Thermo Scientific

Cement Engineering &

Sales Guide
2010

Company Confidential and Proprietary Information 1

Part of Thermo Fisher Scientific
 Thermo Scientific
Cement Engineering & Sales Guide – 2010

Contents

1.0 The Global Cement Industry & Thermo Fisher 50+ Years of Experience in XRF/XRD Technology

2.0 Analysis requirements of a Modern Dry process Cement Plant

3.0 Laboratory Scopes, Automation and Sample Preparation Methodology

4.0 Key Analytical Parameters Monitored and Controlled by Modern Dry Process Cement Plants and
Thermo Fisher Solutions that help derive better productivity:

4.1 Elements and Oxides

4.2 Quality Parameters
4.3 Free Lime
4.4 Sulfate/sulfide contents in cement
4.5 Pozzolan Additions
4.6 Clinker Phases
4.7 Limestone Additions as fillers
4.8 Hot meal analysis of pre‐heaters (cyclones)

5.0 Thermo Fisher Scientific Product Guide

5.1 Choice of Instrument depending on the analytical needs of a cement plant

5.2 Choice of Instrument based on performance and speed of analysis
5.3 Automation Capabilities
5.4 Specifications for Engineering companies to prepare bid documents

6.0 Economic Benefits

7.0 Reference Lists – group based on manufacturers

8.0 Appendix:

8.1 Application Notes and comments

8.1.1 General Oxide Calibration
8.1.2 Free Lime Determination in Clinker
8.1.3 Determination of Limestone Addition in Cement Manufacture

8.2 Articles & Publications

8.2.1 Analysis of Alternate Fuels (AF) – World Cement June 2008
8.2.2 Integrated X‐Ray Analysis – International Cement Review March 2008
8.2.3 Making the right choice – World Cement Mar 2006
8.2.4 Identifying Cement – International Cement Review April 2005
8.2.5 Analytical Solutions – World Cement April 2005
8.2.6 Online Quantification of Clinker – Case Study – World Cement Feb 2004
8.2.7 Power of X‐ray – Ceramic Industry July 2002

8.3 Thermo Fisher Scientific Cement Catalogue ‐ Instrument Solutions for the Cement Industry

Company Confidential and Proprietary Information 2

1.0 The Global Cement Industry:
The world cement industry is a complex structure of local, national, regional and global markets and cement/clinker
movements. The structure is ever changing, being closely tied to changes in a range of variables – including macro‐
economic growth, housing sector booms, public spending levels, trade protectionism, and transportation costs. With
a relatively small number of multinational companies dominating cement capacity in many markets throughout the
world, the cement sector has become even more globalised in recent years. With increasing multinational presence
in growing Chinese, Indian, Middle East and Latin American markets, the structure of world trade in cement and
clinker continues to be dynamic, with the dramatic changes in shipping costs adding a further layer of complexity to
trading patterns. The next 15 years are set to witness further extensive change in cement supply/demand patterns,
as different regions/countries enjoy very different development profiles.

Cement plant layouts and designs have evolved to suit the ever‐changing economic demands. Heavy Machinery and
analytical instruments supporting modern cement plants have also evolved providing greater flexibility, better
detection limits and higher performances. Macro‐Economic growth has continuously pushed the limits of
productivity improvement and has driven innovations to achieve greater control and higher efficiency at all the
stages in cement plants. Plant production capacities have consistently increased supporting the growing market
needs and optimizing manufacturing costs. Today a 2 MTPA (Million Ton Per Annum) cement plant has become the
most common design to adhere the economy.

Thermo Fisher Scientific has partnered with cement industry for the past several decades dealing with many
manufacturers, engineering companies, consultants around the world, establishing themselves as one of the
pioneers in providing innovative technology that help enhance the analytical capabilities and plant performances.
Thermo Fisher manufactures and supports a wide range of analytical instrumentation products for cement industry.
These include process and laboratory automation, emission monitoring systems and limited material handling
systems. In this cement workbook, we will discuss various analysis needs of a cement plant and we will draw
references to several cement production stages where one can secure the advantage of employing innovative
technologies from Thermo Fisher.

Who
Who We
We Are
Are Strengths
Strengths

ƒ $9 billion revenues
Leading provider of ƒ 30,000 employees
Scale
ƒ 350,000 customers
analytical instruments, ƒ 150 countries served
equipment, reagents and ƒ Complete portfolio
Capabilities ƒ World-class technologies
consumables, software and ƒ Commercial reach

services for research, analysis, Experience ƒ 150 years of combined experience

discovery and diagnostics Brand Equity ƒ Pre-eminent brands

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 Thermo Fisher Foot Print in X-Ray Technology - 50 INNOVATIVE YEARS
1st Mid-power sequential
XRF spectrometer –
Advant’X
1st XRF spectrometer 200
with Compact Integrated 0 1st XRF spectrometer
Launch of first cement XRD system - 9800 –
simultaneous XRF - with Full Integrated
Free lime and clinker XRD capability – 9900 X-
74000 phase analyzer ray Workstation
197 199
2 8 200
7
Foundation

2010
1934

2000
1980

1990
1950

1960

1970

199 200
196 3 6
8
1st XRF spectrometer 1st Mid to High power WD-
1st shipment of with Compact XRF spectrometer series –
world’s best selling Integrated XRD channel Advant’X Intellipower
simultaneous XRF - - 8600 – Free lime 200
72000 analyzer for clinker 2
1st Compact WD-XRF
198 199 spectrometer geared for
195 1st Moire fringe
3 6 cement industry–
3 goniometer XRF
1st XRF/robotics Optim’X
spectrometer sys-
spectrometer - 8400 tem -SMS-800
1st simultaneous X-ray
spectrometer 200
0
1st X-ray
powder diffraction
system: X’TRA

Thermo Fisher Scientific, Bulk Elemental Business specializing in X‐Ray technology and innovation was established in
year 1934. The above chart depicts various innovations this company has led during the past 70+ years. Notable
st
among many such successful innovation are the invention of the 1 Moire Fringe Goniometer in 1983, which
introduced a gearless goniometer to the world of X‐rays. This invention changed the way Cement, Steel, Minerals
and Metals industry managed their X‐ray instruments. Gearless goniometer eliminated wear and tear completely
extending the life and reliability of XRF instruments.

Once again, Thermo Fisher Scientific made a significant mark on the X‐ray history by introducing an ARL 8600
Analyzer by combining both XRF and X‐ray Diffraction channel in a simple, easy to use, single instrument in year
1993. This helped cement industries globally to routinely conduct free lime analysis that helped them optimize Kiln
operations resulting in direct cost savings and quality improvements. Analyzing free lime along with elements and
oxides within minutes had become a reality.

Such significant milestones did not slow Thermo Fisher Scientific from continuing to invent better and new
technologies. The ARL 8600 was followed by introduction of a compact X‐ray Diffraction along with XRF analyzer
resulting a ARL 9800 ‐ Total Cement Analyzer. This allowed routine analysis of the important clinker phases, free lime
along with elements and oxides within minutes. ARL 9800 enhanced the ability of cement plants to control the kiln
and end user quality with better precision and optimize operating costs. Analyzing clinker phases and free lime
routinely became a Dream Come True.

