Manuel Utilisateur ACTIVA An

User Manual
ACTIVA
TM
ICP Spectrometers
HORIBA Jobin Yvon S.A.S
16-18 rue du Canal
91 165 LONGJUMEAU
Tel: 33 1 64 54 13 00
Fax: 33 1 69 09 90 88
Web site: www.jobinyvon.com
Prepared by: Odile Hirsch
Technical Documentation Manager
Reviewed by: Olivier Rogerieux
R&D Manager
June 2005 Creation of document
Date Indice Object Modifications
Document Name
Reference 31 088 536
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TABLE DES MATIERES
1. Introduction 8
1.1. About this manual 8
1.2 Use 8
1.3 Technical specification 8
1.4 Name and address of the manufacturer 9
1.5. " Danger " and " Safety hazard " notices 9
1.5.1 Marking on ACTIVA 9
1.5.2. Specific precautions for maintenance 12
1.6. Installation of ACTIVA 12
1.7 Safety precautions. 13
1.8 Identification of commands 14
1.9 Common maintenance of ACTIVA 17
1.10 ACTIVA specification 17
1.10.1 Environmental conditions 17
1.10.2 Instrument caracteristics 17
1.10.3 In/Out 18
2. Emission spectrometry 20
2.1. Principle of atomic emission 20
2.1.1. General information 20
2.1.2. Plasma 21
2.1.3. Radial or axial viewing 22
2.2. Analysis 23
2.2.1. Introduction 23
2.2.2. Qualitative analysis 23
2.2.3. Quantitative analysis 23
2.2.4. Analytical performances 24
2.3. Preparation of samples 29
3. Description of spectrometer 31
3.1. General breakdown of unit 31
3.2. Sample introduction system 31
3.2.1. Nebulizer 33
3.2.2. Spray chamber 37
3.2.3. Choosing a nebulization system 38
3.2.4. Torch 39
3.3 Generator 40
3.3.1. Generator 40
3.3.2. Automatic control functions 41
3.4. Optical system 41
3.4.1. Introduction 41
3.4.2. Illumination system 42
3.4.3. Diffraction grating 42
3.4.5 The detector 42
3.4.5. Polychromator 42
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3.5. Signal processing 43
3.5.1. Electronics of measurement 43
3.5.2 The detector: Symphony system 43
4. Using the spectrometer 44
4.1. Start-up 44
4.1.1. Checks 44
4.1.2. Plasma ignition 44
4.2. Plasma optimisation 44
4.2.1. Generator power 44
4.2.2 Sheath gas 45
4.2.3 Peristaltic pump speed and aerosol flow 45
4.2.4 Influence of integration time on background and signal 46
4.3. Analytical conditions 48
4.4. How to perform an analysis ? 48
4.4.1. Choice of program and choice of lines 48
4.4.2. WAV criteria 50
4.4.3. Peaks criteria 51
4.4.3. Choice of analysis method 52
4.4.4. Analytical optimisation. 57
4.4.5. Method validation 62
4.7.6. Semi-quantitative analysis 63
4.4.7. Analysis of organic substances 65
4.4.8. To ignite a plasma with an unusual solvent (very volatile) 67
5. Accessories 69
5.1. Classical hydride generator (Other: CMA, see 5.3) 69
5.2. " Concomitant Metals analyzer " CMA 73
5.3. Argon Humidifier 77
5.3.1. Principle 77
5.3.2 Filling the humdifier 78
5.3.3. Use 78
5.3.5. Membrane change 78
5.5. Sample handler 80
5.5. Dilution system 81
5.6. Spark ablation 84
5.7. Nitrogen generator 85
6. Maintenance 86
6.1. Correct operation diagnostic 86
6.2. Servicing operations 94
6.2.1. Main preventive maintenance tasks and frequency 94
6.2.2. Maintenance of glass concentric nebulizer 94
6.2.3. Maintenance of JY nebulizer 96
6.2.4. Maintenance of parallel-flow nebulizer 100
6.2.5. Cleaning of glass spray chambers 101
6.2.6. Cleaning the torch 102
6.2.7. Replacement of pump capillary tubes 104
6.2.8. Cleaning the entrance window 105
6.3. In the event of a problem 107
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6.3.1. Absence of signal or low signal 107
6.3.2 Bad instantaneous stability 107
6.3.3. Loss of reference line or zero order 108
6.3.4. Spectralink reinitialisation. 108
6.4. Periodic verification of spectrometers. 108
6.5. Spare parts 1112
6.5.1. How to order 112
6.5.2. Minimum recommended stock 112
7. ANNEXES 113
7.1. Bibliography 113
7.1.1. General works 113
7.1.2. Sample introduction 113
7.1.3. Detector 113
7.1.4. Sample preparation 113
7.1.5. Statistics applied to analytical chemistry 113
7.1.6. Journals 114
7.1.7. Wavelength and interference tables 114
7.2. Wavelengths as a function of matrices 115
7.3. Training 128
7.4. Optical system supplement 128
7.4.1. Illumination system 128
7.4.2. Dispersive system 129
7.4.3 Detector 141
FIGURES
Figure 1 : WAV example 8
Figure 2: ACTIVA size 10
Figure 3: Marking on ACTIVA (frant face) 11
Figure 4: Marking on the ACTIVA spectrometer (side) 12
Figure 5: Commands on front panel 15
Figure 6: Details of commands on gas panel 16
Figure 7: Detail of the front face of the thermoregulation 16
Figure 8: Access to the section switch on the instrument side 17
Figure 9: Detail of the mains exit 17
Figure 10: Connections to camera 24 028 010 19
Figure 11: Connections to camera 24 028 020 20
Figure 12: Mains connections 20
Figure 13: Energy transition 21
Figure 14: Transformation of sample 22
Figure 15 : Magnetic field 23
Figure 16: Calibration line 25
Figure 17: Repeatability and Accuracy 26
Figure 18: Gaussian distribution of spectral background distribution fluctuations 27
Figure 19: Detection of a point among the background noise 27
Figure 20: Smallest detectable signal XL 28
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Figure 21: BEC 29
Figure 22: Influence of matrix 30
Figure 23: Exploded view of the ACTIVA 32
Figure 24: Sample introduction, vertical torch 33
Figure 25: Concentric glass nebulizer 34
Figure 26: JY Nebulizer 35
Figure 27: Parallel-flow nebulizer 36
