REFRATECHNIK

New Developments in Monolithic ProductsNew Developments in Monolithic Products

For the Portland Cement Industry

Mark Weidhaas

Senior Sales Manager

Director of Monolithics

Refratechnik North America, Inc.

I t d ti

Content

Introduction

Cement Bonded Cement Bonded Monolithics

MixMix--CreteCrete Cement Bonded Monolithics

•• ARAR Mix-Crete

•• ZZ--ARAR Mix-Crete

Chemically Bonded Chemically Bonded Monolithics

NanobondNanobond No-Cement Monolithics

EZ EZ Dry Dry No-Cement Monolithics

Conclusions

Consumption of Monolithic Refractory Material

Cement Industry: Areas of Application

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Cement Bonded MonolithicsCement 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 ClMaterial Classes

VIBRATION Castables

SELF LEVELING Castables SELF-LEVELING Castables

PUMPABLE Castables

DRY GUNNITES

SHOTCRETES (Wet Gunning)

MixMix--CreteCrete MonolithicsMonolithics

AR MixAR Mix--Crete Crete Monolithics

AR Products - Riser Duct (after approximately 1 year)( pp y y )

reaction zoneili t i h t ti lsilicate-rich protective layer

unaffected microstructure

Improved Alkali Resistance

high

formation of

protective layer

Al2O

3alkali cu

87 %

bauxite

A up test / 1100 °C /

60 %

andalusite

K2 C

O3

coating-

repellent

40 %

fireclay

low

REFRACLAY 40 JC

25 %

fireclay

SiC 50 % 20–30 % 0 % 5–10 %

fireclay

REFRACLAY 25 JC

AR-Mixcrete Conceptp

The Mixcrete Concept: 6 refractory concretes

for the whole kiln line (static sections of the kiln line)

product combination Al2O3

[wt.-%]SiO2

[wt.-%]SiC

[wt.-%]ratio

( )

• modular / flexible installation

• flexible use of standard products

• graduated SiC contents/concepts [ ] [ ]REFRACLAY 40 LCC + 3 1 38 45 12REFRA-SiC 50 AR 2 1 36 43 17

1 1 32 39 25REFRAMULLITE 60 LCC + 3 1 44 36 16REFRA SiC50AR 2 1 42 35 20

graduated SiC contents/concepts

• zonally adapted product properties

• standardized product range

• smaller number of products REFRA-SiC 50 AR 2 1 42 35 201 1 36 33 27

REFRAMULLITE 63 LCC + 3 1 48 36 13REFRA-SiC 50 AR 2 1 45 35 17

1 1 39 33 25

smaller number of products

• simplified storage

• minimized storage times

• reduced warehousing costs1 1 39 33 25

REFRABAUXITE 75 LCC + 3 1 52 27 16REFRA-SiC 50 AR 2 1 48 27 20

1 1 41 27 27REFRABAUXITE 85 LCC + 3 1 61 17 16

• mixing bag by bag

• easy application

• mixing batches:

3:1 / 1:1 = 100 kgsREFRA-SiC 50 AR 2 1 56 18 20

1 1 47 20 27

3:1 / 1:1 100 kgs

2:1 = 75 / 150 kgs

Alkali Cup Test p

REFRACLAY 40 LCC + REFRA-SiC 50 AR

RCY 40 LCCRCY 40 LCC

3 1 2 13:1 1:12:1

R-SiC 50 AR

Alkali Cup Test p

REFRAMULLITE 60 LCC + REFRA-SiC 50 AR

RME 60 LCC

3 1 2 13:1 1:12:1

R-SiC 50 AR

Alkali cup test p

REFRAMULLITE 63 LCC + REFRA-SiC 50 AR

RME 63 LCC

3 1 2 13:1 1:12:1

R-SiC 50 AR

Alkali Cup Test p

REFRABAUXITE 75 LCC + REFRA-SiC 50 AR

RBE 75 LCC

3 1 2 13:1 1:12:1

R-SiC 50 AR

Alkali Cup Test REFRABAUXITE 85 LCC + REFRA-SiC 50 AR

RBE 85 LCC

3 1 2 13:1 1:12:1

R-SiC 50 AR

AR-Mixcrete – Clinker Cooler Curbs

REFRABAUXITE 85 LCC + REFRA-SiC 50 AR (1:1) REFRABAUXITE 85 LCC + REFRA-SiC 50 AR (1:1)