These innovations changed the way cement plants operated, and were continuously followed by various
introductions depicted in the chart above. Every contribution has lead to the betterment of cement process, cost
optimization and quality improvement initiatives. Today Thermo Fisher Scientific offers a wide variety of products
that suite every need of a cement laboratory. The products include (1) a very basic and simple Quant’X EDXRF table
top analyzer, (2) a compact easy to use and easy to operate Optim’X WD XRF Analyzer for elemental and oxide
analysis, (3) Advant’X 1200 & 2500 that offer mid power range instrument providing greater speed for XRF analysis,
(4) ARL 9900 Total Cement Analyzer combining a complete XRF and a compact X‐ray Diffraction capabilities for free
lime and clinker phase analysis, (5) ARL 9900 X‐ray Workstation that combines full blown X‐ray diffraction and XRF
Analyzer for expanded XRD applications and finally (6) a stand alone X‐ray Diffraction Analyzer.

Thermo Fisher Scientific is strongly committed to "Continuous Innovation" and will aggressively pursue contributing
groundbreaking technical advances to the cement industry. In addition to innovations, Thermo Fisher Scientific has
also invested extensively to create a fantastic global infrastructure that supports our customers 24/7 around the
world.

Company Confidential and Proprietary Information 4

2.0 Analysis requirement of a Modern Dry Process Cement Plant:
Cement contains approximately of 50% ‐ Tricalcium silicate (Ca3SiO5 or 3CaO.SiO2), 25% Dicalcium silicate (Ca2SiO4
or 2CaO.SiO2), 10% Tricalcium aluminate (Ca3Al2O6 or 3CaO .Al2O3), 10% Tetracalcium aluminoferrite
(Ca4Al2Fe2O10 or 4CaO.Al2O3.Fe2O3) and 5% Gypsum (CaSO4.2H2O).

Figure 1: Schematics of a typical dry‐process cement plant

The fundamentals of cement continue to focus on consistency and homogeneity. A Modern Dry process cement
plant (as depicted in Figure 1 above) comprises various stages. We will discuss each one of them briefly below.
Above, you can see these stages very clearly depicted in the schematic.

2.1 Quarry
One of the most important parameter that will influence establishing a successful cement plant is to identify and
qualify suitable quarry site that will cater basic raw material (limestone). It is important to choose suitable reserves
exceeding the design capacity and the planned plant life. A thorough geological investigation to determine the
quality of raw material is highly recommended prior to finalizing a quarry site. Most adopted and suggested
approach is to hire reputed and well known geological investigation firms and use of modern day analytical tools and
instruments to determine the composition of the quarry. Thermo Fisher Scientific provides most advanced and very
compact XRF Analyzers suitable for such applications. ARL Optim’X is one such model is specially designed for rugged
application without the need of external cooling or specialty gases. Identification and mining of raw materials takes
place in the quarry and often the materials are crushed and to some extent pre‐blended to ensure consistent
mixture. Figure 2 below shows typical quarry equipments. These include heavy machinery and earth moving
equipments.

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 Figure 2: Typical Quarry Equipments

2.2 Primary Cement Raw Material – Impurities: Primary raw materials for cement include
limestone, clay, sand, iron ore and bauxite. Most commonly found compositions and impurities are detailed
below.
2.2.1 Limestone (CaCO3)
- MgO, from dolomites
- SiO2 from quartz
- NaCl and KCl from salts
- CaF2 salt

2.2.2 Clay (alumino‐silicates)

- Na2O and K2O from feldspars
- TiO2 from bauxites and other minerals
- MnO from iron ores

2.2.3 Sand (SiO2)

- Na2O and K2O from feldspars
- TiO2 from clays

2.2.4 Iron ore (Fe2O3)

‐ TiO2, MnO, Cr2O3

2.2.5 Bauxite (Al2O3 + Fe2O3)

‐ ‐ TiO2 CaO, SiO2

2.3 Quarrying and Raw Material Homogenization: Cement plant adopts open cast mining for
limestone quarries. The art of quarrying has evolved with use of modern heavy machineries and
sophisticated earth moving tools. The use of analytical instruments to predetermine the approximate
composition of quarried material is widely accepted and has become an integral part of modern dry process
cement plants. A Prompt Gamma Neutron Activation Analyzer providing “on the transport belt” bulk
material analysis is commonly adopted to monitor the approximate composition of quarried raw material. It
allows easy planning of quarry logistics to meet the quality demands and improve mining efficiency. Thermo
Fisher Scientific is the world leader in providing the on‐line bulk material analyzers for these applications
(Cross Belt Analyzers). Quarried limestone and clay are stored using longitudinal or circular stockpiles.
Stacker and Reclaimers improve the homogeneity of raw material by thoroughly mixing the very
heterogeneous composition. In today’s cement industry attaining a standard deviation of less than 5% for
CaCO3 variation is very much possible using the combination of mine planning software’s, on‐line bulk
elemental analyzers and stackers and reclaimers. Figure 3 depicts a circular stacker and reclaimer. A Thermo
Scientific CrossBelt Analyzer system is shown in Figure 4. Stacker Reclaimer is also available in longitudinal
configuration and the selection will depend on space limitations.

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 Figure 3: Circular stacker reclaimer Figure 4: Thermo Scientific Cross belt Analyzer

You will typically find multiple basic raw materials being preblended using a stacker reclaimer, most
commonly mixtures include limestone and clay.

2.4 Raw Mix and Raw Mill: A Raw Mix Station is the first entry point for quarried raw material into the
cement plant. Raw Mix Station normally consists of multiple hoppers or silos equipped with weigh feeders
to accurately feed and mix individual raw materials. Most commonly found a raw mix station consists of 4‐5
hoppers/silos. Thermo Fisher Scientific manufactures and supplies weigh feeders that help control the raw
material feed rates. The blended Raw Material stored by a stacker reclaimer (Figure 3) is transported using
belt conveyors to the respective hoppers. Cement raw materials are mixed in ratios of 80‐85% Limestone,
15% Clay, 1% quartz and other materials that include iron ore, bauxite ore etc., The resultant blend of raw
materials is collectively called as raw mix, and this is fed to a Raw mill for further grinding to finer mix. 80%
of the raw mills are vertical roller mills. The older version of raw mill include ball mills, these are sometimes
augmented by a roller press. Modern Day Vertical Raw Mills have very high production capacities and churn
excellently ground mixtures. The resultant mixture of finely ground raw mix is called raw meal. Raw Meal is
stored in an intermediate storage before being fed to the Kiln.

2.5 Raw Meal Quality Control: It is extremely important to frequently measure the composition of raw
meal (raw material mix after the raw mill) in order to help control the feed rates of different raw materials
to precisely control the desired composition. Raw Mix Hopers are equipped with weigh feeders that can
control even very small quantitative changes. Securing frequent samples of the raw meal, analyzing these
samples using XRF analyzers to determine LSF (lime saturation factor), SM (silica moduli) and AM (alumina
moduli) and feeding the resultant information to an advanced control system will help implement changes
to the variable feedrate of the weigh feeders (see chapter 2.7). This will result in maintaining consistent
composition of raw mix and raw meal. Thermo Fisher Scientific manufactures advanced XRF/XRD Analyzers
for analyzing the raw mix/raw meal. You can have stand‐alone and automated versions of these systems.
Modern dry process cement plants normally adopt an automated system making laboratory part of the
process, this configuration provides excellent flexibility to control the product quality and enhance
productivity. Thermo Fisher Scientific has supplied numerous such systems that are equipped with Thermo
Scientific ARL XRF/XRD Analyzers, automatic sampling systems supplied by Herzog (for example), and
automation software and control systems supplied by FLSmidth, ABB, Polysius, KHD and other major OEMs.
A combination of such tools helps continuously monitor the raw meal samples and analyzing the
composition accurately permits implementing desired changes to the weigh feeders that will change the
quantitative feeding of raw material components as needed. Such a system ensures consistently desired
quality of raw meal. There are several key parameters that are measured at this stage and these parameters
include major and minor oxides.

