Quality assurance system and testing methods in the refractory industry

Stefan Schwarz
Quality assurance system and testing methods in the refractory industry

Agenda

1. Introduction

2. For your safety: Quality assurance & existing standards

3. Comparing apples with apples: Testing methods for…

3.1 physical-mechanical properties
3.2 thermal / thermo-mechanical properties
3.3 chemical-mineralogical properties

4. Final statement
Influences on refractory performance

• Quality of installation
(Customer + RT team)
Influences on refractory performance

• Quality of installation
(Customer + RT team) Low cement castable with SiC & ZrO2
e.g. REFRACLAY 40 Z AR

• Refractory selection
(Customer + RT team)

KRONAL® 50 AR TOPMAG® A1 REFRAMAG® AF KRONAL® 63 AR

Influences on refractory performance

• Quality of installation
(Customer + RT team)

• Refractory selection
(Customer + RT team)

• Engineering concepts
(Customer + RT team)
Influences on refractory performance

• Quality of installation
(Customer + RT team)

• Refractory selection
(Customer + RT team)

• Engineering concepts
(Customer + RT team)

• Quality assurance system

(RT team)
Quality assurance system and testing methods in the refractory industry

Agenda

1. Introduction

2. For your safety: Quality assurance & existing standards

3. Comparing apples with apples: Testing methods for…

3.1 physical-mechanical properties
3.2 thermal / thermo-mechanical properties
3.3 chemical-mineralogical properties

4. Final statement
Quality Assurance System at Refratechnik

faulty material is rejected

faulty material is rejected

faulty material is rejected

Raw material “Green” brick Burned brick

• Selected suppliers • Press control • Manual control

• Samples on delivery • Samples (density…) • Samples (physical properties)
Quality Assurance System at Refratechnik

1. Testing instructions for every production step

2. Regular deviation comparison

3. All determined values are incorporated into our Statistic Process Control system (SPC)

monitoring of properties from raw material to burned brick

Existing standards

DIN: German standard

EN: European standard
DIN EN: German standard (DIN) & European standard (EN)
ISO: International standard
DIN ISO: International standard used as national standard
ASTM: American standard (American Society for Testing and Materials)
AFNOR: French standard
BS: British standard
PRE: Fédération Européenne des Fabricants de Produits Réfractaires,
most of the PRE recommendations have been included in the
EN-standards or have been replaced by EN standards
Existing standards

German standard “DIN” was developed by “Deutsches Institute für Normung”

(founded December 1917)

DIN standards become more and more the basis for European or global standards

Today one third of all European standards (EN) derive from a DIN standard
Quality assurance system and testing methods in the refractory industry

Agenda

1. Introduction

2. For your safety: Quality assurance & existing standards

3. Comparing apples with apples: Testing methods for…

3.1 physical-mechanical properties
3.2 thermal / thermo-mechanical properties
3.3 chemical-mineralogical properties

4. Final statement
Data Sheet: Information of Refractories

Bulk Density
Physical-mechanical
Apparent Porosity properties
Cold Crushing Strength at room temperature

Refractoriness under Load

Pyrometric Cone
Thermal Expansion Thermal/thermo-
mechanical properties
Thermal Shock Resistance
Thermal Conductivity

Chemical-mineralogical
Chemical Analysis properties
Physical / mechanical properties

Physical / mechanical properties at room temperature

• Outer Appearance

• Density

• Porosity

• Cold Crushing Strength (CCS)

• Modulus of Rupture (MOR)

Physical / mechanical properties

Outer Appearance

Dimension and Shape: Permissible Deviation:

B
width A, B ±1,5 mm
length L ±2,0 mm
height H ±1,5 %
flexure and bulging ≤1,0 mm
H

→ Brick can be accepted

L
A

(Published in: Cement-Lime-Gypsum International 42 (1989),

No. 2, P. 57 - 67 (German), P. 79 - 83 (English))
Physical / mechanical properties

Outer Appearance

C Dimension of Edge Damage

If D ≥ 8 mm
A ≤ 40 mm
B+C ≤ 20 mm

→ Brick can be accepted

Published in:
Cement-Lime-Gypsum International 42
(1989),
No. 2, P. 57 - 67 (German), P. 79 - 83 (English)
Physical / mechanical properties

Outer Appearance

Dimension of Corner Damage

If A + B + C ≤ 60 mm
→ Brick can be accepted
C

Published in:
Cement-Lime-Gypsum International 42 (1989),
No. 2, P. 57 - 67 (German), P. 79 - 83 (English)
Physical / mechanical properties

Density (DIN 51 065; substituted by DIN EN 993, part 1 and DIN EN 1094, part 4)