Cooler Curbs after 6 months Cooler Curbs after 4 months

AR-Mixcrete – Kiln Nose Ring

AR-Mixcrete

nose-ring after 12 months

Z Z AR MixAR Mix--Crete 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

product combination Al2O3

[wt.-%]SiO2

[wt.-%]SiC

[wt.-%]ZrO2

[wt.-%]REFRACLAY40LCC+

ratio

• zonally adapted product properties

• standardized product range

• smaller number of products

REFRACLAY 40 LCC + REFRAZIRCON Z AR 1 1 45 37 5 9

REFRAMULLITE 60 LCC +REFRAZIRCON Z AR 1 1 49 30 7 9

• simplified storage

• minimized storage times

• reduced warehousing costs

REFRAMULLITE 63 LCC +REFRAZIRCON Z AR 1 1 52 31 5 9

REFRABAUXITE 75 LCC +• mixing bag by bag

• easy application

• mixing batches:

1:1 = 100 kgs

REFRAZIRCON Z AR 1 1 53 25 7 9

REFRABAUXITE 85 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 Chemically Bonded MonolithicsMonolithics

Chemically Bonded Monolithics

Phosphate Bonded

Alumino – Orthophosphate (AlPO4) Bond

• H S T °C ( °F)• Heat Setting T > 500 °C (930 °F)

Plastics

Ramming MixesRamming Mixes

2 Component Castables / Dry Gunning Mixes

NANOBONDNANOBOND (Sol-Gel) System

EASY EASY DRY DRY Bond Systemy

NANOBONDNANOBOND MonolithicsMonolithics

NANOBOND Content

Introduction

Performance Characteristics

• Storage, curing and drying

• CCS, CMOR, PLC

• Sticking properties

• Acid resistance

Product Groups

• VIBRATION CASTABLE

• SELF LEVELING CASTABLE (P bl )• SELF-LEVELING CASTABLE (Pumpable)

• DRY GUNITE

• SHOTCRETE (Pumpable)

Introduction

Nanobond name derived from the chemical Liquid Binder No.1

• Aqueous colloid dispersion / suspensions of amorphous SiOAqueous colloid dispersion / suspensions of amorphous SiO2

• Uncured spherical particles 5 – 75 nm

• S l h d ff l l d b d l d h d ff• Solutions with different particle size, particle distribution and solid phase content different reactivity

Introduction

Sol-gel reaction / polymerization

• S t t i t • System contains one or more components 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 3 t k i (d & t) t t 24 th (CA 12 th )• 2 or 3 component packaging (dry & wet) storage up to 24 months (CA < 12 months)

• 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 reactionsLiquid 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, PLCcold crushing strength

140

coldmodulusof rupture 406080

100120140

ccs [

N/m

m²]

cold modulus of rupture

10

15

20

N/m

m²]

020

110 800 1000 1200 1400 1500

temperature [°C]REFRAJETCAST Nanobond F-60 AR/R REFRAJETCAST LC F-60 AR/R

0

5

10

110 800 1000 1200 1400 1500

cmor

[N

permanent linear change

0,0

temperature [°C]REFRAJETCAST Nanobond F-60 AR/R REFRAJETCAST LC F-60 AR/R

-0,4

-0,3

-0,2

-0,1plc

[%]

-0,5110 800 1000 1200 1400 1500

temperature [°C]REFRAJETCAST Nanobond F-60 AR/R REFRAJETCAST LC F-60 AR/R

Performance characteristics

Sticking properties to other surfaces, MACARBON brick

RSC NB S-60 R

carbon brick

B k MACARBON b i k i h

carbon brick

Broken MACARBON brick with

rough, dusty surface

RSC NB S 60 RRSC NB S-60 R• Treatment: thermal shock: 10 x 1200°C (200°C/h)

• Both materials still joinedNo 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°C (200°C/h)!Treatment: 5 x 1000 C (200 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

k h b dNo cracks in the bond area

REFRATECHNIKDrake Cement – Cyclone 4 (Nov 2013)

6 MT - RJC NB F-60AR Vernier Repairs

Performance characteristics

Acid attack on refractory castables

• Boiled in 70% sulphuric acid

cube 50 mm in sul. acid 70 wt.% at 20°C after 1 minute

f hafter 2 hours

Nanobond Product TypesNanobond Product Types

Material Types & Installation Methods

• Vibration Cast Activator in Dry ComponentVibration Cast Activator in Dry Component

• Self-Leveling Castable Activator in Dry Component

• Dry Gunite Activator in Dry Component

• P C t D A ti t dd d i Mi• Pump Cast Dry Activator added in Mixer

• Shotcrete Liquid Activator added at Nozzle

REFRATECHNIK

EASY EASY –– DRY DRY MonolithicsMonolithics

REFRATECHNIK

Easy Dry: Concept

Product Philosophy:Product Philosophy:

• no cement technology (<0.2 % CaO)• only one component-system for castables

1300 °C + K2CO3, K2SO4, KCl, CaSO4

y p y• only two component-system for JETCAST®-applications • easy installation with water comparable to CAC containing refractory concretes• storage and installation comparable to LC-refractory concretes storage and installation comparable to LC refractory concretes

- reduced water addition of 5.5 - 7.5 %- typical wet mixing time of 3 - 5 min for vibration and JETCAST®-applicationsh i ll ti t d b di• chemically activated bonding

• 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 cement industry: Easy Dry Low cement Nanobond

Temperature sensitivity storage + installation (water) (water) (silica sol

≥ 5 °C)

Drying out and heating-up safety

pp y y y

Apparent porosity / alkali resistance

Permanent linear change

Microstructural strength / abrasion resistance

Microstructural elasticity / TSR

Ratio microstructural strength/elasticity

Refractoriness / hot modulus of rupture

comparable respectively

high level of propertiesimproved worse

REFRATECHNIKDrying Out and Heating-Up

Recommendation

Installation Details

Installation Details

Cement Bonded Monolithics:

• Potable Water for Mixing

• Mix 5 Minutes Minimum

• Water Range

• Material & Water Temp > 50 F

h h lf f• 6 – 12 Month Shelf Life

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 th Sh lf Lif• 12 – 24 Month Shelf Life

Shipping “Freeze Watch” Indicators

Material OK Material Frozen in TransportMaterial OK Material Frozen in Transport

Liquid Binder No 1 – The Numbers

DensityDensity

1000 - 1350 Kg / M3

1.0 - 1.35 Kg / Liter

2 20 2 98 Lb / Lit 2.20 - 2.98 Lb / Liter

8.33 – 11.28 Lb / Gal

9.81 Lbs / Gal (Avg)

Liquid Binder No 1 - Mixing Examples

For REFRAREFRACASTCAST Nanobond F-60 AR :

150 Kg Batch (6 x 25 Kg / 55 Lb Sacks) 800 Kg Batch (1764 Lb Sack) 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)

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

27.0 Lbs LB#1 : 150 Kg Dry Mix

Using 9.81 Lbs / Gal Density

144.0 Lbs LB#1 : 800 Kg Dry Mix

Liquid Binder No 1 – Health Concerns

Nanobond Accelerant Details

Shotcrete Materials:

• Wet mix with Liquid Binder No 1

Vibration Casting Materials

• Dry Accelerant included in dry mix• Wet mix with Liquid Binder No 1

• Wet mix pumped to installation site

• Liquid Accelerator added to high pressure air at the nozzle

Dry-Gunning Materials

• Dry Accelerant included in dry mix

Pump Casting Materials:

• Li ht b l d d

q g p

(~0.7 wt% to Dry Mix)

• Frost free storage! > 5°C / 41°F• Light-brown colored powder

• Addition of 0.1 - 0.2 wt% to Dry Mix

• Initial set within 60 minutes at 70 °F

• Gelling within seconds plastic material on the surface

• NO addition of Powder Accelerator or additional water!

Initial set within 60 minutes at 70 F

• Without accelerator very long setting time (~days)

!

• Without addition of any 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 t h littl ff t tti ti• Ambient temps have little effect on setting times

• Mixing and Transport Equipment must be clean (No CA!)• Mixing and Transport Equipment must be clean (No CA!)

• Application Temp > 1500 FApplication 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

h h lf f• 6 Month Shelf Life

REFRATECHNIK

ConclusionsConclusions

Cement Bonded Cement Bonded Monolithics Conclusions

High Initial Strengths at Room Temperature

Single Component Castable Mixes – Just add Potable Water

Two Component Jetcast Mixes 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

NanobondNanobond Conclusion

Two Component Material: Dry Mix + Liquid Binder Extended Shelf Life

A il bl i 50 E i ti Q liti V Sh t Ti f S i l D l t Available in > 50 Existing Qualities Very Short Time for Special Developments

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!

Wet mixing with Liquidbinder No. 1 NO Additional WaterWet g w t qu db de No. NO dd t o a Wate

Different Accelerators as Activators for Different Installation Methods

EZ Dry EZ Dry Monolithics Conclusions

High Initial Strengths at Room Temperature

Single Component Castable Mixes Just add Potable Water 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 to LC-Refractory Concretesp y

Thank YouThank You