2.6 Major, Minor Oxide and Impurities (Elements and Compounds):

2.6.1 Moduli for CaO, SiO2, Al2O3, Fe2O3
2.6.2 MgO, Cl, SO3, Alkalis Na & K, P2O5 etc

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 Elements Effects and Influences
Na2O and K2O Hydration probabilities and Lifetime
MgO (Periclase) Hardness
Cl Pre‐heater and kiln
P2O5 and TiO2 Hydration C3A phase
MnO, Cr2O3 Color
CrVI Legislation
Heavy metals Legislation

2.7 Quality Parameters:

LSF, SM, AM, which are determined based on the oxide concentrations.

The silica ratio represents the burnability of a raw mix. The burnability impacts how much energy is
put into the system. As the ratio of silica to alumina plus iron increases, it becomes harder to
“burn” — harder to combine the raw materials into the phases we want. As the ratio decreases,
the tendency for fluxing (the ability of the solid materials to become liquid) increases, and the
combining reactions become easier. Another consideration is that silica present as quartz is
generally more difficult to combine than silica present as silicates.

The alumina‐to‐iron ratio is important because it controls the potential C3A/C4AF ratio in the
finished cement, which is important because of sulfate resistance, heat generation, and admixture
compatibility issues.

The lime saturation factor controls the potential C3S to C2S ratio in the finished cement. C3S
governs the early age strength development while C2S governs the later age strength.

100 ⋅ Cao
LIMESTONEFACTOR =
2.8 ⋅ SiO2 + 1.18 ⋅ Al2O3 + 0.65 ⋅ Fe2O3
SiO2
Silicaratio =
Al2O3 + Fe2O3
Al2O3
AlRatio =
Fe2O3

2.8 Cyclone, Kiln and Cooler: Raw Meal storage prior to the kiln ensures continuous supply of raw meal
for kiln operations while allowing flexibility to operate the raw mills in shifts. Equipping the storage silos
with blending capabilities will enhance further blending of the raw meal. Such arrangements to have
blending silos are soon becoming rare due to availability of advanced analytical tools that help maintain
excellent consistency of raw material. The kiln is the heart of cement plant where actual transformation of
raw material happens (Figure 6). It is very crucial to measure several key parameters while the raw meal
transitions through the cyclones and kiln. These include qualitative and quantitative analysis of Hot Meal at
Calciner, Clinker, Fuels & Alternate fuels and raw
materials. Once again, use of advanced analytical
instrumentation is highly recommended to accomplish
quick and accurate analysis of these samples. Thermo
Fisher Scientific provides the most advanced and
trouble free XRF/XRD Analyzers to complete this
analysis. Figure 5 shows a typical cement plant kiln.

Figure 5: Cement plant kiln

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2.9 Analysis of Clinker: Clinker Analysis will include
2.9.1 Indirect phase estimation using XRF for chemical analysis of CaO, SiO2, Fe2O3, Al2O3 , MgO,
K2O, SO3 , Na2O + some other elements like P, Cl, Cr, Mn depending on the plant and
need

2.9.2 Determination of the moduli and the oxides, in analogy to raw meal analysis

2.9.3 Theoretical Clinker phases can be calculated using Bogue’s equation but the results are
only approximate and do not necessary indicate the true phase composition of the
clinker. X‐ray diffraction provides better truer phase information.

Bogue equations are the following:

%C3S = (%CaO ‐ %CaO free) x 4.07 ‐ (%SiO2 x 7.6 + %Fe2O3 x 1.43 + %Al2O3 x 6.72)
%C2S = %SiO2 x 2.87 ‐ C3S x 0.75
%C4AF = %Fe2O3 x 3.04
%C3A = %Al2O3 x 2.65 ‐ %Fe2O3 x 1.69

These are modified Bogue equations that include a correction for free lime hence
showing that free lime determination in each clinker sample is very useful.

2.10 Alternate Fuels:

Refer the Article “Analysing AF Elements” by Ravi Yellepeddi, Marc Dupayart and Didier Bonvin of Thermo
Fisher Scientific published in World Cement June 2008. This is enclosed in the appendix

Alternate fuels is a growing trend in cement industry, these help optimize the production costs while
helping the environment get rid of unwanted waste. However, the compositions of alternate fuels can vary
a lot. It is highly recommended to have analytical instrumentation with investigative capabilities to ensure
accurate analysis and to maintain the desired chemical balance of product. Commonly used alternate fuels
are listed below:

Liquid waste Fuels Tar, chemical wastes, distillation residues, waste solvents, used oils,
wax suspensions, petrochemical waste, asphalt slurry, paint waste, oil
sludge

Solid waste Fuels Petroleum coke (“petcoke”), paper waste, rubber residues, pulp sludge,
used tires, battery cases, plastics residues, wood waste, domestic
refuse, rice chaff, refuse derived fuel, nut shells, oil‐bearing soils,
sewage sludge

Gaseous waste Landfill gas, pyrolysis gas

2.10.1 Alternate Fuel Analysis: Using Thermo Fisher XRF/XRD solutions one can accomplish
measuring all the different types of alternate fuels:

Company Confidential and Proprietary Information 9

 - Due to solid solution effects, cement is able to buffer poisonous
elements in the lattices of the phases. This can be monitored (Eco‐
Cements) using Thermo Fisher XRD Analyzers
- Liquid samples are investigated: e.g. used oils (possible in ARL Advant’X
and ARL Optim’X – needs liquid analysis option)
- Analysis of the sediments in waste oils (possible in ARL Advant’X and
ARL Optim’X – needs liquid analysis option)
- Ash analysis, kiln dust‐filter analysis
- Alternate Fuels also contribute to several elements of concern, listed
below:

2.10.2 Combustibles:
- S from coal and oil (oil is possible in ARL Advant’X and ARL Optim’X –
needs liquid analysis option)
- P2O5 and Cl from (biological) waste
- Heavy trace elements from all types of waste materials viz. As, Ba, Cd,
Co, Cr, Cu, Hg, Mo, Ni, Pb, Sb, Se, Sn, Tl, V & Zn

2.10.3 Additional Impurities: In addition to the routine process analysis of Hot Meal from
Calciner, Clinker, Fuels & Alternate Fuels it is also crucial to analyze the Cl and SO3
composition to prevent blocking the production. Below we provide summary of the
damaging effects these two parameters have:
Cl (Chlorine):
- Internal Cl circuit causes enrichment of Cl
- Material gets sticky blocking the heat exchange tower
- Concentration range: 1‐2.5 %

SO3 (Sulfur Trioxide):

- Material gets sticky blocking the heat exchange tower
- Concentration range: 1‐2 %

2.11 Standard Analysis and Frequency Employed by Modern Dry Process Cement Plants

Routine Analysis Frequency of Analysis

Raw Mix Analysis 04/hour
Kiln Feed 01/hour
Raw Materials 01/ Day
Clinker 01/hours
Cement 01/hours during dispatch
Combustibles 01/day to 01/ month

Company Confidential and Proprietary Information 10

3.0 Laboratory Scopes, Automation and Sample Preparation
Methodology: Cement plant capacities are defined in terms of Million Tons Per Annum (MTPA)
and Laboratory capabilities differ based on the capacity of the cement plant and the desired applications.
Below are some typical examples of Laboratory Scope based on the plant capacity.

