Cement Solutions I:
From the Research Lab to the Production Plant –
Cost Savings with Automated Quantitative X-ray Diffraction
Welcome Speakers
Arkady Buman
Holger Cordes
Technical Sales Support, XRF Madison, WI
Senior Applications Scientist, XRD Madison, WI
Today’s Topics New challenges in cement production Use of powder X-ray Diffraction (XRD) in controlling cement production
New Challenges in Cement Production Accurate clinker phase determination using alternative fuels Mill control Additive control in blended cements Quantification of Lime stone additions Quantification of Pozzolan admixtures, such as flyash, blast furnace slags, and silica fume Quantification of raw materials
Why X-ray Diffraction? Example: TiO2 (Anatase / Rutil)
Anatas (black)
Rutil (yellow) BOTH ARE 100% TiO2
Why X-ray Diffraction? Phase
Structure
XRD Pattern P o w d e r C e ll 2 . 2
Anatase 101
21063
200
10532
202
213
112
103
204
211
105
004
Anatase 0 25
30
35
40
45
50
55
60
Tetragonal TiO2 P o w d e r C e ll 2 . 2
Rutile
211
6033
101
016
25
Trigonal TiO2
30
35
002
220 210
200
111
Rutil 40
45
50
55
60
Why X-ray Diffraction? Each crystalline phase has a distinctive pattern (“fingerprint') Ö QUALITATIVE PHASE ID
Intensity of the reflections from a phase are proportional to the concentration of the phase in the mixture Ö QUANTITATIVE PHASE ANALYSIS
The width of the reflection is a function of the crystallinity of the phase
WHY DO WE NEED TO KNOW THIS?
Important Phases/Components: Clinker Clinker Clinkerphase phase
Name Name
Relevance Relevance
C3S/C2S C3S/C2S
Alite/Belite Alite/Belite
Hardness Hardness
C3A C3A
Aluminate Aluminate
Setting Settingtime time
C4AF C4AF
Brownmillerite Brownmillerite
Color, Color,Fe-content Fe-content
CaO CaO
Free FreeLime Lime
Kiln Kilntemperature temperaturecontrol control
Ca(OH)2 Ca(OH)2
Calciumhydroxide Calciumhydroxide
Kiln Kilntemperature temperaturecontrol control
Important Phases/Components: Cement Cement Cementphase phase
Name Name
Relevance Relevance
CaSO4·xH2O CaSO4·xH2O
Gypsum GypsumPhases Phases
Dehydration Dehydration/ /setting settingtime time
CaCO3 CaCO3
Calcite Calcite
Limestone Limestoneaddition addition3% 3%
Mg Mgphases phases
Periclase Periclase/ /Dolomite Dolomite
Mg-rich Mg-richquarries quarries
Glass Glass
Amorphous AmorphousPhase Phase
CEM CEMIII III/ /Reactivity Reactivity
Important Phases/Components: Raw Materials Material Material
Name Name
Relevance Relevance
Ca,Mg Ca,Mg(CO3) (CO3)
Limestone Limestone
Kiln KilnFuel Fueldosage dosage
SiO2 SiO2
Quarz Quarz
Grind Grindability ability
BF BFSlag Slag
Blast BlastFurnace FurnaceSlag Slag
CEM CEMIII III/ /Cost Cost
CaSO4x CaSO4xXH2O XH2O
Gypsum GypsumPhases Phases
Dosage Dosagefor forblend blend
Bypass/Dust Bypass/Dust
Sulfide, Sulfide,Spurrite Spurrite
Dosage Dosageand andDeposits Deposits
Audience Poll Please use your mouse to answer the question on the right of your screen: What methods are you currently using for phase determination? (Check all that apply): Freelime by titration only XRD channel in system Powder X-ray Diffraction Microscopy Bogue calculation None
XRD. . . Why Not More? XRD has been used on cement, clinker and minerals since the 1950’s Qualitative phase identification and standard-based quantification were the early applications. • Initially all these tasks were very cumbersome and difficult and needed either manual evaluation or expensive computer hardware. With the first fully shielded X-ray diffractometer (PDP controlled), our D500, Bruker started the move from University to Industry. Introducing PC-based diffraction software and developing a very intelligent search match for phases enabled non-PhD users to get meaningful results.