Bulk Density: quotient of mass of material and its volume (including the pores)

Measuring and weighing of test sample (or the water displacement method)

Brick grade Bulk density [g/cm3]

Magnesia-Chromite 2.9 - 3.2
Corundum 3.0 - 3.2
Magnesia-Spinel 2.8 - 3.1
Bauxite 2.6 - 3.0
Fireclay 1.9 - 2.3
Silica 1.8 - 1.9
Insulating bricks < 1.6
Physical / mechanical properties

Apparent Porosity (DIN 51 056; substituted by DIN EN 993, part 1)

Apparent porosity (AP) determined: AP = bulk density · water absorption [%]

Total porosity (TP) calculated: TP = (density - bulk density) x 100/density

closed pore

open pore
blind pore

blind pore
Physical / mechanical properties

Apparent Porosity (DIN 51 056; substituted by DIN EN 993, part 1)

Apparent porosity (AP) determined: AP = bulk density · water absorption [%]

Total porosity (TP) calculated: TP = (density - bulk density) x 100/density

closed pore

open pore
blind pore

blind pore
Physical / mechanical properties

Apparent Porosity (DIN 51 056; substituted by DIN EN 993, part 1)

• Apparent porosity: only open pores which can be infiltrated by water

• Measured by exchanging air in brick with e.g. water and weighing sample afterwards
Physical / mechanical properties

Cold Crushing Strength - CCS (DIN 51 067; substituted by DIN EN 993, part 5 and DIN EN 1094, part 5)

σ pressure = F/A (A = Sample area vertical to the force) [N/mm2]

• indications about refractory structure (e.g. ceramic bonding of grains, burning temperature)

• conclusions regarding porosity, thermal conductivity, thermal shock resistance, abrasion

resistance

• possibility to control the homogeneity of brick production

Physical / mechanical properties

Cold Crushing Strength - CCS (DIN 51 067; substituted by DIN EN 993, part 5 and DIN EN 1094, part 5)

Cold crushing strength values of

several refractory brick grades

Brick Grade CCS [N/mm2]

Silica 15 - 50
Fireclay 12 - 70
Corundum 35 - 80
Magnesia 50 - 110
Magnesia-Chromite 30 - 70
Magnesia-Spinel > 40
Insulating Brick 3 - 20
Physical / mechanical properties

Cold Crushing Strength - CCS (DIN 51 067; substituted by DIN EN 993, part 5 and DIN EN 1094, part 5)

• CCS only determined at room temperatures

material behaviour will differ under operational conditions

• To evaluate the material behaviour under operational conditions thermo-mechanical testing

methods are applied
Physical / mechanical properties

Modulus of Rupture (MOR) DIN 51 048, part 1 (substituted by DIN EN 993, part 6)

• Resistance to deformation under bending load

• Bending strength: σ bending = 3⋅F⋅I/(2⋅b⋅h2) [N/mm²]

F
I = distance between blades,
b = width of sample,
h = height of sample pressure load

tensile load
Physical / mechanical properties

Modulus of Rupture (MOR) DIN 51 048, part 1 (substituted by DIN EN 993, part 6
Thermal properties

• Pyrometic Cone Equivalent (“Seger Cone”)

• Thermal Expansion
• Thermal Conductivity
• Softening behaviour under Temperature and Load
- Refractoriness under Load (RUL)
- Refractories under Load (Differential)
- Thermal Expansion under Load (Creep)
• Thermal Shock Resistance
• Hot Modulus of Rupture (HMOR)
Thermal properties

Pyrometric Cone Equivalent (PCE) DIN 51 063 (substituted by DIN EN 993, part 12)

• Refractories do not have specific melting points, but become soft within a temperature interval
• Usually softening point not given in °C, but determined with Seger Cone (developed by Dr.
Seger, 1886)

Refractories are divided into

PCE-No.
Seger cone ISO-cone-No. according to °C
fire-resistant < 17 below ISO 150 below 1500
refractory 17 - 36 min. ISO 150 min. 1500
highly refractory > 36 min. ISO 180 min. 1800
Thermal properties

Pyrometric Cone Equivalent (PCE) DIN 51 063 (substituted by DIN EN 993, part 12)
1)
Seger Cone No. Melting temp. Seger Cone No. 1) Melting temp.
according to ISO °C according to ISO °C
17 150 1500 32.5 172 1720
18 152 1520 33.5 174 1740
19 154 1540 34 176 1760
20 156 1560 35 178 1780
26 158 1580 36 180 1800
27 160 1600 37 183 1830
27.5 162 1620 38 186 1860
28 164 1640 39 188 1880
29 166 1660 40 190 1900
30 168 1680 41 194 1940
31 170 1700 42 198 1980
1)
Small Seger cone, Temperature increase 2.5 °C/min. = 150 °C/h
Thermal properties