3.1 Plants Exceeding 1 MTPA: Laboratories of a modern dry process cement plant are an
extension of process and help control the quality based on both qualitative and quantitative
analysis. Following are the list of equipments that are normally employed by plants exceeding 1
MTPA:
3.1.1 Sample Transportation systems to collect raw mix, raw meal, clinker and cement
samples at regular interval. There are options available to customers to implement
either an automatic transfer of samples to central lab or to manually collect and
transport these samples. Partial automation is also implemented based on the frequency
of analysis.
3.1.2 Sample preparation equipments
3.1.3 Integrated WDXRF and XRD Analyzer capable of providing accurate analysis of oxides,
elements, compounds, all clinker phases and free lime (see details in Table 1).
3.1.4 Expert software to collect the analysis provided by the XRF/XRD Analyzer to control the
feed rates of raw mix hoppers.
3.1.5 An additional WDXRF system to conduct investigative work of alternate fuels, and new
raw materials (see details in Table 1).

3.2 Plants below 1 MTPA & above 0.5 MTPA: For smaller plants, one has to very carefully
select which portion of sample extraction will be automated. This will depend on the frequency
and need of analysis. Most suitable scope is recommended below:
3.2.1 Automated sample transportation for raw meal samples and manual sample
transportation for all other samples.
3.2.2 Sample preparation equipment
3.2.3 Integrated WDXRF and Compact XRD system capable of analyzing elements, oxides,
important phases of clinker and free lime (see details in Table 1).
3.2.4 Expert software to control the raw mix weigh feeder feedrates.

3.3 Grinding Plants and Plants below 0.5 MTPA: grinding plants will need a compact and
trouble free XRF device with minimal sample transportation automation. The most suited scope
will include
3.3.1 Sample extraction systems
3.3.2 Manual sample transportation
3.3.3 Sample preparation equipment
3.3.4 Compact XRF system (see details in Table 1).

Refer the Article “Analytical Solutions” published in World Cement 2005, by Ravi yellepeddi, Raphael
Yerly, Andre Kohler and Anton Kleyn and Didier Bonvin of Thermo Fisher Scientific discussing intelligent
analytical X‐ray solutions for cement industry

Company Confidential and Proprietary Information 11

4.0 Key Analytical Parameters Monitored in Modern Dry
Process Cement Plants: Here we will discuss various analysis performed in a cement
plant, their implications, benefits and some of the analysis details.

4.1 Elements and Oxides: X‐ray Fluorescence (XRF) analysis for chemical composition of
cements and raw materials is the most widely used technique. It is the main workhorse of the
cement plant laboratory, providing important information on the chemical makeup of a given
sample. It is an essential quality‐control tool, used to assure the proper composition of the initial
cement raw material blends and of the final product, since it furnishes data on the amounts of
major cement oxides such as CaO, SiO2, Al2O3, and Fe2O3 present. Chemical analysis by XRF,
together with chloride and alkali determinations, is used in evaluation of alternate raw materials
and to map quarries. XRF results also are vital in assessing and troubleshooting problems. Often it
is the first step in evaluating burnability, and can be used to help identify causes of problems such
as buildups, contamination, and discoloration.
X‐ray Diffraction (XRD) is often performed to establish the mineralogical composition of samples
and to complement XRF analysis. XRF provides quantification of the elements, while XRD is used to
identify actual compounds (phases). XRD identifies substances based on their crystalline atomic
structure. Clinker and cement phases can, therefore, be identified and quantified. The analysis also
is particularly important for identifying unknown materials, such as those in buildups and
contaminants.
Most commonly used ingredients in basic cement raw material mix consists of limestone, clay,
sand (silica), iron ore and bauxite. In order to ensure proper mix of these constituents one has to
measure several elements and oxides. XRF/XRD is the only known, most flexible technology that
can provide analysis of all these elements and oxides. Below is a list of all the elements and oxides
with their respective contribution in making good quality cement:
Element Oxide Typical Range Influence in the cement process

Ca CaCO3 42‐45% One of the Major oxides found in Raw Mix, contributed by limestone
CaO 59‐66% One of the Major Oxide concentration originating from Limestone
The second Major oxide found in Raw Mix, contributed by Silicious
Si SiO2 12‐17% material

Al Al2O3 2‐3% The third Major Oxide found in Raw Mix, contributed by Bauxite addition
The fourth Major Oxide found in Raw Mix, contributed by addition of Iron
Fe Fe2O3 1‐1.5% Ore
This oxide is contributed by Limestone and influences hardness of
Mg MgO 0.5‐0.7% cement. In exxcess will affect the productivity
K K2O 0.5‐0.6%
S SO3 0.4‐0.7% Excess of Sulfur concentration creates heat exchange blockage
Concentrations in excess will affect the hydration probability and lifetime
Na Na2O 0.1‐0.9% of end product

Cl ‐ Excess of Chlorine will create sticky material blocking the heat exchanger
P P2O5 Affects the hydration of C3S phase
Ti TiO2 Affects the hydration of C3S phase
Mn MnO Affects the color of cement
Cr Cr2O3 Affects the Color and Legislation of end product
All the important elements and oxides stated above can be measured using an XRF technology.
There are additional elements that cement plants would be interested in if they employ alternate
fuels. These will include
- S from coal and oil
- P2O5 and Cl from (biological) waste
- Heavy trace elements from all types of waste materials viz. As, Ba, Cd, Co, Cr, Cu,
Hg, Mo, Ni, Pb, Sb, Se, Sn, Tl, V & Zn
- SO3 and Cl

Company Confidential and Proprietary Information 12

 4.2 Quality Parameters: Quality parameters are calculated based on the concentration of
several elements. The three most commonly used quality parameters include LSF, SM and AM. The
main oxides contributing to these quality parameters include CaO, SiO2, Fe2O3, and Al2O3. Some
of the cement companies based on the specific material characteristics use formulas that take into
account additional oxides.

100 ⋅ Cao
LIMESTONEFACTOR =
2.8 ⋅ SiO2 + 1.18 ⋅ Al2O3 + 0.65 ⋅ Fe2O3
SiO2
Silicaratio =
Al2O3 + Fe2O3
Al2O3
AlRatio =
Fe2O3

4.3 Free lime analysis in clinker

What is Free Lime and why is it monitored?

Composition of cement:
Portland cement consists of Clinker and Gypsum, below you will find the details of each component.

Cement = Clinker + Gypsum

Clinker : CaO (bonded), SiO2, Fe2O3, MgO, Al2O3, Na2O, K2O, SO3, Cl and free CaO
Gypsum : CaSO4.2H2O

By burning raw mix (a mixture of limestone, clay and corrective additions) at Temperature above 1350°C ,
clinker is obtained.

The mineral compounds present in a typical clinker are:

• Allite C3S = (CaO)3 (SiO2)1 50‐70%

• Bellite C2S = (CaO)2 (SiO2)1 15‐30%
• Aluminate C3A = (CaO)3 (Al2O3)1 5‐10%
• Ferrite C4AF = (CaO)4 (Al2O3)1 (Fe2O3)1 5‐15%
• Free lime = Free CaO 0.5‐5%
• some MgO, K2O and Na2O

An important reaction occurring in the kiln is :

C2S + Free CaO ‐‐‐‐‐> C3S (1350°C < Temperature < 1550°C)

The higher the C3S content, the more resistance the cement will have, therefore monitoring the free lime
content in the clinker can give an idea of the future resistance of the cement.

Key Points for Cement Production

During the production:

• Temperature = Energy
Burning conditions in the kin
Phases
• For the user: Volume expansion
Setting Time
Resistance

Company Confidential and Proprietary Information 13

 The Free lime content in cement can vary between :
0.5% < CaO < ~ 5%

To get CaO < 0.5%

• A lot of Energy is needed because the temperature in the kiln must be kept very high
• Refractory linings of the kiln will need to be replaced more often
• Higher milling energy required because the clinker produced is harder
‐‐‐> this leads to higher costs

If CaO > 5% (in Germany, a limit is set at 3.5%)

as CaO + H2O ‐‐‐‐> Ca(OH)2

In presence of high level of free lime, hydration of cement will result in Volume expansion and Less
resistance

Therefore, an accurate control of the Free Lime content of clinker is needed to control the quality of the
product and monitor the temperature of the kiln. This has been done traditionally by wet chemistry (e.g.
titration) and more recently by using X‐ray diffractometers.