Figure 28: Principle of ultrasonic nebulizer 37
Figure 29: Scott spray chamber 38
Figure 31: Sheath device 40
Figure 32 Vertical torch 41
Figure 33: Optical system 42
Figure 34: Grating principle 43
Figure 28: Monochromator 43
Figure 35: Influence of solution uptake 47
Figure 36: Influence of aerosol pressure 47
Figure 37: Influence of integration time n the relative standard deviation on background 48
Figure 39: Limits of confidence for a concentration 55
Figure 40: Example of WAV 66
Figure 41: Organic plasma 68
Figure 42: Hydride Generator 73
Figure 43: CMA chamber, principle 74
Figure 44: "CMA" chamber 78
Figure 45: Argon humidifier, principle 78
Fifure 47: Argon humidifier schematic 79
Figure 47: Membrane change 80
Figure 49: Dismounting the membrane 80
Figure 50: Sample handler JY AS 500 81
Figure 51: Dilution system 82
Figure 52: Diluter needle 83
Figure 53: Dilution needle adjustments 84
Figure 54: Solvent diffusion 84
Figure 55: Spark ablation 85
Figure 56: Nitrogen generator 87
Figure 57: Diagnostics: resolution 91
Figure 58: Diagnostic : transfert d'nergie (1) 92
Figure 59: Diagnostic :energy transfer (2) 93
Figure 60: Diagnostic : transfert optique 93
Figure 61: Diagnostcs: nebulization system 94
Figure 62: Dismountong of the optical channel 107
Figure63: Optical gun 107
Figure 64: Window holder 107
Figure 65: Plasma with Y 1 g/L solution 108
Figure 66: Vrification certificate (1) 111
Figure 67: Verification certificate (2) 112
Figure 68: Illumination system 131
Figure 69: Diffraction 132
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Figure 670: The difference of functioning 133
Figure 71: Two orders 134
Figure 72 : ACTIVA dispersive system 134
Figure 73: Diffraction : grating and prism 138
Figure 74: Gratings manufacture 139
Figure 75: Engraving machioe 140
Figure 76: Grating graving 140
Figure 77 :Holographic record 141
Figure 78: Profil d'un rseau 141
Figure 79: CCD with back illumination 144
Figure 80: Quntum efficienty front illumination (a) back illumination (b) 144
Preface
ACTIVA is an ICP spectrometer developped by keeping the strengths of HORIBA Jobin Yvon spec-
trometers. New technologies have been developed to enhance speed and productivity.
The main strong points of the HORIBA Jobin Yvon spectrometers are the following:
- high and constant resolution on a wide spectral range,
- sensitivity,
- flexibility: access to all wavelengths,
- quality of the optics: high luminosity, low level of stray light and very low level of optical aberra-
tions.
ACTIVA uses the plateform developped for the ULTIMA 2 family:
- spacious sample introduction space,
- Efficient and robust solid state RF generator,
- Smart Hood gas exhaust,
- Optical system allowing to get a large spectral range with good resolution,
- ANALYST
TM
software.
The ACTIVA has also the following characteristics:
- new optical interface,
- Solid state detector, with advanced technology,
- Measurement electronics: Symphony ultra fast, high dynamic of measurement,
- software ACTIVAnalyst
This spectrometer allows the analysis of large spectral windows called WAV (Wavelength Analytical
View). it means simultaneous acquisition of a wide spectral range including eventually several lines
of the same element, several elements and the background of each line.
Figure 1 : WAV example
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1. Introduction
1.1. About this manual
This manual applies to the HORIBA Jobin Yvon ICP spectrometer:
ACTIVA
TM
This manual is divided into the following seven chapters:
Chapter 1 INTRODUCTION Safety instructions.
Chapter 2 EMISSION SPECTROMETRY General information on ICP-AES
Chapter 3 DESCRIPTION OF SPECTROMETER Main parts of spectrometer:
description
Chapter 4 USING THE SPECTROMETER How to use the spectrometer:
start-up, plasma optimisation,
how to perform an analysis
Chapter 5 ACCESSORIES Description and use of various
accessories (nebulizers, chambers,
etc.)
Chapter 6 MAINTENANCE How to check correct operation of
the spectrometer and perform user
maintenance operations
Chapter 7 APPENDICES Bibliography, glossary, index,
wavelength tables, etc.
Carefully read sections 1.2 to 1.10 concerning the safe use of HORIBA Jobin
Yvon spectrometers. We decline all responsibility in the event of a problem
arising from incorrect use of the spectrometer.
1.2 Use
ACTIVA
TM
is a plasma emission spectrometer (ICP-AES) for the determination of
concentration of elements in a sample. Samples are mainly introduced in the spec-
trometer in a liquid form. The elements are determined either qualitatively either
quantitatively. The spectrometer is used with other analytical techniques in labora-
tories for the analysis of samples or process control.
ACTIVA
TM
was design in order to be used by trained person only. Its use, optimi-
zation and its daily maintenance should be done only by qualified people.
1.3 Technical specification
Model: ACTIVA
TM
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Weight: 195 kg (430 lb)
Dimension: 727 x 1430 x 750 mm (28.6 x 56.3 x 29.5 in).
Figure 2: ACTIVA size
1.4 Name and address of the manufacturer
ACTIVA
TM
was designed and manufactured by:
HORIBA Jobin Yvon SAS
Division Emission
16-18 rue du Canal
91165 LONGJUMEAU
FRANCE
A technical assistance can be obtained from your local reprensative or from our
after sales service: (33) 1 64 54 13 42.