XRD. . . More and More Quantitative XRD in the past could only be done using either internal standards (RIR) or by calibration with reference material. Standard (reference) based approach • Very similar to XRF approach • One or more peaks are unique to a phase and are not overlapped • Relationship between Intensity and Concentration is developed by measuring characterized reference samples using the same parameters
This works very well for simple systems such as CaO Freelime or the limestone addition or Respirable Quartz • Characteristic peaks are available and not overlapped • Reference materials can be characterized (titration) or mixed
X-ray Diffraction Systems for Powders
D8 ADVANCE: modular, expandable research system 13
D4 ENDEAVOR: compact system, high throughput, quality control, automation ready
Methods for Quantitative XRD Classical Reference Material Based
Quantitative XRD Phase Analysis Conventional Quantitative Analysis measurement range
I
y
y
y %
Solid Solution Effects Schematical Representation
NIST RM's 8486, 8487, 8488 Solid Solution Effect for C3S C3S C2S
17000
16000
15000
14000
13000
12000
C3S C2S
11000
Lin (Counts)
10000
C3S
C3S
9000
8000
7000
C3A
6000
5000
C3S
4000
3000
C4AF C2S
2000
1000
0 28.5
29
30
31
32
2-Theta - Scale
33
34
35
Preferred Orientation Effects Schematical Representation
Randomly oriented powder
Highly textured sample
NIST RM 8486 Preferred Orientation Effects C3S C2S
17000
16000
15000
14000
13000
12000
C3S C2S
11000
Lin (Counts)
10000
C3S
C3S
9000
8000
7000
C3A
6000
5000
C3S
4000
3000
C4AF C2S
2000
1000
0 28.5
29
30
31
32
2-Theta - Scale
33
34
35
NIST RM's 8486, 8487, 8488 Conclusions Alite (C3S) exhibits strong peak shifts due to changes in chemical composition and varying intensities due to changes in both chemical composition and preferred orientation effects o C3A and C4AF clearly remain at the same positions
The various background of the patterns is directly related to the various iron content of the clinkers o Abundance of C4AF
Reliable clinker quantification is impossible using traditional XRD methods
Can a “Classical” Approach Work Here? NIST RM's 8486, 8487, 8488 Solid Solution Effect for C3S
C3S C2S
17000
16000
15000
14000
13000
12000
C3S C2S
11000
Lin (Counts)
10000
C3S
C3S
9000
8000
7000
C3A
6000
5000
C3S
4000
3000
C4AF C2S
2000
1000
0 28.5
29
30
31
32
2-Theta - Scale
33
34
35
Quantification Without Standards The Rietveld method generates a calculated diffraction pattern from the phase list and their structures, that is compared with the observed data. The differences between observed and calculated diffraction patterns are minimized using least-squares procedures.
Observed pattern Calculated pattern
Difference
Refinement
Methods for Quantitative XRD Rietveld Method 2 The Rietveld method: A direct standardless full-pattern approach to quantitative phase analysis • No standards • No calibration
Independent of equipment and sample properties such as tube aging, solid solution effects, and preferred orientation • No drift correction required
More and More. . . Lots of calculations required, as well as many parameters, limited the application to mainframes and Unix workstations (1994) • (none to be found in a cement plant) • Time to result for a sample > 120 minutes best case
The Rietveld “Refinement” uses many parameters; turn-on sequence and values need to be constrained to create meaningful results • Solid background in crystallography is required • Interactive type approach • Refinement needs to be tuned to instrument to empirically determine the instrument response function to constrain some refinement parameters
Faster and faster PC’s allowed this technique to mature (e.g. ZEROQUANT on 1997, WINRIET), but still an expert was needed to control it, with time to result still > 15 minutes
Breakthrough. . . Changed the Industry Using the PC platform and adapting the code to utilize Fundamental Parameters to describe the instrument function, new software was born. Instead of a parameter turn-on sequence and pure interactive approach, it uses a phase list and recipe and does not require ANY user input during its run.