The Total Cement Analyzer allows controlling free lime and all other elements in clinker at the same time,
on the same sample and with just one instrument.

Guarantees for Free Lime Analysis in Clinker

Using an Integrated XRD system on ARL 9900 “Total Cement Analyzer” and using clinker samples ground for
20s with two 200 mg grinding pills (to particle size less than 150 microns), the Guaranteed sensitivity at
3600W:
300 cps/%
(This is 4 times higher than a conventional XRD instrument)

Guaranteed Precision at 3600W:

1.5% relative

Examples of Guarantee:

For free lime content of 2 %

reproducibility of ± 0.03 % on ten repeat measurements

For free lime content of 1 %

reproducibility of ± 0.015 % on ten repeat measurements

Guidelines for Free Lime calibration :

It is preferable to do the free lime calibration at the customer site after successful installation of the XRF‐
XRD instrument for various reasons: There are no commercial free lime standards available (because free
lime is not stable in air due to reactivity with humidity: CaO+H2O Æ Ca(OH)2). The samples for free lime
calibration have to be obtained from the responsible chemist on‐site. The nominal values of free lime
concentrations are obtained by wet chemical method and are plotted against the intensity values obtained
for free lime from the Free Lime Channel or the Compact Integrated XRD System. At least 5 clinker samples
should be supplied with free lime concentration varying from about 0.3% to as high as possible. Such
clinker samples can be collected during a kiln shut‐down or start up. Clinker/cement samples for free lime
determination should be prepared carefully in order to achieve correct and reliable results due to the
reactivity of free lime with humidity.

Company Confidential and Proprietary Information 14

 4.4 Determination of sulfate/sulfide contents in cement
The so‐called “slag cement” is obtained by mixing up to 65 percent of Ground Granulated Blast furnace Slag
(GGBS) with Portland cement. The properties of slag cements are broadly similar to those of Portland
cement, but with higher slag content they have an increased resistance to chemical attack. GGBS are
obtained by the water quenching of blast furnace slags followed by fine grinding. Addition of slags is
generally quantified using XRF and not XRD.

When slags are added to cements as additives or fillers, one can "trace" them by the presence of sulphide
i.e. S2‐ in contrast to sulphate (SO4)2‐. Sulphate comes from gypsum and other forms (alkali sulphates) in
cement whereas sulphide form comes only from the slag. The percentage determination of GGBS addition
can be measured by XRF due to the special signature that differentiates sulfur and sulfate, i.e. the position
of the S kα moves slightly depending on the Sulfur valence. Alternatively sulfate provokes a small satellite
peak near the S kβ peak.

S_K b
0.8 (SO 4)2- versus S2-
0.7
Intensity [Kcps]

0.6
0.5
0.4 S_K b_sat
0.3 C ement
0.2 + slag
0.1
Slag only
99.6 100.0 100.4 100.8 101.2 101.6 102.0 102.4
Angle 2 Theta (Degree)

Figure 6: Comparison of Scans on S kβ peak for samples 1 and 2. The satellite peak on the right side
represents Sulfate which is present only in sample 1.

When using 600W or 1200W power, it is advised to use a special fixed channel for analysis of this S kβ
satellite peak to allow longer counting time while the goniometer is measuring the other elements. When
offering a higher power instrument, the analysis of this S kβ satellite peak can be measured by our universal
goniometer using the Ge111 crystal for improved resolution and sensitivity.

Measuring this peak will allow to quantify the sulphate part of the cement. If you measure the usual S kα
peak, you will get the total sulphur (sum of sulphide from the slag and sulphate from the other components
in cement). The differences between these two quantities gives you the sulphide part, which "traces" the
slag content.

4.5 Pozzolan Additions Monitoring:

Pozzolans are defined as being materials having no intrinsic binding properties, but when finely ground and
in presence of humidity react with lime to form insoluble stable compounds with binding properties.

Natural pozzolans have been first found in Italy from volcanic origin (region of Pozzuoli, hence their name).
They are used as filler in cement in various countries, e.g. Italy, Turkey, Greece or India to name a few. XRD
can be used to quantify pozzolan additions in some suitable cases depending on the crystallinity of the
pozzolan phase. Sometimes this phase can be amorphous which would make determination by XRD more
difficult.

Company Confidential and Proprietary Information 15

 The following data show some results obtained on Italian cement samples containing various amounts of
pozzolanic materials.

A well‐defined XRD peak can be seen for pozzolan in Figure 8.

K counts per second
Pozzolane
1.2
CaCO3
1.1

1.0 C3S
0.9

0.8

0.7 CaO
0.6

0.5

118 120 122 124 126 128 130 132

Angle 2 Theta (degrees)

Figure 7: XRD scan over cement with and without pozzolan addition

The above XRD pattern obtained on three cement samples shows the presence of Free Lime (CaO), Alite
(C3S), Limestone (CaCO3) and Pozzolan phases:

‐ Sample 17 (green curve) shows the intense pozzolan peak at 2.51 Å.

By correlating, the intensities of this peak related to pozzolan a calibration curve can be developed.

4.6 Clinker Phases ‐ Analysis of C3S, C2S, C3A and C4AF by XRD:
Introduction

Monitoring of the four main phases in clinker namely C3S, C2S, C3A and C4AF can be done using X‐ray
diffraction (XRD). While different manufacturers propose a stand‐alone XRD for this purpose, an integrated
XRF‐XRD instrument is the most convenient solution because it can do both the elemental analysis and the
phase analysis on the same clinker sample.

One of the difficulties is the lack of suitable standards for all these phases. It is very easy to do qualitative
identification of different diffraction peaks in clinker phases. However, if quantitative analysis is needed,
calibrations are a way to get the information required for each individual phase in the clinker. This requires
standard samples with known concentrations of individual phases (C3S, C2S, C3A and C4AF). Unlike free
lime which can be quantitatively determined with wet chemical methods for producing standards, these
other clinker phases can be estimated using optical microscopy or Rietveld and similar analysis (Visual
Crystal) on a separate X‐ray diffractometer. Care must be taken as such estimations can present high error
margins and are not always reproducible.

The factors of influence on the 28‐day strength are multiple: (i) soluble alkalies, (ii) alite content, (iii) alite
size and (iv) MgO and other plant specific parameters. Nevertheless the level of the C3S (alite) content can
give a good preliminary prediction about the 3‐day and 7‐day strength.

Using the Compact Integrated XRD system of ARL 9900 Total Cement Analyzer to monitor theses phases

Thanks to the high sensitivity of our integrated XRD system, trend analysis can be performed on these
phases. Apart from the free lime analysis, the Compact Integrated XRD system can also measure the most
important clinker phase namely C3S (Alite), C2S (belite), C3A and C4AF using well characterised samples.
Many installations have successfully obtained straight calibration curves for the four clinker phases.

Company Confidential and Proprietary Information 16

 However, quantitative analysis will require customer’s own calibration standards since they are plant‐
specific. This can be done as part of the Clinkerquant calibration that Thermo Fisher Scientific can offer
together with the ARL 9900 Total Cement Analyzer.