1.5. " Danger " and " Safety hazard " notices
" Danger ": indicates procedures to adopt to avoid damage or destruction
of the instrument or other equipment.
" Safety hazard ": indicates a potential safety hazard, with procedure to be
followed to avoid injury.
1.5.1 Marking on ACTIVA
1430 mm
275 mm
605 mm
45 mm
727 mm
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Figure 3: Marking on ACTIVA (frant face)
(1) SAFETY HAZARD: Push and lock the sliding window before
starting the generator.
(1) SAFETY HAZARD: plasma is an UV source as well as an
heat source. Never try to light plasma with the door open.
Never short-circuit the door safety device. Never look
through the chimney when the plasma is lit. Do not place
anything on the chimney.
(2) SAFETY HAZARD: Cut the current before intervention.
(3) SAFETY HAZARD: Caution risks of burns. Extraction tube
required.
Figure 4: Marking on the ACTIVAspectrometer (side)
(1) SAFETY HAZARD: Cut the current before
intervention
(2) SAFETY HAZARD: Caution, risks of burns.
Extraction tube required.
(1) SAFETY HAZARD: Cut the current before
intervention.
This logo indicates that the product at the end of life should
have a specific treatment.
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1.5.2. Specific precautions for maintenance
Safety hazard: Covers or pieces opening, expect those which can be opened
by hand only, can give access to dangerous zones.
The instrument must be disconnected from the source of voltage before remo-
ving covers.
Before intervening on the instrument where all the covers are open, wait for
at least 3 minutes to allow the capacitors to discharge.
The important components for safety should be replaced only by components
provided by HORIBA Jobin Yvon. Even if the components seem equivalent
the characteristics are not identical.
After a deconnection or an intervention on the gas lines, do the verifications
to avoid any leak.
1.6. Installation of ACTIVA
The conditions for the installation of ACTIVA are described in the preinstallation
manual 31 088 538.
The installation can be done only by a qualified technician from HORIBA Jobin
Yvon or his local representative. At delivery of ACTIVA, it is necessary to observe
the aspect of the packaging.
In case of damage:
There are 2 shock indicators : " tiltwatch " to keep instrument upright, " shock-
watch " to detect any shocks. If some damage is discovered, leave the instrument
in its original container and packaging. Claim on carrier's delivery note immediate-
ly, clearly stating what is observed.
Example: tilt indicator turned red, carton box have scratches on top left end, com-
ments must be very precise
Within a period of 3 working days maximum, a registered letter must be sent to the
carrier, stating that they are responsible for the damages, with a request for them to
supply an immediate inspection report. According to the contract incoterms, this
letter must be done by either the customer (EXW, FCA, CFR, CIP) or by HORIBA
Jobin Yvon (if DDU in some European Communities).
N.B.: NEVER open boxes if external damages are suspected. Refuse the goods and
send them back to the carrier's warehouse, if possible. This will obviously state the
carrier's responsabilities beyond dispute.
We recommend that you keep the original packaging for any subsequent transfer of
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the instrument.
1.7 Safety precautions.
For correct, safe use of the spectrometer and its accessories, the operator and
maintenance personnel must be thoroughly familiar with the general safety
procedures, in addition to the specific precautions detailed in this manual.
- " Danger " and " Safety hazard " notices are indicated in the manual
wherever necessary. Labels are also attached to the instrument where
necessary.
- Users should never enter his hand into the spectrometer except in sam-
ple case.
- Instrument and accessory covers should only be removed by maintenance
personnel who have been informed of the risks of electrical shock. The
electrical power supply must be disconnected from the instrument at least
three minutes before intervening to allow the capacitors to discharge.
- The torch sliding window should be set in the right position, pushed and
locked afetr each torch removal in order to close the torch shielding.
- Always follow the laboratory safety rules.
- When conducting spectroscopic observations, toxic and corrosive and/or
flammable substances are used. Samples can be toxic or radioactive. All
general precautions related to handling of chemical substances should
be observed. For radioactive substances, additional training is required.
- The laboratory should be adequately ventilated in case of use of toxic
products. Store the solvants in adequate cabinets or hoods.
- The laboratory should be adequately ventilated and no flame should be
lit near the instrument and its accessories. Carefully read the instructions
detailed in the pre-installation manual relative to extraction systems.
- Wear always protections for eyes, skin and dresses when dangerous che-
mical products are used.
- In laboratory always wear protective googles against splash
- The ultraviolet rays produced by the plasma are dangerous for the eyes
and skin. Special goggles can be worn to directly view the plasma. Even
with protective goggles, radiation can be dangerous. Do not operate the
plasma without closing the compartment protection door. Never short-
circuit the safety devices.
- Never look at the plasma directly through the chimney.
- Be careful not to spill corrosive solvents on the instrument, in particular
on the mechanical parts.
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- Be sure to empty the drain when full. Do not forget that the recupera-
tion and the waste disposal is under your responsability and shoud be done
with respect to the regulations. Do not forget that analyzed solutions can
contain acids (chlorydric, sulfururic, nitric, hydrofluorydric...), organics
solvents or other dangerous solvent: take necessary precautions to the
manipulations.
- If a dangerous substance is spread over the instrument, the user has the
responsability to decontaminate the accessibles parts of the instrument
with the appropriate substances.
- Argon is required to operate the plasma. Nitrogen is also used to purge
the spectrometer. Before connecting, check that the gases are properly
identified.Verify the entrance pressure and the lack of weak before the
start of the instrument.
- Under no circumstances should a safety device ever be inhibited or short-
circuited. The safety devices are there for your safety.
- Never light the plasma when the extraction systems are not operating:
various gases such as ozon can be emitted by the torch.
- The instrument should be linked to the electrical pannel of the labora-
tory by a conductor of the appropriate section: the earth link should be
in conformity with the current regulations.
- Be sure that the air entrance below the instrument are not obstructed.