TOPAS
TOPAS Standardless Quant
The unique TOPAS allows fully automated quantitative phase analysis from XRD data without any user input. Typical calculation times are dehydration effect • Too high Bassanite will have detrimental effect • Too long milling will cost money; mill is a large factor in energy consumption • All three sulfate phases have a different solubility • The ratio of the sulfates controls the setting behavior of the cement • The production process influences the sulfates as cement milling • Dehydrates gypsum to bassanite or even anhydrite • Typically in process control only the total SO3 content is monitored by XRF
Sulfates in Cement with TOPAS
TOPAS Hkl approach
From RR data
Quantitative Phase Analysis of Cements Quality and Process Control Cement • control of CO2 set points • control of dehydration characteristics in ball mill • control of amount of amorphous compounds • prediction of strength development in combination with other results • keeping a fingerprint of every sample as reference • check of competitor products
Quantification of Blast Furnace Slag Cements with TOPAS
Quantification of Blast Furnace Slag Cements with TOPAS How to quantify amorphous amounts like blast furnace slag in CEM III by Rietveld analysis? 20,000
We can calculate the crystalline phases
19,000 18,000 17,000 16,000 15,000 14,000
But how to handle amorhous humps as indicated by the blue curve?
13,000
Counts
12,000 11,000 10,000 9,000 8,000 7,000 6,000 5,000
background
4,000 3,000 2,000 1,000 0 10
15
20
25
30
35
40
2Th Degrees
45
50
55
60
65
Quantification of Blast Furnace Slag Cements with TOPAS Rietveld analysis can only take into account crystalline phases, which are normalized to 100 wt.% Using Rietveld analysis, amorphous phase abundances can only be quantified by adding a standard (spiking method) In an automated plant laboratory this is not a favored approach or practical at all. It even would be an additional source of error. If the amorphous part of the slag could be treated as its own phase, it could be seamlessly integrated into the Rietveld analysis.
Measurement Data: Blast Furnace Slag Sample: Slag sample of the VDZ Round Robin (2006): Material 1 High quality blast furnace slag 2,000 1,800 1,600
Counts
1,400 1,200 1,000 800 600 400 200 0 10
15
20
25
30
35
40 45 50 2Th Degrees
55
60
65
70
75
80
Round Robin VDZ 2006/7 In 2006 the VDZ (German Cement Works Association) organized a Round Robin focused on quantitative phase analysis of blast furnace slag cements using XRD methods. Three different BFSlag Cement samples to be analyzed were distributed to the participants. In all samples, slags of almost amorphous composition have been used. The pure slags have been made available to the participants as well.
Round Robin VDZ 2006/7 Results:
Results reference method
Application to the VDZ Round Robin Samples: Results Accuracy and Precision (values in wt. %, SD in brackets/1σ)
Every sample was measured 5 times (D4 ENDEAVOR, LynxEye Detector) The same emperical value for the mass of the hkl_phase was used for all samples Reference values: Sample 1 Sample 2 Sample 3 • sample 1: 25,0 wt.% Measurement 1 25,0 67,2 71,7 • sample 2: 67,0 wt.% Measurement 2 25,1 67,3 71,9 • sample 3: 72,0 wt.% Measurement 3
24,7
67,0
71,6
Measurement 4
25,1
67,3
71,9
Measurement 5
25,3
67,0
71,5
Mean
25,1
67,2
71,7
0,2
0,2
0,2
SD
TOPAS Improves Process and Quality Control
Effects can be seen which other methods do not detect at all (Bogue) or only after long analysis (microscopy)
Control of the alkali mass flow (C3A cubic/orthorhombic, Alkalisulphates) – very important for Cement Setting Behavior
Closer operation to the limits of the process (saving of energy and expensive raw materials) – instead of blind following of traditional LSF (Lime Saturation Factor), Silica and Alumina module
Freelime analysis can be done more reliably with TOPAS – interference stability!
Control of the cement milling – dehydration of the sulphates
TOPAS (Total Pattern Analysis Solutions) Benefits: Reliable results Does not break down when sample composition changes like
other packages Best available reproducibility
Latest generation Rietveld software
The Time for XRD is Now. . . From pick-up to result in less than 5 minutes! As fast as XRF Quantitative XRD enhances ability for process and quality control. Real phases equals real information. Cost savings will cover instrument investment • High margin cement is no accident. . . or luck. . . Push-button approach brings XRD to the control room
Automation Software AXSLAB Push Buttons to Start Routine Jobs Simply click a button to start a sample or a batch job Configurable by the user
Automation Software AXSLAB User Interface with Color-coded Results Table
Quantitative Rietveld Analysis Cement Industry Milestone reference: Paul, M., Hornung, D., Enders, M. & Schmidt, R. (2004): 'Process monitoring in a cement plant: The combination of optimized preparation procedures for clinker and cement and Rietveld analysis' World of Cement, 2, 35-42.