Read the article “on‐Line Quantification of Clinker” a Case Study published in World Cement Feb 2004, by
Jairo Rueda, Henry Santamaria, Jorge Montana, Nestor Bernal and Renan Jaimes of Cement Paz Del Rio
S.A., Colombia and Bertrand Jequier and Felix Torres of Symtek, Columbia, present the results of on‐line
quantification of clinker phases using an integrated XRF‐XRD instrument

Using the X‐ray Workstation to monitor theses phases ‐ No standard samples needed

Thermo Scientific ARL 9900 X‐ray Workstation is the most advanced system that overcomes all the
difficulties faced in calibrating the clinker samples. Because this unique instrument integrates a full X‐ray
diffraction system inside the XRF instrument, the analysis of any phases required for cement industry can
be performed. There is no limitation. Furthermore, Visual Crystal the specific software module
complementing the integrated XRD system allows doing standard‐less X‐ray diffraction analysis. Therefore
no standard samples are needed to measure the most important clinker phase namely C3S (Alite), C2S
(belite), C3A and C4AF as well as other phases like periclase, limestone,

4.7 Analysis of Limestone additions in Cement using the ARL Total Cement
Analyzer:
There is a growing demand and interest in the cement industry to monitor the concentration of limestone,
of which calcium carbonate (CaCO3) is the main constituent, in the final product. For example, recent
European regulations permit the addition of limestone as filler up to concentrations of 30% depending on
the quality of the cement required. Therefore, it becomes very important and economically interesting to
control the concentrations of calcium carbonate in cement in order to guarantee the quality and conformity
of the final product.

CaCO3 analysis on the Total Cement Analyzer

On the other hand, the innovative X‐Ray Diffraction (XRD) system integrated into the ARL 9800 XP Total
Cement Analyzer, is capable of analysing only a specific phase (calcite in this case). In addition, XRD
intensities are not affected by the factors mentioned above, because

o The high energy of the incident radiation used allows to measure a much larger
volume of sample (about 10 times larger) than in XRF; this makes the XRD
analysis more representative
o Surface contamination, organic binders or grinding aids do not contain the
CaCO3 phase and will therefore not alter the limestone analysis
o The phase of interest, calcite, is measured directly and exclusively.

Note that a traditional XRD instrument cannot achieve the CaCO3 analysis because of overlap of the calcite
lines by X‐ray tube lines (from the Cu anode of the tube, an Rh‐anode tube is used in the Total Cement
Analyzer) and lack of sensitivity.

Conclusion

Using the innovative XRD system integrated into the ARL 9900 Total Cement Analyzer, limestone (CaCO3) in
cement and free lime (CaO) in clinker can be quantified with (a) good sensitivity (b) reliability and (c)
excellent stability.

Routine raw mix, clinker and cement process control on Na2O, MgO, Al2O3, SiO2, SO3, K2O, CaO, Fe2O3 for
example is carried out either with fixed channels or with by the ARL gearless goniometer. The latter can also
do analysis of any other elements, which may be required in the range boron to uranium.

Company Confidential and Proprietary Information 17

 The combination of XRF and XRD in the same instrument can now provide complete quality control of
clinker and cement. Separate instruments or methods are no longer required resulting in significant savings
from increased operator efficiency and lower running costs.

4.8 Hot meal analysis: degree of decarbonatation:

X‐ray diffraction system allows also to control the degree of decarbonatation of hot meal in the various
cyclone stages (= raw meal found in the pre‐heaters). The limestone (CaCO3) found in the raw meal
transforms into CaO due to the heat that goes from room temperature to 900°C at the last stage of the pre‐
heating tower when getting close to the kiln.

• CaCO3 Æ CaO + CO2

X‐ray Fluorescence cannot distinguish CaO vs. CaCO3, as it is an elemental technique that considers only the
total Ca content present in the sample. Integrated X‐ray diffraction can distinguish between CaO and CaCO3
and monitor the extent of this transformation. Figure 9 illustrates the mechanism of transformation and the
peak intensity changes depending on the cyclone stage considered.

- C aO
8 -
Intensity [K cps]

7 -
C aC O3
6 -

5 -

4 -

3 -
C aO C a(OH)2
2 -

1 -

0 -
2.8 2.7 2.6 2.5 2.4

Figure 8: Sample 1 (raw meal) shows only the limestone XRD peak. Samples 2 and sample 3 (from different
cyclone stages) show the conversion of CaCO3 into lime (CaO). While this figure shows scans over the
various representative peaks in routine analysis only the peak analysis of CaO and CaCO3 is required (20s
analysis time each).

Company Confidential and Proprietary Information 18

5.0 Thermo Fisher Scientific Product Guides: In this section we provide
simple, user friendly product selection guides for that are based on analytical needs of cement plant, based
on the performance and speed of analysis desired by the cement plant and based on automation
capabilities. In addition, we also provide a list of salient features Engineering companies need to include in
their bid documents to procure XRF and X‐ray Diffraction instruments.

Refer the Article “Making the Right Choice” published in World Cement March 2006 by Geoffory Butynck
of Heidelberger Cement CBR‐Plant Belgium, Michael Principato, Heidelberger Cement Technology Center,
Germany and Ravi Yellepeddi and Didier Bonvin of Thermo Fisher Scientific, presenting a case study that
illustrates how analytical needs in a cement plant can be matched to wide range of X‐ray solutions
available.

5.1 Choice of Instrument based on analytical needs of a cement plant.

5.1.1 Notes:
‐ Equipment Wattage: Thermo Fisher Scientific can offer the 9900 series with 3600‐
Watt power rating for 20% faster analysis compared to 2500‐Watt system, but the
higher power system requires an external water chiller.

‐ Fixed Channels: Thermo Fisher Scientific provides the option of increasing the
number of fixed channels to a maximum of 15. Each fixed channel improves the
analysis speed by 10 to 20 seconds

Company Confidential and Proprietary Information 19

 ‐ Sealed Channels: Thermo Fisher also offers optional sealed fixed channels for
elements F, Na and Mg. These will avoid the usage of P10 gas (Ar/10%CH4).

5.2 Choice of Instrument based on the performance and speed of analysis:

ARL 9900 - Guaranteed Performance for Cement Applications

2500 Watt System 1200 Watt System
Guaranteed Guaranteed Guaranteed Guaranteed
Analyte Range Repeatability (%) Repeatability (%) Repeatability (%) Repeatability (%)
1 Sigma at Mid 1 Sigma at Mid 1 Sigma at Mid 1 Sigma at Mid Range
Range in 30 Sec Range in 8 Sec Range in 30 Sec in 8 Sec

CaO 37-49 0.029 0.058 0.042 0.083

Al2O3 2.0-4.0 0.010 0.020 0.015 0.029
SiO2 10.0-19.0 0.020 0.040 0.029 0.058
Fe2O3 0.5-2.5 0.006 0.012 0.008 0.017
MgO 0.5-2 0.010 0.020 0.015 0.029
K2o 0.1-2 0.004 0.007 0.006 0.010
SO3 0.1-2 0.004 0.009 0.006 0.012
Na2O 0.1-2 0.009 0.016 0.012 0.023
Cl 0.005-0.1 0.001 0.001 0.001 0.002
Table 2: Performance for cement application

In the table above you will note the guaranteed repeatability of a 2500‐watt and 1200 watt ARL 9900 systems.

All major cement producers worldwide accept the performance levels achieved by the ARL 9900 at 2500‐watt power
within 30 seconds. Table 2 shows also 8 Sec performances if you need higher speed.

The standard formula that relates the power ratings and performance:

1. Example: If you keep time constant and you would like to find out how power affects the performance:

a. A 2500‐watt system will provide repeatability of 0.029 for CaO within 30 seconds.
b. In order to determine what a 1200‐Watt system would offer in 30 seconds for the same element,
one has to multiply the repeatability with square root of the fraction of 2500 divided by 1200.