Non respect of the instructions of the manual or use of the instrument other than
those specified in this manual can compromise the protection insured by the instru-
ment and generate a danger.
1.8 Identification of commands
Figure 5: Commands on front panel
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The available commands on the gas panel and thermoregulations are precised in the
two following figures.
Figure 6: Details of commands on gas panel
The nebuliser pressure is adjusted by a precision nanometer, the value of the pres-
sure can be read on the screen Automatism of the ActivaAnalyst software.
The plasma, auxiliary and sheath gas flowrate are read on flowmeters. These flo-
wrates can be adjusted with a simple screwdriver.
The supply of the radio-frequency generator (RF) is controlled via a switch on the
gas pannel. Cutting this supply allows to suppress the noise made by the fan of the
RF generator, and to stop the air flow going through the generator.
Figure 7: Detail of the front face of the thermoregulation
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The thermoregulation of the spectrometer case can be stopped by setting the switch
on 0.
The set point for temperature can be adjusted with a screw driver. This operation is
done during the installation by the HORIBA Jobin Yvon Engineer. No further adjust-
ment is required.
The green light emitting diode (LED) is lit when the thermoregulation system is
heated or when the system is off.
Figure 8: Access to the section switch on the instrument side
This mains breaker can be use to switch on or off. the power of the spectrometer
Before any intervention in the spectrometer, the supply should be shut off.
Figure 9: Detail of the mains exit
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Couper lalimentation
avant toute intervention
Turn off power before ser-
vicing
I
0
Disjoncteur Principal
Main Breaker
This output is protected by two fuses, one for each phase.
1.9 Common maintenance of ACTIVA
Change the peristaltic pump tubes and the capillaries as soon as they have some tra-
ces of wear. Their wear can alter the instument performance and a failure of these
tubes can lead to leaks of liquids in the instrument.
Before each start, verify the absence of leak on the gases lines (argon and nitrogen)
and water line.
The panels and sheet metal cleaning can be done with a tissue impregnated with alco-
hol.
External fuses can be replace if required. It is forbiden to remove the panels to access
to internal fuses, only an HORIBA Jobin Yvon engineer or its representative can do
it.
1.10 ACTIVA specification
1.10.1 Environmental conditions
Climatic conditions of use Use inside
Altitude below 1000 meters (3000 feet)
Temperature between 18 and 24 C
(64 to 75 F)
Maximum relative humidity of 80%
Pollution degree Degree 2. Non conductive pollution only.
Connection to the electric Fluctuations of the voltage not exceeding
supply network +- 10% of the nominal voltage.
Normal presence of transient overvoltage
on the power supply: installation category II.
1.10.2 Instrument caracteristics
Voltage range 230 V
Frequency range 50 - 60 Hz
Absorbed power 5kVA
Network connection Monophased connected by cord or
permanently.
Functioning mode Continuous
Caracteristics of external Auxiliary output: 230V/600VA
circuits under dangerous Protected by 2 fuses (5x20-T 3.15A)
voltage
Instrument mobility Fixed
Protection systems Combined differential (30 mA) and mains
breaker (32A).
Internal fuses: 8 x 32 - 4A (spectrometer side)
Fluids Argon
Nominal input pressure: 5 bars
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Maximal input pressure: 6 bars
Flowrate at nominal pressure: 12-25 L/min
Nitrogen
Flowrate at nominal pressure: 0.5-6 L/min
Water
Flowrate at nominal pressure: 2-3 L/min
Regulations Safety: EN 61010-1 and EN 61010-2-061
Electromagnetic compatibility: EN 61326
1.10.3 In/Out
1.10.3.1 Connections with camera 24 028 010
Figure 10: Connections with camera 24 028 010
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1.10.3.2. Connections with camera 24 028 020
Figure 11: Connections with camera 24 028 020
1.10.3.3 Mains connections
Figure 12: Mains connections
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2. Emission spectrometry
2.1. Principle of atomic emission
2.1.1. General information
A given atom has a large number of possible energy levels.
An emission spectrum is produced by an electronic transition from a high ener-
gy level E
n
to a lower energy level E
m
. The acceptable transitions are given by
the quantum mechanics selection rules.
A quantity of energy Q is transferred to an atom by collision with another
particle, resulting in the excitation of the atom. An electron from an outer layer
of the atom is excited to a higher energy level. Following this electron excita-
tion, the electron returns, in one or several stages, to its original energy level.
The atomic emission technique measures the energy lost by an atom passing
from an excited state to a lower energy state.
The energy is released in the form of light rays with a wavelength , or more
specifically, in the form of a photon with a frequency v carrying energy h x .
A given atom has a great number of energy levels available.
Figure 13: Energy transition
The atomic emission spectrum is composed of discrete spectral lines.
The number of photons emitted is proportional to the number of atoms of
the element present.
To be excited, the sample must be atomised, meaning dissociated into free ions
or atoms.
For a liquid sample, the atomisation process can be schematised as follows.
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Figure 14: Transformation of sample
Depending on the species excited, the lines have different names:
* emission from an atom: line I
* emission from an ion once ionised: line II
* emission from an ion twice ionised : line III
In the plasma, lines I and II are frequently observed; lines III are rarely obs-
erved and lines of a higher degree are not observed. This is due to the ener-
gies involved.
2.1.2. Plasma
The emission phenomena takes place in a plasma. A plasma is more or less an
ionised gas, electrically neutral. The gas used is argon.
Plasma creation:
An argon flow travels through a crystal tube inside a solenoid. The lines of
force, generated by the magnetic fields are directed along the axis of the sole-
noid inside the tube and take the form of an ellipse on the outside.
An electrical discharge is created to arc the plasma by partially ionising the gas
in the torch.
The electrons produced are subjected to the magnetic field induced and cir-
culated along the axis of the crystal tube describing annular circuits. Induced
or eddy currents are thus produced. The electron path is stopped by collision,
resulting in heating and ionisation of the other gas atoms. The plasma main-
tains itself.
