10
5
permanent linear change
0
110
800
1000
1200
1400
0,0
1500
temperature [°C]
REFRAJETCAST Nanobond F-60 AR/R
REFRAJETCAST LCF-60 AR/R
-0,1
plc [%]
cmor [N
N/mm²]
20
140
120
100
80
60
40
20
0
-0,2
-0,3
-0,4
-0,5
110
800
1000
1200
1400
1500
temperature [°C]
REFRAJETCAST Nanobond F-60 AR/R
REFRAJETCAST LCF-60 AR/R
Performance characteristics
Sticking properties to other surfaces, MACARBON brick
RSC NB S-60 R
carbon brick
BBroken
k MACARBON brick
b i k with
ih
rough, dusty surface
•
Treatment: thermal shock: 10 x 1200°C (200°C/h)
•
Both materials still joined
RSC NB S-60
S 60 R
No cracks
carbon brick
Performance characteristics
Sticking properties to other surfaces, high alumina castable surface
EN Norm 1402-5, Type A (230x114x64 mm)
Casting No.1 (bottom):
REFRACAST MC B-83 AL
Casting No.2 (on top):
REFRACAST Nanobond B-90 AL
Treatment: 5 x 1000
1000°CC (200
(200°C/h)!
C/h)!
Performance characteristics
Sticking properties to other surfaces, high alumina castable surface
after temperature treatment:
MOR (N/mm2), test regarding “sticking strength”
MOR = 21,7 N/mm2
Failure not in the contact area MCC – Nanobond
No cracks
k in the
h bbondd area
Drake Cement – Cyclone 4 (Nov 2013)
6 MT - RJC NB F-60AR Vernier Repairs
REFRATECHNIK
Performance characteristics
Acid attack on refractory castables
• Boiled in 70% sulphuric acid
after 1 minute
cube 50 mm in sul. acid 70 wt.% at 20°C
after
f 2 hours
h
Nanobond Product Types
Material Types & Installation Methods
• Vibration Cast
Activator in Dry Component
• Self-Leveling Castable
Activator in Dry Component
• Dry Gunite
Activator in Dry Component
• Pump
P
C t
Cast
D AActivator
Dry
ti t added
dd d in
i Mixer
Mi
• Shotcrete
Liquid Activator added at Nozzle
REFRATECHNIK
EASY – DRY Monolithics
REFRATECHNIK
Easy Dry: Concept
Product Philosophy:
• no cement technology (<0.2 % CaO)
• onlyy one component-system
p
y
for castables
• only two component-system for JETCAST®-applications
1300 °C + K2CO3, K2SO4, KCl, CaSO4
• easy installation with water comparable to CAC containing refractory concretes
• storage and installation comparable to LC
LC-refractory
refractory concretes
- reduced water addition of 5.5 - 7.5 %
- typical wet mixing time of 3 - 5 min for vibration and JETCAST®-applications
• chemically
h i ll activated
ti t d bonding
b di
• safe and faster dry out and heating up-procedure
• physical properties comparable to LC-refractory concretes
• refractoriness comparable to LC-refractory concretes
• alkali resistance comparable to LC-refractory concretes
REFRATECHNIK
Easy Dry: Systems Comparison
Application
pp
cement industry:y
Temperature sensitivity storage + installation
Easyy Dryy
(water)
Drying out and heating-up safety
Low cement
(water)
Nanobond
(silica sol
≥ 5 °C)
Apparent porosity / alkali resistance
Permanent linear change
Microstructural strength / abrasion resistance
Microstructural elasticity / TSR
Ratio microstructural strength/elasticity
Refractoriness / hot modulus of rupture
improved
comparable respectively
high level of properties
worse
Drying Out and Heating-Up
Recommendation
REFRATECHNIK
Installation Details
Installation Details
Cement Bonded Monolithics:
• Potable Water for Mixing
• Mix 5 Minutes Minimum
• Water Range
• Material & Water Temp > 50 F
• 6 – 12 Monthh Shelf
h lf Lifef
Installation Details
Nanobond No Cement Monolithics:
• Liquid Binder No. 1 - Translucent liquid
• Used for All Nanobonds
• Mixing Ratio Range
• Storage > 5°C / 41°F (Do Not Freeze)
• 12 – 24 M
Month
th Sh
Shelflf Lif
Life
Shipping “Freeze Watch” Indicators
Material OK
Material Frozen in Transport
Liquid Binder No 1 – The Numbers
Density
 1000 - 1350 Kg / M3
 1.0 - 1.35 Kg / Liter
 2.20
2 20 - 2.98
2 98 Lb / Liter
Lit
 8.33 – 11.28 Lb / Gal
 9.81 Lbs / Gal (Avg)
Liquid Binder No 1 - Mixing Examples
For REFRA
REFRACAST
CAST Nanobond F-60 AR :