CaO Repeatability for 1200 Watt system = 0.029 X (square root of (2500/1200)) = 0.042

2. Please note, you can achieve the 0.029 on a 1200‐Watt system, however you will have to increase the
time required for analysis. Below is how you can determine the time required by a 1200 system to
achieve repeatability equivalent to a 2500 Watt system:

a. Time required by a 1200 Watt system to match 2500 CaO repeatability =30 sec X (2500/1200) = 30
sec X 2.08 = 62.5 seconds

Please find below (Table 3) an overview of all applications that can be adressed in cement industry with the various
versions of integrated XRD devices that we can fit inside our ARL 9900 instruments.

Company Confidential and Proprietary Information 20

 XRD Device Free lime channel Compact XRD NeXRD in X-ray Usefulness
system Workstation
Application 2500W version
1 Free lime At 600W in 40s At 600W in 40s 10s Control of over-heating/under-
At 1200W in 20s At 1200W in 20s heating in the kiln
At 2500W in 10s At 2500W in 10s Prevents cement expansion
At 3600W in 6s At 3600W in 6s problems

2 Hot meal (CaCO3 vs CaO) At 1200W in 120s At 1200W in 120s 60s Prevention of clogging of cyclones
At 2500W in 60s At 2500W in 60s (pre-heaters)
At 3600W in 40s At 3600W in 40s

3 Limestone additions in At 1200W in 120s At 1200W in 120s 60s Quality control per cement type
cement At 2500W in 60s At 2500W in 60s regulations
At 3600W in 40s At 3600W in 40s

4 Quartz in raw meal At 1200W in 40s At 1200W in 40s 10s (main quartz peak Prevention of dramatic loss of
At 2500W in 20s At 2500W in 20s can be used) cement resistance in case of high
At 3600W in 14s At 3600W in 14s content (2-3%) of large quartz
crystals in raw meal.
5 Clinker phases N.A. At 1200W in 160s Available (see 7) Better than Bogue equations.
C3S, C2S, C3A, C4AF At 2500W in 80s Prediction of cement resistance
At 3600W in 60s (1day, 3day, 7day strength) with
C3S evolution (higher C3S = better
resistance).
6 Pozzolan additions to N.A. At 1200W in 60s* 30s Quality control per cement type
cement (subject to At 2500W in 30s* regulations
conditions: amorphous At 3600W in 20s* *Subject to conditions: amorphous
to crystalline ratio, etc..) to crystalline ratio, etc..
7 Complete phase analysis N.A. Clinker phase 5 to 10 minutes Clinker phases : C3S, C2S, C3A
analysis : see 1 & 5 ortho, C3A cubic, C4AF, arcanite
(K2SO4), periclase, free lime
8 C3A orthorombic vs C3A N.A. N.A. Available (see 7) C3A cubic provides good early
cubic in clinker resistance of cement
Comment : Nice information to get, but it is very difficult to choose which process or kiln parameters to modify in order to correct for C3A
orthorombic presence once detected
9 Periclase (free MgO) N.A. N.A. Available (see 7) Prevents cement expansion
problems
Comment : Only interesting in case of unusually high dolomitic limestone quarry
10 Gypsum hemi-hydrate in N.A. N.A. 40s Monitoring of under- or over-
cement (bassanite) heating in cement mill
Comment : Bassanite XRD analysis is only done afterwards, which means it is too late to correct. It is better to control the mill temperature to
monitor the gypsum dihydrate and hemi-hydrate in cement during milling.
11 Langbeinite in hot meal N.A. N.A. Available Prevention of clogging of cyclones
(pre-heaters)
Comment : Clogging risks can be already monitored using CaCO3 vs CaO levels in hot meal

Table 3: Overview of all applications that can be adressed in cement industry with the various versions of
integrated XRD

Company Confidential and Proprietary Information 21

 5.3 Automation Capabilities
All Thermo Fisher XRF and XRD systems are capable of automation interface. Our design flexibilities allow
end user to configure every model to suit the process control need and the number of samples analyzed.

We have designed a very special automation interface tool, X‐Y Sample Loader, which enables both our
Advant’X and 9900 ARL systems to be linked to full automation preparation equipments and establish
process control. We have discussed below in detail the specification, configuration and guide to select such
an interface

Figure 9: X‐Y Sample loader linked to transport belt Figure 10: Automated XRF‐XRD system in a cement plant
lab

OEM X‐Y Sample Loader on ARL 9900 Series

The OEM X‐Y Sample Loader has been designed in order to connect an ARL 9900 series spectrometer to an
automatic sample preparation station generally for pressed powders through transport belt(s). It was
conceived and developed for our main OEM Engineering Company customers. These companies integrate
the ARL 9900 series instrument with OEM X‐Y Sample Loader into their own developed Computer Based
Automation Systems for on‐line use such as:
o AutoLab System from ABB Switzerland
o QCX/Robolab System from FLS Automation, Denmark
o ROMIX System from KHD, Germany
o POLAB System from Polysius, Germany

If no OEM engineering company is involved in the project, Thermo Electron SA can propose a sample and
analysis management system called SMS‐XY in order to manage the automatic analysis of the production
samples, run SPC checks, perform automatic recalibrations at times when the instrument is not busy for
analysis of production samples (see separate Product Specifications Sheet).

Belt(s) from right of instrument Belt(s) from left and rear of instrument
Figure 11: Examples of possible configurations of OEM X‐Y sample loader fitted on ARL 9900

Company Confidential and Proprietary Information 22

 Questionnaire for project start‐up

The preliminary questions, which have to be answered in case such a system is to be ordered by a
customer, are the following:

Automatic samples (=samples that will come on the transport belt)

1. Are the automatic samples pressed in steel rings?

• If not, how are they pressed?

2. Which are the diameter and the height of the rings?

Diameter = Height =
3. After analysis, will the rings be sent back to the preparation machines and cleaned?

4. In case fusion beads must be loaded what is their diameter?

5. Will the fusion beads travel on the same belt as the pressed samples?
6. Do the fusion beads travel on the transport belt with the analysis surface upwards?
7. What will be the shortest time between arrivals of two successive samples on the belt?
Belts

8. How many incoming transport belts will be fitter? One or two?

9. Is there an outgoing transport belt?
10. From which side of the instrument should the belt(s) come? (see Figure 1)
X‐Y sample loader

11. How many classification baskets?

By default, none is fitted, but up to three baskets can be installed.

12. What are the dimensions (diameter and height) of the customer’s manual samples and setting‐up
samples (SUS)?
This allows determining the type of supports that should be provided for SUS and manual samples

13. How many of each type of sample supports does the customer need? Four supports are supplied as
standard. Additional ones should be ordered specifically.

14. Is there a need to analyse odd shape samples and/or thin samples manually?
In this case, a sample cassette of 31mm aperture should be used and a specific calibration should be
performed.
Host computer and communication

15. Which OEM Engineering Company will supply the automatic sample preparation system (ABB, FLSmidth,
KHD or Polysius)?
16. Will it be a new system?
• If not, when was it installed?
• Which version is it?

17. What kind of software link will be used: serial line or network?
We prefer to work with LAN using a TCP‐IP protocol

18. What kind of protocol of communication will be used?

19. If no external computer system will exist, an infrared detector can start sample pick up as soon as it
sees a sample on the belt, but this means that only one type of sample can be analysed and always
with the same calibration program. It this required?

Company Confidential and Proprietary Information 23

 20. If no external computer system will exist, a remote sample identification can be done manually via a PC
screen duplicating the WinXRF screen of the instrument PC and located away from the instrument for
example by the preparation machines. Is this required?