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Figure 15 : Magnetic field
Gas used:
The gas generally used is argon which, like all rare gases, is monatomic, che-
mically inert and has a high ionisation energy (15.6 eV). A certain number of
advantages are provided by argon:
- Emission of a relatively simple spectrum producing little spectral inter-
ference in emission spectrometry,
- Capacity to atomise, ionise and excite most of the elements of the per-
iodic table,
- Absence of formation of stable composites between argon and elements,
- Lower cost than that of other rare gases as it is the most widely availa-
ble (1 % in air).
Its only limitation is its low thermal conductivity compared to that of
molecular gases such as nitrogen or oxygen.
During heating, the argon ions transfer energy to the atoms present in the sam-
ple solutions.
2.1.3. Radial or axial viewing
Certain spectrometers observe the plasma along its axis (axial viewing) while
others observe laterally (radial viewing).
The choice of viewing is made when the instrument is purchased.
The choice depends on the applications for which the instrument is intended.
Advantages of HORIBA Jobin Yvon radial viewing:
- Very good detection limits.
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- Less matrix effects than an axial viewed plasma.
- Less interference effects, in particular for organic substances.
- No limitation on types of matrices.
- No need to optimise the height of observation by element since the area
observed is very large.
- High linear range.
- Less torch maintenance.
- Optimisation of torch is facilitated.
2.2. Analysis
2.2.1. Introduction
As discussed in section 2.1.1., an atom subjected to a plasma emits characte-
ristic photons. This property makes it possible to perform a qualitative
analysis.
The number of photons emitted is proportional to the number of atoms of
the considered element. This is the basis of the quantitative analysis.
2.2.2. Qualitative analysis
A qualitative analysis consists of searching for the elements in an unknown
sample.
Viewing the characteristic lines of the elements performs this search.
Since two elements can have the same wavelengths or two very similar wave-
lengths, an element must have at least two well-known wavelengths. The lines
recorded reveal the presence of an element. An approximate quantification
can also be performed.
To select the lines, see the wavelength tables in section 7.2. Note that expe-
rience will play a major role in interpreting the spectra.
This semi-quantitative analysis can be performed very rapidly using the " Image"
tool.
2.2.3. Quantitative analysis
The quantitative analysis links the energy emitted to the number of atoms
contained in the sample.
Atomic emission is not an absolute method. The relation existing between
the intensity emitted by a line and the concentration of the associated ele-
ment must be calculated: this is called the line calibration curve.
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The advantage of ICP-AES is that these calibration curves are, in most cases,
linear to several orders of concentration.
Great care must be taken in calculating these curves as they will determine the
ultimate accuracy of the analysis.
Figure 16: Calibration line
2.2.4. Analytical performances
An emission spectrometer provides a large number of analytical performance fea-
tures: accuracy, repeatability, reproducibility, selectivity, robustness, sensitivity, detec-
tion limit, linearity, dynamic range
The main terms are defined below:
Accuracy The accuracy of an instrument is its capacity to give results that are free of
systematic error, meaning having a good degree of exactitude.
The accuracy is evaluated by the difference between the measured mean
value and the true value of element concentration.
Blank Matrix without analytes.
Detection limit Smallest concentration which can be detected with certainty with respect
to a blank.
Error Deviation between the mean value and the true value.
Fidelity Capacity of an instrument to give good repeatability.
Long term stability Equivalent to repeatability over a long period of time (several hours).
Precision Corresponds to repeatability and reproducibility.
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Quantification limit Concentration corresponding to a given repeatability (for example 5 %).
Repeatability Represents the fluctuations of the signal during a single reading under the
same measurement conditions.
Reproducibility Represents the fluctuations of the signal when one of the
measurement parameters has varied.
Robustness Capacity of the plasma to accept different changes without significant
variation in element concentration. These changes can come from the matrix,
the analytical parameters or the environment.
Sensitivity Slope of the calibration line; signal intensity versus concentration.
Uncertainty Estimation within which the true value is located.
Repeatability, reproducibility and accuracy:
These three terms are often understood to mean the same thing.
Repeatability and reproducibility are expressed as a relative standard deviation.
The only difference is the fact that for reproducibility, one of the parameters
has varied.
Accuracy is a principle that can be difficult to measure. It is evaluated using
certified reference materials. It mainly depends on the calibration curve and
the preparation of samples.
The repeatability and accuracy concepts can be summarised using a target. The
true value being the centre of the target.
Figure 17: Repeatability and Accuracy
The second case is better than the third, even though the result seems bad
(high relative standard deviation).
Detection limits (LOD), Quantification limit (LOQ)
Here, we assume that the fluctuation of the spectral background follows a
Gaussian distribution defined by its standard deviation .
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Figure 18: Gaussian distribution of spectral background distribution fluctuations
The detection limit is derived from the signal that will be statistically possible
to extract from the background. This comes down to stating the following
question: does a measurement point belong to the background or to the signal?
K corresponds to a safety coefficient. The higher the k, the easier it will be to
differentiate a signal point from a background point.
Figure 19: Detection of a point among the background noise
The previous figure represents the overlap of the fluctuations of background
B and signal S as a function of the deviation between the two mean values,
expressed in multiples of standard deviation.
The figure below shows the influence of the coefficient k on the percentage
of error.
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Figure 20: Smallest detectable signal X
L
The IUPAC recommends applying k = 3. The percentage of error is then 13%.
Three equivalent formulas are used to express the detection limit:
(C
L
., limit concentration) :
(1) C
L
= 3 C S
B
/S
(2) C
L
= 3 C RSD
B
/SBR
(3) C
L
= 3 BEC RSD
B
Where:
S: net signal of solution
C: concentration of solution measured.
s
B
: standard deviation of blank
RSD
B
: standard deviation relative to blank
SBR: signal to background ratio
BEC: Background Equivalent Concentration
Formula (2) is mainly used for plasma optimisation. Formula (3) is used to
calculate the detection limits for a given matrix following a calibration (auto-
matic calculation in the ICP acquisition software).