Quantitative Rietveld Analysis Cement Industry The cement industry is currently the fastest growing application area for quantitative Rietveld analysis The question is not IF, but WHEN the Rietveld method will be implemented for quality optimization and process control in ALL cement plants Paul, M. (2004)
Sample Preparation – Key to Success Ring and puck mill traditionally used will o Dehydrate the cement o Destroy crystal structure -> amorphous o Settings for XRF usually too long for XRD o Easy to automate Mortar mills o Too slow o Fine for XRD o Cannot be automated Mortar and pestle o Too slow x 2 o Operator dependent Powder mounts • too operator dependent • Not reproducible
Sample Preparation
Pressed pellets (steel rings) • Gentle grinding: free lime, sulfate phases, calcite • Uniform pressure: preferred orientation effects • Automation: Application in routine analysis
Automatic Preparation Module
Features:
Grinding with or without bind sample Predefined procedures for typical materials (RM, CLI, CM) Simple entry of individual parameters One button operation Predefined special programs (only grinding, only pressing)
Manual sample input Fine grinding mill Grinding aid dosing Tablet press Tablet cleaning Steel ring magazine
6 00
1260
Compact module for automatic sample preparation
60 0
Material in
Tablet out
POLAB® APM: Automatic Sample Preparation Module
new machine with sample changer
Lab Automation – AXSLAB Configuration: D4 with APMplus APMplus
D4 ONLINE
AXSLab User Interface Automation Control Transfer of results via LAN, e.g. to plant control system, LIMS system, Blending Software
Lan network
Thank you for attending! Please provide feedback by completing our brief survey. Also, please type any questions you may have in the Q&A panel.
www.bruker-axs.com
Upcoming events: Apr 20-24
ICMA, Reno, NV
May 7
Cement Solutions II Webinar: Improved C-114 Qualification with WDXRF
May 18-22
IEEE/PCA, Miami, FL
Oct 5-9
MS&T, Pittsburgh, PA
From the Research Lab to the Production Plant –
Cost Savings with Automated Quantitative X-ray Diffraction
Welcome Speakers
Arkady Buman
Holger Cordes
Technical Sales Support, XRF Madison, WI
Senior Applications Scientist, XRD Madison, WI
Today’s Topics New challenges in cement production Use of powder X-ray Diffraction (XRD) in controlling cement production
New Challenges in Cement Production Accurate clinker phase determination using alternative fuels Mill control Additive control in blended cements Quantification of Lime stone additions Quantification of Pozzolan admixtures, such as flyash, blast furnace slags, and silica fume Quantification of raw materials
Why X-ray Diffraction? Example: TiO2 (Anatase / Rutil)
Anatas (black)
Rutil (yellow) BOTH ARE 100% TiO2
Why X-ray Diffraction? Phase
Structure
XRD Pattern P o w d e r C e ll 2 . 2
Anatase 101
21063
200
10532
202
213
112
103
204
211
105
004
Anatase 0 25
30
35
40
45
50
55
60
Tetragonal TiO2 P o w d e r C e ll 2 . 2
Rutile
211
6033
101
016
25
Trigonal TiO2
30
35
002
220 210
200
111
Rutil 40
45
50
55
60
Why X-ray Diffraction? Each crystalline phase has a distinctive pattern (“fingerprint') Ö QUALITATIVE PHASE ID
Intensity of the reflections from a phase are proportional to the concentration of the phase in the mixture Ö QUANTITATIVE PHASE ANALYSIS
The width of the reflection is a function of the crystallinity of the phase
WHY DO WE NEED TO KNOW THIS?