21. If no engineering company is involved in the project, Thermo Electron SA can propose a sample and
analysis management system called SMS‐XY in order to manage the automatic analysis of the
production samples, run SPC checks, perform automatic recalibrations at times when the instrument is
not busy for analysis of production samples, etc.. (see separate Product Specifications Sheet)

Before reception of an order for such an automatic system, additional information is required, e.g. for the
physical adaptation of the belt to the X‐Y loader, exact positioning of the instrument in the laboratory or
other details.

Company Confidential and Proprietary Information 24

 5.4 Specification to assist Engineering companies for tender
preparation
You will note below some of the key specification an engineering company and or customer
interested in procuring a suitable XRF and XRD analyzers should include in their tender or bid
specifications. These specifications are designed based on the extensive knowledge Thermo Fisher
has in supplying laboratory automation technology for cement plants globally for the past 50 years.
In order to make it very convenient for the end users we have designed these general
specifications based on the design requirements of a modern cement plant and the globally
accepted quality standards.

In addition to the laboratory, equipment specified below the plants might also need automation
systems. We recommend they consult with suitable automation equipment suppliers like Herzog,
Pfaff, etc and seek their recommendations.

5.5 Equipment Specification for Plants above 1 MTPA:

o Number of sample analysis per day = 80 to 120
o Integrated elemental, free lime and clinker phase analyzer with power rating
exceeding 1100 Watts
ƒ Major and Minor Oxides: CaO, SiO2, Fe2O3, Al2O3, MgO, Na2O, SO3,
K2O etc
ƒ Cl, S
ƒ Clinker Phases C3S, C2S, C3A and C4AF
ƒ Free Lime
o No external water chillers required
o The X‐Ray tube should be positioned above the sample to avoid contamination of
sample
o Single X‐Ray tube should be used for both XRF and X‐Ray Diffraction analysis
providing optimized operating costs
o Oxide, free lime and clinker calibration
o Proven Experience in interfacing with process control software packages supplied
by Industry majors
o Network and serial interface capabilities
o User Friendly software packages
o Compact Laboratory foot print and space requirement
o A Compact WD XRF back system to be used for routine Oxide analysis that will
not need external chillers.
o Supplier need to have experience exceeding 10 years
o Local support and spare parts availability, invoice in local currency preferred.
o Warranty 12 months from the date of commissioning or 18 months from the
date of shipment.
o Reference list containing more than 100 instruments installed successfully in
cement applications globally

5.6 Equipment Specification for Plants below 1 MTPA & above 0.5 MTPA:
o Number of sample analysis per day = 60 to 80
o Integrated elemental, free lime and clinker phase analyzer with power rating
exceeding 1100 Watts
ƒ Oxides: CaO, SiO2, Fe2O3, Al2O3, MgO, Na2O, SO3, K2O etc
ƒ Cl, S
ƒ Clinker Phases C3S, C2S, C3A and C4AF
ƒ Free Lime
o No external water chillers

Company Confidential and Proprietary Information 25

 o The X‐Ray tube should be positioned above the sample to avoid contamination of
sample
o Single X‐Ray tube should be used for both XRF and X‐Ray Diffraction analysis
providing optimized operating costs
o Oxide, free lime and clinker calibration
o Proven Experience in interfacing with process control software packages supplied
by Industry majors
o Network and serial interface capabilities
o User Friendly software packages
o Compact Laboratory footprint and space requirement
o Supplier need to have experience exceeding 10 years
o Local support and spare parts availability, invoicing preferred in local currency
o Warranty 12 months from the date of commissioning or 18 months from the
date of shipment.
o Reference list containing more than 100 instruments installed successfully in
cement applications globally

5.7 Laboratory Equipment Specification for Grinding Plants and Plants below
0.5 MTPA:
o Number of sample analysis per day = 40 to 60
o A compact WD XRF system to perform routine analysis of all the major and minor
oxides
ƒ Major and Minor Oxides: CaO, SiO2, Fe2O3, Al2O3, MgO, Na2O, SO3,
K2O etc
ƒ Cl, P
o No external water chillers
o Power requirements should be 50 W and above
o Small laboratory foot print
o User friendly software
o Supplier need to have experience exceeding 10 years
o Local support and spare parts availability, invoicing preferred in local currency
o Warranty 12 months from the date of commissioning or 18 months from the
date of shipment.
o Reference list containing more than 100 instruments installed successfully in
cement applications globally

Company Confidential and Proprietary Information 26

6.0 Economic benefits
Quarry exploration
• Bore hole sample analysis on XRF Analyzer provides effective tool for mine planning and selecting
areas for exploration.
• Continuous sampling and evaluation of the crushed limestone quality one can optimize the high
grade consumption and also limit the quality deterrents

Automatic raw mix control

• Control the material homogeneity and the standard deviation of lime saturation factor and other
quality parameters.
• Optimize the consumption of high grade limestone and other expensive additives like Iron Ore and
Bauxite
• Eliminate the intermediate blending requirement thus saving capital investment

Free lime analysis in clinker

• Regular free lime monitoring in clinker allows to control the burning conditions in the kiln
• Clinker with too low free lime level
• Requires more heating energy
• Waste of fuel
• More wear of kiln lining
• Waste of refractories
• Less grindability
• More energy required for milling
• Return on investment of less than 6 months have been reported by many customers

Clinker phases
• Help predict the 3‐day and 7‐day strength and apply correction in case of problem (more grinding
or other)

Alternate fuels
• Enables plant to use alternative fuels (tyres, animal meal, wood chips, plastic refuse, used oils,
petroleum sludge, etc..)
• Reduces fuel costs

Company Confidential and Proprietary Information 27

Appendix A
Comments on the Application Note 41301: (Included in the Appendix)

"Free Lime Determination in Clinker using the ARL 9900 Total Cement Analyzer"

Application note nr. 41301 is appended. The scans on Figure 1 illustrate the advantage of having a high sensitivity for
free lime. Even at low concentrations, e.g. 0.5 %, the free lime peak is clearly seen thanks to the close‐coupled optics
of the Total Cement Analyzer.

To make a calibration for free lime, the best method is to measure selected clinker samples by wet chemistry while
measuring them also on the Total Cement Analyzer. An example of such a curve is shown in Figure 2.

The standard error of estimate in Table 1 expresses the excellent accuracy that can be obtained, i.e. below 0.1 %.
The limiting factor is in fact the accuracy of the wet chemistry results. Table 1 shows also an important point: the
sensitivity of the Total Cement Analyzer for Free Lime. It has been boosted by a factor 4 with some changes in design
of our integrated XRD system and reaches now 600 cps/%. This is about 8 times more sensitivity than a conventional
diffractometer !

Another important point in favour of the Total Cement Analyzer is that the analysis of free lime is performed under
vacuum. In a traditional diffractometer, the analysis is carried out under air. This leaves plenty of time for the free
lime in the sample to react with air moisture. This reaction is rather quick meaning that with a traditional
diffractometer reproducibility tests as in Table 2 would show a constant diminution of the free lime concentration. A
2‐day long‐term test as explained in the text is simply impossible with traditional XRD.

Table 2 shows that the free lime analysis can be carried out almost concurrently with the XRF analysis on the same
sample. In fact, the XRF analysis is performed first on the fixed channels or the goniometer, then the XRD system
analyses the free lime. For comparison purposes with previous tests, we have used in this application note a
relatively long counting time, 100 seconds. However, thanks to the high sensitivity obtained now on the Total
Cement Analyzer, a shorter counting time, e.g. 30 seconds, could be used without problem.

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