The BEC is represented on the next figure. It corresponds to the concentra-
tion for which the signal is equal to the background (S = B or SBR = 1).
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Figure 21: BEC
BEC is the absolute value of the ordinate at the origin of the calibration
curve when no background correction is applied. If a background correction
is applied, use formula (2).
For the detection limit, RSD is expressed:
Therefore, for k = 3, RSD = 47 %.
To define the quantification limit, you define the maximum desired RSD, for
example 5 or 10 %.
RSD = 10 %, for LOQ = 4.5 LOD
RSD = 5 %, for LOQ = 10 LOD
RSD = 2 % for LOQ = 30 LOD
Generally, the minimum LOQ used = 3 LOD.
The detection limit is an estimation.
The quantification limit is a measurement.
The detection limit can be calculated in water or in a special matrix. It is very
important to know the detection and quantification limits for each of the appli-
cations.
Robustness
Depending on the composition of the matrix, the same concentration of an
element will not give the same signal.
For example, 5 ppm of Mg in water or in NaCl 10 g/L does not give the same
net intensity.
2 ) / 1 ( k RSD =
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Figure 22: Influence of matrix
To minimise this difference, the most robust plasma possible must be used.
The robustness can be evaluated by the ratio between two lines (an ionic line
and an atomic line). For this purpose, we use the ratio provided by two
Magnesium lines:
Mg II 280 nm/ Mg I 285 nm.
The higher the ratio, the more robust the plasma is.
A plasma is robust when the ratio of magnesium is greater than 6. In this
case, the plasma is in thermodynamic equilibrium.
Note: the Mg ratio is calculated with the following formula:
Net intensity Mg II x Background Mg I
Mg ratio =
Net intensity Mg I x Background Mg II
2.3. Preparation of samples
The samples are usually introduced into the plasma in solution form but solids,
finely divided, can also be used. Care should be taken in obtaining a solution of a
solid sample since there is a risk of loss of element, or contamination.
The final solution obtained by the analyst depends on the nature of the sample and
the concentration of elements to be determined.
Two main types of sample preparation are used for ICP analysis:
Humid attack.
Dry attack.
Humid attack with acids.
Acids, whether single or in a mixture, use their oxidising or reducing properties.
Care must be taken with respect to possible loss of volatile elements. For example,
loss of As, Se, Sn in the form of chloride in the presence of HCl. Creation of pre-
cipitates of Ca, Ba, Pb also represents a possible error in the presence of H
2
SO4.
Open and closed microwave systems are increasingly used in laboratories.
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Dry attack
Alkaline fusion is often used, as well as high-temperature calcination (450 - 600 C)
with acid recovery of ashes. Care must be taken with respect to contaminants intro-
duced by the reagents. Losses by volatilisation and insolubilisation can be more
than negligible.
Remarks:
- Whatever the type of solution, the quantity of acid or flux must be as low as pos-
sible to ensure minimum perturbation of the plasma. Certain acids are prefera-
ble to others as they perturb the plasma less.
Order of preference (from more favourable to least favourable): HNO
3
, HCl,
HCLO
4
, H
2
SO
4
, H
3
PO
4
.
- Caution, HF requires a specific sample introduction system.
- Na has a high depressive effect on sensitivity.
- The presence of hydrofluoric acid can result in the formation of Ca, Mg Mn
fluoride precipitates. This occurs frequently during mineralisation of geological
products, even after evaporation of the hydrofluoric acid. This can be avoided by
adding a few drops of boric acid.
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3. Description of spectrometer
3.1. General breakdown of unit
A plasma emission spectrometer comprises of five main parts:
1. A system which carries the sample into the plasma
2. A generator which applies energy to the plasma
3. An optical system which analyses the spectrum emitted by the plasma
4. A signal processing system for qualitative and quantitative analysis of the emit-
ted radiation.
5. A computer system forming the interface with the user.
The principle of each sub-assembly is described in the following pages.
Figure 23: Exploded view of the ACTIVA
3.2. Sample introduction system
The samples introduced in the plasma are either in liquid form or in the form of
fine solid particles suspended in the liquid. The diameter of the particles must not
exceed ten microns.
The sample introduction system comprises:
- A nebulizer which creates the spray,
- A spray chamber which sorts the droplets,
- A sheath device to sheath the spray,
- A burner to take the spray into the plasma.
The introduction system depends on the type of sample analysed. In this section,
we will see how to select the best assembly.
The next figure provides a schematic view of the sample introduction system for a
laterally viewed plasma.
Figure 24: Sample introduction, vertical torch
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3.2.1. Nebulizer
The nebulizer creates a spray whose grain size must be less than 10 m. Droplets
greater than 10 m are sorted out in the spray chamber.
3.2.1.1. Concentric nebulizer
The pneumatic nebulization technique uses the Venturi effect to suck
in and transform the solution into a spray.
Concentric nebulizers: These are the most widely used nebulizers.
Two types of concentric nebulizers are proposed, glass and metal.
For these nebulizers, the gas and liquid flows are coaxial.
For the glass nebulizer (borosilicate), the end of the liquid supply capilla-
ry tube is recessed to limit any possible clogging.
This nebulizer is referenced: TR-xx-Cy where xx is the operating pres-
sure and y the rated solution flow.
Figure 25: Concentric glass nebulizer
Pressure examples:
20 0.7 - 1.6 10 - 24
30 1.7 - 2.7 25 - 40
50 2.8 - 3.5 41 - 60
Examples of flow rates:
0,5 0,3 0,6
1 0,7 1,4
2 1,5 2,4
3 2,5 3,5
Indication Cy Utilisation range (ml/min)
Indication xx Utilisation Utilisation
range (bars) range (Psi)
The stainless steel concentric nebulizer has the advantage of being adjus-
table.