Important Phases/Components: Clinker Clinker Clinkerphase phase
Name Name
Relevance Relevance
C3S/C2S C3S/C2S
Alite/Belite Alite/Belite
Hardness Hardness
C3A C3A
Aluminate Aluminate
Setting Settingtime time
C4AF C4AF
Brownmillerite Brownmillerite
Color, Color,Fe-content Fe-content
CaO CaO
Free FreeLime Lime
Kiln Kilntemperature temperaturecontrol control
Ca(OH)2 Ca(OH)2
Calciumhydroxide Calciumhydroxide
Kiln Kilntemperature temperaturecontrol control
Important Phases/Components: Cement Cement Cementphase phase
Name Name
Relevance Relevance
CaSO4·xH2O CaSO4·xH2O
Gypsum GypsumPhases Phases
Dehydration Dehydration/ /setting settingtime time
CaCO3 CaCO3
Calcite Calcite
Limestone Limestoneaddition addition3% 3%
Mg Mgphases phases
Periclase Periclase/ /Dolomite Dolomite
Mg-rich Mg-richquarries quarries
Glass Glass
Amorphous AmorphousPhase Phase
CEM CEMIII III/ /Reactivity Reactivity
Important Phases/Components: Raw Materials Material Material
Name Name
Relevance Relevance
Ca,Mg Ca,Mg(CO3) (CO3)
Limestone Limestone
Kiln KilnFuel Fueldosage dosage
SiO2 SiO2
Quarz Quarz
Grind Grindability ability
BF BFSlag Slag
Blast BlastFurnace FurnaceSlag Slag
CEM CEMIII III/ /Cost Cost
CaSO4x CaSO4xXH2O XH2O
Gypsum GypsumPhases Phases
Dosage Dosagefor forblend blend
Bypass/Dust Bypass/Dust
Sulfide, Sulfide,Spurrite Spurrite
Dosage Dosageand andDeposits Deposits
Audience Poll Please use your mouse to answer the question on the right of your screen: What methods are you currently using for phase determination? (Check all that apply): Freelime by titration only XRD channel in system Powder X-ray Diffraction Microscopy Bogue calculation None
XRD. . . Why Not More? XRD has been used on cement, clinker and minerals since the 1950’s Qualitative phase identification and standard-based quantification were the early applications. • Initially all these tasks were very cumbersome and difficult and needed either manual evaluation or expensive computer hardware. With the first fully shielded X-ray diffractometer (PDP controlled), our D500, Bruker started the move from University to Industry. Introducing PC-based diffraction software and developing a very intelligent search match for phases enabled non-PhD users to get meaningful results.
XRD. . . More and More Quantitative XRD in the past could only be done using either internal standards (RIR) or by calibration with reference material. Standard (reference) based approach • Very similar to XRF approach • One or more peaks are unique to a phase and are not overlapped • Relationship between Intensity and Concentration is developed by measuring characterized reference samples using the same parameters
This works very well for simple systems such as CaO Freelime or the limestone addition or Respirable Quartz • Characteristic peaks are available and not overlapped • Reference materials can be characterized (titration) or mixed
X-ray Diffraction Systems for Powders
D8 ADVANCE: modular, expandable research system 13
D4 ENDEAVOR: compact system, high throughput, quality control, automation ready
Methods for Quantitative XRD Classical Reference Material Based
Quantitative XRD Phase Analysis Conventional Quantitative Analysis measurement range
I
y
y
y %
Solid Solution Effects Schematical Representation
NIST RM's 8486, 8487, 8488 Solid Solution Effect for C3S C3S C2S
17000
16000
15000
14000
13000
12000
C3S C2S
11000
Lin (Counts)
10000
C3S
C3S
9000
8000
7000
C3A
6000
5000
C3S
4000
3000
C4AF C2S
2000
1000
0 28.5
29
30
31
32
2-Theta - Scale
33
34
35
Preferred Orientation Effects Schematical Representation
Randomly oriented powder
Highly textured sample
NIST RM 8486 Preferred Orientation Effects C3S C2S
17000
16000
15000
14000
13000
12000
C3S C2S
11000
Lin (Counts)
10000
C3S
C3S
9000
8000
7000
C3A
6000
5000
C3S
4000
3000
C4AF C2S
2000
1000
0 28.5
29
30
31
32
2-Theta - Scale
33
34
35
NIST RM's 8486, 8487, 8488 Conclusions Alite (C3S) exhibits strong peak shifts due to changes in chemical composition and varying intensities due to changes in both chemical composition and preferred orientation effects o C3A and C4AF clearly remain at the same positions
The various background of the patterns is directly related to the various iron content of the clinkers o Abundance of C4AF
Reliable clinker quantification is impossible using traditional XRD methods
Can a “Classical” Approach Work Here? NIST RM's 8486, 8487, 8488 Solid Solution Effect for C3S
C3S C2S
17000
16000
15000
14000
13000
12000
C3S C2S
11000
Lin (Counts)
10000
C3S
C3S
9000
8000
7000
C3A
6000
5000
C3S
4000
3000
C4AF C2S
2000
1000
0 28.5
29
30
31
32
2-Theta - Scale
33
34
35
Quantification Without Standards The Rietveld method generates a calculated diffraction pattern from the phase list and their structures, that is compared with the observed data. The differences between observed and calculated diffraction patterns are minimized using least-squares procedures.