Pyrometric Cone Equivalent (PCE) DIN 51 063 (substituted by DIN EN 993, part 12)

• PCE determined by comparing unknown ceramic samples to the deformation of

known standard samples (consisting of prefabricated alumina and silica mixtures).
• Cone is defined as fallen when its top is touching the ground plate

Sample cone
Thermal properties

Pyrometric Cone Equivalent (PCE) DIN 51 063 (substituted by DIN EN 993, part 12)

Installation of sample and Seger cone on achieving

Seger cone on the substrate its specific cone temperature

80 - 85°
90°

Hermann Seger, 1839 - 1893

Thermal properties

Thermal Expansion (DIN 51 045)

Expansion curves of most refractories are more or less linear with increasing temperature and
reversible
Thermal properties

Thermal Expansion (DIN 51 045)

• Important for determining the thermal shock resistance

• Important in service: allowance for expansion (expansion joints, cardboards)
Thermal properties

Thermal Expansion (DIN 51 045)

stamp
thermocouple
Thermal properties

Thermal Conductivity up to 1600 °C with Hot Wire Method (DIN 51 046)

Thermal conductivity of refractories can be determined according to 3 methods:

• Hot wire method according to DIN EN 993, part 14-15

• Calorimetric method according to ASTM C 201 and C 202, C 417, C 182
• Laser-flash method

Significant differences between hot wire and calorimetric method

(values of calorimetric method up to 25 % lower compared to hot wire method values).

Values of laser-flash method within accuracy limit of the hot wire method.

Hot wire method and ASTM method most common methods regarding refractories.
Thermal properties

Thermal Conductivity up to 1600 °C with Hot Wire Method (DIN 51 046, substituted by DIN EN 993, part 14-15)

Material Thermal conductivity

at 1000 °C [W/(m K)]
Magnesia 4.4
Magnesia Chromite 2.5
Magnesia Spinel 2.8
Magnesia Hercynite 2.6
High Alumina 2.1
Fireclay 1.2
Insulating Brick 0.6
Iron 28.0

Thermal conductivity important for calculating heat loss of rotary kilns

and layout of refractories
Thermal properties

Thermal Conductivity up to 1600 °C with Hot Wire Method (DIN 51 046, substituted by DIN EN 993, part 14-15)

Thermal conductivity depends mainly on

• Service temperature
• Chemical & mineralogical composition of refractory material
• Porosity
• Pore size
• Brick firing temperature/ceramic bonding
• kiln process conditions (i.e. infiltration)
Thermo-mechanical properties

Refractoriness under Load (RUL) DIN 51 064

• RUL is a function of the content and the degree of distribution of low melting point flux agents
(impurities)

• RUL is determined by constant heating up of 50mm x 50mm sample cylinders under 0,2 N/mm2

• Change in height of the cylinders is plotted with magnification factor 10 on a diagram

 Thermo-mechanical properties

Refractoriness under Load (RUL) DIN 51 064

Culmination point
Expansion

+5mm
~2mm

ta: 3mm below culmination

-5m
Silicate brick
Deformation

Chromite brick
Magnesia brick
Fireclay brick

te: 10mm below culmination

Thermo-mechanical properties

Refractoriness under Load (RUL) DIN 51 064

Characteristic temperatures are ta , te and tb with corresponding compression values.

ta: Initial temperature of softening, derived from intersection of test curve and horizontal line
which is 3mm below the culmination point of sample test curve (~0.6 % compression of
test sample)

te : Final temperature, reached when the sample test curve has dropped 10mm below the
culmination point (~20 % compression of test sample)

t b: Should a testing sample collapse the final temperature is indicated as tb

Thermo-mechanical properties

Refractoriness under Load (RUL) DIN 51 064

Brick grade ta /°C

Fireclay 1300 - 1550
Corundum 1600 - 1750
Silica >1660
Magnesia-Chromite >1550
Magnesia-Hercynite 1600
Dolomite 1700
Magnesia-Spinel >1700
Carbon brick no softening
Thermo-mechanical properties

Refractories under Load (Differential) DIN 51 053, part 1 (substituted by DIN EN 993, part 8)

Refractories under Load (Differential) was developed in order to:

• eliminate errors, resulting from inherent expansion of the test equipment

• to test in an oxidizing atmosphere

The RUL (Differential) is determined by constant heating of 50mm x 50mm

sample cylinders under a pressure of 0,2 N/mm2
But specimens have an internal bore hole (permitting sensors on lower and upper sample side)