An adjustable needle and a fixed nozzle form the device. By moving
the needle toward the nozzle, the fluid flow section, at constant pres-
sure, is reduced while the speed of flow increases. This increase in speed
creates a high vacuum resulting in suction of the liquid and formation
of the aerosol.
Concentric glass nebulizer:
Inside diameter: 0.3 mm
Utilisation: Water or clean organic solution (no particles). Maximum 10
g/L salt or 300 g/L with argon humidifier.
Advantage: Excellent sensitivity
Disadvantage: Frequent clogging (particles and chemical reaction)
HJY concentric nebulizer:
Inside diameter: 0.7 mm or 1 mm depending on model.
Utilisation: Water or organic solution. Viscous product (organic or bio-
logical).
Advantage: High sensitivity, particles accepted.
Disadvantage: Tricky to adjust.
Figure 26: HJY Nebulizer
3.2.1.2. Parallel-flow nebulizer
This is a PEEK and Teflon parallel-flow pneumatic nebulizer whose
design has been patented. All types of acids can be nebulized, including
hydrofluoric acid. By its design, salt formation at the end of the nebu-
lizer is practically non-existent, thus making it possible to nebulise solu-
tions with a high salt content (30%).
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Figure 27: Parallel-flow nebulizer
Parallel-flow nebulizer:
Inside diameter: 0.3 mm
Utilisation: Water solution, HF or clean organic (no particles).
Advantage: Very good sensitivity, little chemical reaction.
Disadvantage: Deterioration of capillary tube over time.
3.2.1.3. Ultrasonic nebulizer
Numerous advantages for the ICP are provided by an ultrasonic nebu-
lizer.
- Improved sensitivity due to a finer aerosol that is therefore easier
to transport (factor of 5 to 20 on detection limits).
- Aerosol is more regular.
- It eliminates solvent.
- Quantity of aerosol injected in the plasma is very high. (> 95 %)
However, certain elements which are too volatile are not or only mode-
rately improved (Se, Hg).
The nebulization efficiency strongly depends on the matrix; it is there-
fore very important to use standards that are close to the samples.
A model specifically adapted to volatile products (alcohol, petroleum
products, etc.) is available.
Figure 28: Principle of ultrasonic nebulizer
Principle:
A piezo electric crystal is excited by a generator at its resonance fre-
quency. The crystal vibrations are transmitted to the sample. The aero-
sol produced is driven by an argon current, transporting it through a
desolvation system to eliminate the solvent. The solvent, for example,
distilled water, cools the central area of the plasma. It is the source of
molecular band emissions seen in ICP-AES. In addition, it limits the
quantity of sample that can be introduced into the plasma.
By removing almost all the solvent, the sample is now a dry aerosol,
which is carried into the plasma.
The maximum acid concentrations for good nebulization are as follows:
Sulphuric acid: 5 %
Hydrochloric acid: 25 %
Nitric acid: 25 %
Boric acid: 5 %
Perchloric acid: 5 %
NO Hydrofluoric acid (because of glassware)
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3.2.2. Spray chamber
Prior to introduction into the plasma, the aerosol passes through the spray
chamber where the large droplets are eliminated. The waste liquid is evacua-
ted through teh drain. Flow stability is very important for the quality of the
analysis.
Two types of spray chambers are used:
- Scott chamber
- Cyclone chamber
Scott chamber
Figure 29: Scott spray chamber
This is a sedimentation chamber: the aerosol takes a certain path. The larger
droplets fall to the bottom of the chamber since their speed is insufficient to
exit the chamber.
This model comes in glass or in an inert material to withstand the hydrofluo-
ric acid.
Scott chamber (about 100 ml)
Utilisation: All solutions.
Advantage: Can be used with any nebulizer
Disadvantage: Less sensitivity than cyclone chamber, longer rinsing time.
Cyclonic spray chamber
Figure 30: Cyclonic spray chamber
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The aerosol arrives in the chamber by a cyclone effect and only the
fine droplets reach the sheath device.
This chamber comes in glass or inert material.
Cyclonic chamber (about 50 ml)
Utilisation: Water or organic solution not too much salt content (< 40 g/l)
Advantage: Excellent sensitivity
Disadvantage: Only accepts a glass concentric nebulizer or parallel-flow nebu-
lizer.
3.2.3. Choosing a nebulization system
The instrument is supplied in its standard configuration with a glass concen-
tric nebulizer and a cyclone chamber.
The choice is made in accordance with the data in the table below:
Glass concentric Cyclone Very high Very high Water solution, no HF,
and/or clean oils
Scott, glass High Very high Water solution, without HF,
and/or high salt concentra
tions and/or clean oils
JY nebulizer Scott, glass Very high Very high Water or organic solution
without HF, and/or high
salt concentrations and/or
suspended particles.
Scott, inert High Very high Water or organic solution
material with HF, and/or high
salt concentrations and/or
suspended particles.
Parallel flow Cyclone Very high High Water solution, no HF,
nebulizer glass and/or clean oils
Cyclone, inert Very high High Water solutions with HF.
material
Scott, glass High High Water solution aqueuse ,
without HF, and/or high salt
concentration, and/or clea
ned oils.
Scott, inert High High Water solutions, with HF,
material and/or with high salte
concentrations and/or clea
ned oils.
Micro-concentric Scott, glass High High Water or organic solution
nebulizer or inert material with ou without HF ideal
for analysis micro-volumes
Nebulizer Spray Sensibility Repeatability Applications
chamber
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3.2.4. Torch
The aerosol is transported to the plasma through a sheath device and a set of
torch tubes.
Sheath device
This device sheathes the aerosol in an argon gas. Introducing this additional
gas provides the following advantages:
- Possibility for passing solutions of up to 350 g/L without clogging or
contaminating the injector tube,
- For alkalines,
- Plasma is cooled for improved excitation efficiency,
- Changes in the observation height.
For alkalines, the additional sheath gas is controlled by the software and the
automatic control functions.