Observed pattern Calculated pattern
Difference
Refinement
Methods for Quantitative XRD Rietveld Method 2 The Rietveld method: A direct standardless full-pattern approach to quantitative phase analysis • No standards • No calibration
Independent of equipment and sample properties such as tube aging, solid solution effects, and preferred orientation • No drift correction required
More and More. . . Lots of calculations required, as well as many parameters, limited the application to mainframes and Unix workstations (1994) • (none to be found in a cement plant) • Time to result for a sample > 120 minutes best case
The Rietveld “Refinement” uses many parameters; turn-on sequence and values need to be constrained to create meaningful results • Solid background in crystallography is required • Interactive type approach • Refinement needs to be tuned to instrument to empirically determine the instrument response function to constrain some refinement parameters
Faster and faster PC’s allowed this technique to mature (e.g. ZEROQUANT on 1997, WINRIET), but still an expert was needed to control it, with time to result still > 15 minutes
Breakthrough. . . Changed the Industry Using the PC platform and adapting the code to utilize Fundamental Parameters to describe the instrument function, new software was born. Instead of a parameter turn-on sequence and pure interactive approach, it uses a phase list and recipe and does not require ANY user input during its run.
TOPAS
TOPAS Standardless Quant
The unique TOPAS allows fully automated quantitative phase analysis from XRD data without any user input. Typical calculation times are dehydration effect • Too high Bassanite will have detrimental effect • Too long milling will cost money; mill is a large factor in energy consumption • All three sulfate phases have a different solubility • The ratio of the sulfates controls the setting behavior of the cement • The production process influences the sulfates as cement milling • Dehydrates gypsum to bassanite or even anhydrite • Typically in process control only the total SO3 content is monitored by XRF
Sulfates in Cement with TOPAS
TOPAS Hkl approach
From RR data
Quantitative Phase Analysis of Cements Quality and Process Control Cement • control of CO2 set points • control of dehydration characteristics in ball mill • control of amount of amorphous compounds • prediction of strength development in combination with other results • keeping a fingerprint of every sample as reference • check of competitor products
Quantification of Blast Furnace Slag Cements with TOPAS
Quantification of Blast Furnace Slag Cements with TOPAS How to quantify amorphous amounts like blast furnace slag in CEM III by Rietveld analysis? 20,000
We can calculate the crystalline phases
19,000 18,000 17,000 16,000 15,000 14,000
But how to handle amorhous humps as indicated by the blue curve?
13,000
Counts
12,000 11,000 10,000 9,000 8,000 7,000 6,000 5,000
background
4,000 3,000 2,000 1,000 0 10
15
20
25
30
35
40
2Th Degrees
45
50
55
60
65
Quantification of Blast Furnace Slag Cements with TOPAS Rietveld analysis can only take into account crystalline phases, which are normalized to 100 wt.% Using Rietveld analysis, amorphous phase abundances can only be quantified by adding a standard (spiking method) In an automated plant laboratory this is not a favored approach or practical at all. It even would be an additional source of error. If the amorphous part of the slag could be treated as its own phase, it could be seamlessly integrated into the Rietveld analysis.