150 Kg Batch (6 x 25 Kg / 55 Lb Sacks)
1.74 – 1.93 Gal : 100 Kg (Mixing Ratio)
1.84 Gal : 100 Kg (Avg)
2.75 Gal : 150 Kg (6 x 25 Kg sacks)
 Using 9.81 Lbs / Gal Density
 27.0 Lbs LB#1 : 150 Kg Dry Mix




800 Kg Batch (1764 Lb Sack)
1.74 – 1.93 Gal : 100 Kg (Mixing Ratio)
1.84 Gal : 100 Kg (Avg)
14.68 Gal : 800 Kg
 Using 9.81 Lbs / Gal Density
 144.0 Lbs LB#1 : 800 Kg Dry Mix
Liquid Binder No 1 – Health Concerns
Nanobond Accelerant Details
Vibration Casting Materials
• Dry Accelerant included in dry mix
Shotcrete Materials:
Dry-Gunning Materials
• Dry Accelerant included in dry mix
• Wet mix pumped to installation site
Pump Casting Materials:
• Light-brown
Li ht b
colored
l d powder
d
• Wet mix with Liquid Binder No 1
q Accelerator added to high
g pressure
p
air at the nozzle
• Liquid
(~0.7 wt% to Dry Mix)
•
Frost free storage! > 5°C / 41°F
• Gelling within seconds  plastic material on the surface
• Addition of 0.1 - 0.2 wt% to Dry Mix
• NO addition of Powder Accelerator or additional water!
• Initial set within 60 minutes at 70 °FF
• Without addition of any Accelerator  very long setting
time (days)!
• Without accelerator  very long setting time (~days)
!
Other Nanobond Considerations
•
Less No 1 Liquid Binder amount  shorter setting time
•
More No 1 Liquid Binder amount  longer setting time
•
A bi t temps
Ambient
t
have
h little
littl effect
ff t on setting
tti times
ti
•
Mixing and Transport Equipment must be clean (No CA!)
•
Application Temp > 1500 F
Installation Details
EZ Dry No Cement Monolithics:
• Potable Water for Mixing
• Mix 5 Minutes Minimum
• Water Range
• Material & Water Temp > 50 F
• 6 Monthh Shelf
h lf Lifef
REFRATECHNIK
Conclusions
Cement Bonded Monolithics Conclusions
 High Initial Strengths at Room Temperature
 Single Component Castable Mixes – Just add Potable Water
 Two Component Jetcast Mixes
 6-12 Month Shelf Life
 Long Dry-Outs (Temp Holds at 500, 1000 & 1500 °F)
 Material Temp > 50 °F to Install Properly
 Can be Difficult to Install at Low Temps
 Need to Add SiC / Zirconia / AZS to increase Alkali Resistance
Nanobond Conclusion
 Two Component Material: Dry Mix + Liquid Binder  Extended Shelf Life
 Available
A il bl in
i > 50 Existing
E i ti Q
Qualities
liti  Very
V Short
Sh t Ti
Time for
f Special
S ilD
Developments
l
t
 Short Setting Time  Hardening Time  Start Heating Up
 No Chemical Bonded Water  Very Easy Dry Out  Up to 100°C /Hr Heatups
 Same CCS and CMOR like CA-Bonded Materials > 800°C (1500 °F)
 Less Problems with Difficult Application Conditions (humidity, temperature)
 Excellent Sticking Properties to Other Refractory Materials  Hot and Cold Repair
 Storage of Liquidbinder No.1 Always > 5°C!
t Liquidbinder
qu db de No. 1  NO Additional
dd t o a Water
Wate
 Wet mixingg wwith
 Different Accelerators as Activators for Different Installation Methods
EZ Dry Monolithics Conclusions
 High Initial Strengths at Room Temperature
 Single Component Castable Mixes – Just add Potable Water
 Two Component Jetcast Mixes
 6 Month Shelf Life
 Short Dry-Out Schedules
 Chemically Activated Bonding
 Physical Properties Comparable to LC-Refractory Concretes
 Refractoriness Comparable to LC-Refractory Concretes
 Alkali Resistance Comparable
p
to LC-Refractoryy Concretes
Thank You

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