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%

510 %

2030 %

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

45

37

REFRAMULLITE60 LCC+
REFRAZIRCON Z AR

49

30

REFRAMULLITE63 LCC+
REFRAZIRCON Z AR

52

31

REFRABAUXITE75 LCC+
REFRAZIRCON Z AR

53

25

REFRABAUXITE85 LCC+
REFRAZIRCON Z AR

60

18

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 <150C / 302F
NB Dry out schedules with heating rates up to 100C / hr (212F / hr)
CA: 3 to max. 50C
/ 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

>100C
>100 C

Nanobond
Hydraulic bond (CA)

Performance characteristics
CCS, CMOR, PLC

ccs [N/mm]

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/mm]

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 1200C (200C/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
1000CC (200
(200C/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 20C

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 > 5C / 41F (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! > 5C / 41F

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 100C /Hr Heatups
Same CCS and CMOR like CA-Bonded Materials > 800C (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 > 5C!
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