…Measured temperatures for RUL (Differential) are lower than RUL values !
Thermo-mechanical properties

Refractories under Load (Differential) DIN 51 053, part 1 (substituted by DIN EN 993, part 8)

Curve example of Refractories under Load

Characteristic temperatures are

t0: temperature of highest expansion
(Dmax (%): maximum expansion)
t05: 0.5 % compression from the
temperature of highest expansion
t1 -t5: 1 - 5 % compression from the
temperature of highest expansion
t f: temperature of breaking sample
Thermo-mechanical properties

Thermal Expansion under Load (Creep)DIN 51 053, part 2 (substituted by DIN EN 993, part 9)

Thermal expansion under load (Creep) is a long-term testing method

50mm x 50mm sample cylinders with internal bore hole heated at a constant speed
and under a load of 0,2 N/mm2
Samples are held for 10 to 50 h under a constant load

Sample compression is given in relation to the test time as a measure

of creep at a defined testing temperature

… temperature + pressure + time

Thermo-mechanical properties

Thermal Expansion under Load (Creep)DIN 51 053, part 2 (substituted by DIN EN 993, part 9)
Characteristic values:
Curve example of Creep under Load
Dmax (%): maximum expansion of
the loaded sample
z24 - z14
flow rate: v14-24 = [%/h]
10
Thermo-mechanical properties

Thermal Expansion under Load (Creep)DIN 51 053, part 2 (substituted by DIN EN 993, part 9)
Thermo-mechanical properties

Thermal Shock Resistance DIN 51 068, part 1/2 (substituted by DIN EN 993, part 11)

Thermal shock resistance mainly depends on thermal conductivity, thermal expansion, difference in
temperature, strength and elastic behaviour
Thermo-mechanical properties

Thermal Shock Resistance DIN 51 068, part 1/2 (substituted by DIN EN 993, part 11)

• Sample bricks heated up to 950°C and subsequently quenched with air or running cold water
• Test is repeated until test sample is destroyed
• The number of cycles is a term for the thermal shock resistance

Two testing methods can be applied:

• air quenching method (heating up to 950°C)

• water quenching method (heating up to 950°C, only applicable for brick grades which are not
effected by hydration)
Thermo-mechanical properties

Hot Modulus of Rupture (HMOR) DIN 51 048, part 1 (substituted by DIN EN 993, part 7)

1200 °C
Thermo-mechanical properties

Hot Modulus of Rupture (HMOR) DIN 51 048, part 1 (substituted by DIN EN 993, part 7)

HMOR characterized by:

1.Structural configuration of the refractory material
2.Amount and properties of occurring melts

HMO R (N/mm2)
Testing temperature (°C) 1200 1400 1500
Magnesia, low iron content > 14 11 8
Magnesia, high iron content > 12 5 1
Magnesia-Chromite > 10 5 3
High Alumina > 25 18 7
Zirconia > 25 > 25 > 18
Thermo-mechanical properties

Hot Modulus of Rupture (HMOR) DIN 51 048, part 1 (substituted by DIN EN 993, part 7)

Equipment to determine the melting behaviour of material.

Thermo-mechanical properties

Hot Modulus of Rupture (HMOR) DIN 51 048, part 1 (substituted by DIN EN 993, part 7)

Photo series of test

sample under different
temperatures.
Chemical-Mineralogical Properties
Chemical-Mineralogical Properties

Chemical Analysis (Determination of Chemical Composition)

Typical Methods:

• Wet Chemistry

• Atomic Absorption Spectroscopy (AAS)

• X-Ray Fluorescence Spectroscopy (XRF)

• Routine quality control, raw material analysis,

wear analysis of refractory products
Chemical-Mineralogical Properties

Cup Corrosion Test DIN 510 69

Alkali test of a high alumina Alkali test of a SiC containing high
brick with K2CO3 alumina brick with K2CO3
Chemical-Mineralogical Properties

Mineralogical investigations with X-ray diffraction

X-ray diffraction diagram of a used

magnesia-spinel brick grade, salt
infiltrated
Chemical-Mineralogical Properties

Microscopical techniques

• Light Microscopy (transmitted light and reflected light microscopy)

• Microprobe Analysis (WDS, EDS)

• Scanning Electron Microscopy (SEM)

Advantages of these microscopic investigation compared to other investigation methods:

Diagnosis of mineral phases composition in raw materials, refractory products etc.