Measurement Data: Blast Furnace Slag Sample: Slag sample of the VDZ Round Robin (2006): Material 1 High quality blast furnace slag 2,000 1,800 1,600
Counts
1,400 1,200 1,000 800 600 400 200 0 10
15
20
25
30
35
40 45 50 2Th Degrees
55
60
65
70
75
80
Round Robin VDZ 2006/7 In 2006 the VDZ (German Cement Works Association) organized a Round Robin focused on quantitative phase analysis of blast furnace slag cements using XRD methods. Three different BFSlag Cement samples to be analyzed were distributed to the participants. In all samples, slags of almost amorphous composition have been used. The pure slags have been made available to the participants as well.
Round Robin VDZ 2006/7 Results:
Results reference method
Application to the VDZ Round Robin Samples: Results Accuracy and Precision (values in wt. %, SD in brackets/1σ)
Every sample was measured 5 times (D4 ENDEAVOR, LynxEye Detector) The same emperical value for the mass of the hkl_phase was used for all samples Reference values: Sample 1 Sample 2 Sample 3 • sample 1: 25,0 wt.% Measurement 1 25,0 67,2 71,7 • sample 2: 67,0 wt.% Measurement 2 25,1 67,3 71,9 • sample 3: 72,0 wt.% Measurement 3
24,7
67,0
71,6
Measurement 4
25,1
67,3
71,9
Measurement 5
25,3
67,0
71,5
Mean
25,1
67,2
71,7
0,2
0,2
0,2
SD
TOPAS Improves Process and Quality Control
Effects can be seen which other methods do not detect at all (Bogue) or only after long analysis (microscopy)
Control of the alkali mass flow (C3A cubic/orthorhombic, Alkalisulphates) – very important for Cement Setting Behavior
Closer operation to the limits of the process (saving of energy and expensive raw materials) – instead of blind following of traditional LSF (Lime Saturation Factor), Silica and Alumina module
Freelime analysis can be done more reliably with TOPAS – interference stability!
Control of the cement milling – dehydration of the sulphates
TOPAS (Total Pattern Analysis Solutions) Benefits: Reliable results Does not break down when sample composition changes like
other packages Best available reproducibility
Latest generation Rietveld software
The Time for XRD is Now. . . From pick-up to result in less than 5 minutes! As fast as XRF Quantitative XRD enhances ability for process and quality control. Real phases equals real information. Cost savings will cover instrument investment • High margin cement is no accident. . . or luck. . . Push-button approach brings XRD to the control room
Automation Software AXSLAB Push Buttons to Start Routine Jobs Simply click a button to start a sample or a batch job Configurable by the user
Automation Software AXSLAB User Interface with Color-coded Results Table
Quantitative Rietveld Analysis Cement Industry Milestone reference: Paul, M., Hornung, D., Enders, M. & Schmidt, R. (2004): 'Process monitoring in a cement plant: The combination of optimized preparation procedures for clinker and cement and Rietveld analysis' World of Cement, 2, 35-42.
Quantitative Rietveld Analysis Cement Industry The cement industry is currently the fastest growing application area for quantitative Rietveld analysis The question is not IF, but WHEN the Rietveld method will be implemented for quality optimization and process control in ALL cement plants Paul, M. (2004)
Sample Preparation – Key to Success Ring and puck mill traditionally used will o Dehydrate the cement o Destroy crystal structure -> amorphous o Settings for XRF usually too long for XRD o Easy to automate Mortar mills o Too slow o Fine for XRD o Cannot be automated Mortar and pestle o Too slow x 2 o Operator dependent Powder mounts • too operator dependent • Not reproducible
Sample Preparation
Pressed pellets (steel rings) • Gentle grinding: free lime, sulfate phases, calcite • Uniform pressure: preferred orientation effects • Automation: Application in routine analysis
Automatic Preparation Module
Features:
Grinding with or without bind sample Predefined procedures for typical materials (RM, CLI, CM) Simple entry of individual parameters One button operation Predefined special programs (only grinding, only pressing)
Manual sample input Fine grinding mill Grinding aid dosing Tablet press Tablet cleaning Steel ring magazine
6 00
1260
Compact module for automatic sample preparation
60 0
Material in
Tablet out
POLAB® APM: Automatic Sample Preparation Module
new machine with sample changer
Lab Automation – AXSLAB Configuration: D4 with APMplus APMplus
D4 ONLINE
AXSLab User Interface Automation Control Transfer of results via LAN, e.g. to plant control system, LIMS system, Blending Software
Lan network
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