– AND their configuration (textural/structural criteria, pore shape and size etc.)
Chemical-Mineralogical Properties

Mineralogical investigations with Reflected Light Microscopy

Unused magnesia-spinel brick grades with different raw material composition:

Chemical-Mineralogical Properties

Mineralogical investigations with Scanning Electron Microscopy (SEM)

Example: Hydration of Magnesia

crack formation, caused by formation of brucite (Mg(OH)2 hexagonal, tabular-like brucite

Acc.V Spot Magn Det WD Exp Acc.V Spot Magn Det WD Exp Acc.V Spot Magn Det WD Exp
25.0 kV 4.0 540x SE 9.8 17 CRB Analyse Service GmbH 25.0 kV 4.0 10000x SE 9.9 13 CRB Analyse Service GmbH 25.0 kV 4.0 7800x SE 9.6 17 CRB Analyse Service GmbH
Chemical-Mineralogical Properties

Mineralogical investigations with Scanning Electron Microscopy (SEM)

Example:
Salt efflorescences (salt crystals) on a packing cardboard due to sea water impact
Final statement

Apparent Porosity

Thermal Cold Crushing

Shock Strength
Resistance

Bulk Density Thermal Conductivity

The physical-mechanical, thermal, thermo-mechanical and chemical-mineralogical

properties of refractory material correspond and influence each other
Final statement

Apparent Porosity

Thermal Cold Crushing

Shock Strength
Resistance

Reliable quality control is one main part of the final refractory

performance in your plant.

Bulk Density Thermal Conductivity

The physical-mechanical, thermal, thermo-mechanical and chemical-mineralogical

properties of refractory material correspond and influence each other
Standards and draft standards for mechanical testing methods of dense refractory products (at room temperatures)
Mechanical property DIN EN (prEN) DIN ASTM ISO BS AFNOR PRE

Bulk density DIN EN 993-1 DIN 51065 T.2 C 830 5017 3.8 (EN) NF ISO 5017
DIN EN 1094-4 C 20
C 914
Porosity DIN EN 993-1 DIN 51056

Gas permeability DIN EN 993-4 DIN 51058 C 577 8841 3.9 (EN) NF B 40-324

Pore size distribution DIN 66133 3.16

Cold crushing strength DIN EN 993-5 DIN 51067 C 133 10059-1 4.3 B 40-314 R 14-1
DIN EN 1094-5 10059-2 NF B 40-322 R 14-2
NF B 40-342

Cold modulus of rupture DIN EN 933-6 DIN 51048 T.2 C 133 5014 4.4 (EN) NF ISO 5014

Hot modulus of rupture DIN EN 993-7 DIN 51048 C 583 5013 4.5 NF B 40-302
C 1099
E-modulus E DIN 51942 C 855 12680-1 B 40-311
(resonance) (resonance)
C 1419 (echo) B 40-312
(echo time)

Abrasion resistance DIN EN 993-20 DIN 52108 C 704 (stream 4.6

(grinding abr.) abrasion)
Standards and draft standards for thermo-mechanical testing methods of dense refractory products
Thermo-mechanical property DIN EN (prEN) DIN ASTM ISO BS AFNOR PRE

Seger cone DIN EN 993-12 DIN 51063 C 24 528 5.2 B 40-305

1146 NF ISO 528

After skrinage DIN EN 993-10 DIN 51066 T.1 C 133 2478 5.10 NF 40-325

Refractoriness under load DIN 51064

Refractoriness under load DIN EN 993-8 DIN 51053 T.1 C 16 1893 4.9 NF B 40-326 (ISO)
(differential)
Thermal exp. under load DIN EN 993-9 DIN 51053 T.2 C 832 3187 NF B 40-327 (ISO)
(creep)

Thermal expansion DIN EN 993-19* DIN 51045 T.1-T.5 C 832 5.3 B 40-308
5.4
5.14
Thermal conductivity DIN EN 993-14 & - DIN 51046 T.1 C 201 8894-1 5.5 NF B 40-316
15 C 202 8894-2 5.6 B 40-303
C 1113
Thermal shock resistance DIN EN 993-11 (air) DIN 51068 (water) C 1100 5.11 R 5-1
DIN 51045 (air) (ribbon R 5-2
test)
C 1171

* in preparation
Standards and draft standards for chemical testing methods of dense refractory products
Chemical property DIN EN (prEN) DIN ASTM ISO BS AFNOR PRE

Cup corrosion test DIN 51069 T.2 C 768 8890 5.13 R 34

C 874 10080

CO resistance C 288 3.10

Hydration resistance C 456 12676 3.14

Sulfuric acid resistance DIN EN 993-16 DIN 51102 T.1 8890 3.12 B 40-323
10080 3.15

Oxidation resistance C 862

(SiC bricks)

Resistance to caustic solution DIN 51103