The sheath device is a patented HORIBA Jobin Yvon system.
Figure 31: Sheath device
The torch can be entirely disassembled and is comprised of three concentric
tubes:
1. Outer tube made of quartz.
2. Intermediate or auxiliary tube made of quartz.
3. Central injector tube, made of alumina.
These three tubes delimit three channels through which the argon passes:
- The outer channel, where the argon arrives tangentially, receives the "cooling"
argon.
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- The intermediate channel receives (when necessary) an argon flow (auxilia-
ry gas) to raise the plasma cone of the injector (organic solutions).
- The central channel is intended for the sample in aerosol form carried by
the vector argon resulting from the nebulization and sheath.
Figure 32 Vertical torch
1 : outer tube
2 : inner tube
3 : injector
4 : centering piece
5 : insert
6 : connector
3.3. Generator
3.3.1. Generator
The generator supplies the energy required to produce and maintain the plas-
ma.
It comprises three main parts:
1. The power supply.
2. The oscillator which converts the power into a radio frequency energy (RF)
at 40.68 MHz.
3. The adapter unit which transfers the energy to the plasma.
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3.3.2. Automatic control functions
The automatic control functions ensure:
- Starting and stopping of the plasma,
- Programming and control of the gases (cooling gas, sheath gas, auxiliary
gas),
- Control of nebulization flow and pressure,
- Programming and control of the peristaltic pump,
- Control of the safety devices (generator safety devices, gas safety devices,
external safety devices, etc.).
The automatic control functions comprise:
* A dual-channel pump,
* A pressure regulator,
* An electronic assembly,
* A control screen on computer.
3.4. Optical system
For more information concerning the optical system, refer to part 7.4.
3.4.1. Introduction
The spectrometer is made of three parts:
- The illumination system.
- The dispersive system.
- The detector
Figure 33: Optical system
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3.4.2. Illumination system
The illumination system transfers the light emitted by the plasma to the spec-
trometer entrance. The system comprises one miror, which forms the optical
image of the plasma on the spectrometer entry slit. This optical system allows
to see the optimal zone of the plasma of 6 mm height.
3.4.3. Diffraction grating
The grating is the core of the spectrometer. The grating is formed by a glass
support covered by a photosensitive film on which a large number of paral-
lel lines are printed holographically (between 1800 and 4320 lines/mm).
The grating diffracts the light. Like the prism, but more effectively, it breaks
down white light into separate wavelengths.
Figure 34: Grating principle
3.4.5 The detector
The detector is a scientific camera equipped with a CCD detector which, with
its 2048 x 512 pixels, is able to analyse spectra up to 16 nm. These spectra are
also named Wavelength Analytical View.
For higher analytical accuracy, an internal standard can be used. The intensi-
ty of the standard is measured by an additional monochromator called H20.
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3.5. Signal processing
3.5.1. Electronics of measurement
The electronics of measurement pilotes the spectrometer. It has several elec-
tronic boards. The number of boards depends on the configuration of the
spectrometer and its option.
Electronic boards:
Motherboard: interconnects the following boards
Mono board: includes the motor command (MONO)
Motor Drive board: includes the motor command (DRIVER)
CPU board: has the microprocessor which manage all the meaurement elec-
tronics
3.5.2 The detector: Symphony system
The principal components of the Symphony detection system are:
- Symphony CCD camera
All symphony cameras use the high performance CCD detector specially designed
for spectroscopy. The choice of the detector depends on the applications.
- Controlor of the Symphony camera
The functions of the controlor are the supply of power, the temperature of the
detector regulation, the control of the exit signal, the conditioning of the CCDs
video signal and the numerisation of pixel information.
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4. Using the spectrometer
4.1. Start-up
4.1.1. Checks
Before igniting or programming ignition of the plasma, perform the following
checks.
1-Check that the solution-pump-nebulizer circuit is free of any leaks and that
the connections are tight.
2-Check operation of the aspirating system used to remove hot gases/fumes.
3-Check the gas connections and supply: argon, nitrogen and compressed air
(possibly).
4- Check that the water cooling circuit operates.
For the last two operations you can select Controls on the automatism screen.
4.1.2. Plasma ignition
The plasma is ignited automatically.
If the plasma does not ignite on the first attempt, try again, as this may be due
to air in the capillary tubes. To have better purge, hold the controls button
of the automation screen.
4.2. Plasma optimisation
Various parameters are optimised according to the desired analysis quality. A fast
analysis does not require the same adjustment as trace analysis.
The analytical optimisation is performed using an instrument that operates correct-
ly. You can consider that the instrument is mechanically adjusted.
The optimisation is performed according to the analytical requirements specific to
each application.
4.2.1. Generator power
The choice of power depends on the solvent:
For example:
Water solution with little salt concentration: 900 W
Water solution: 1000 W
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Water solution with high salt concentration: 1100 W - 1200 W
Organic solution: 1200 W - 1400 W
If the samples do not have a matrix with a constant composition, the generator power
should be increased with respect to the above data to decrease any possible matrix
effects.
4.2.2 Sheath gas
Two values are required: one for all the elements except alkalines, and one for alka-
lines.
The first value corresponds to the maximum level of the SBR curve (Mg 285) as a
function of the sheath gas. The SBR (Mg 285) is the net signal on the Mg background
at 285 nm, (Signal to Background Ratio).
The second value corresponds to the maximum level of the SBR curve (Na) as a
function of the sheath gas.
Typical values:
First value: 0.1- 0.2 l/min.
Second value: 0.8 - 1 l/min.
A high sheath gas flow will be used for Na and K only for concentrations below 1
ppm.
4.2.3 Peristaltic pump speed and aerosol flow
Each time the nebulizer or type of nebulizer is changed, it is necessary to optimise:
- The peristaltic pump flow,
- The aerosol flow, via the nebulization pressure,
The peristaltic pump:
- Always gives the same quantity of aerosol whatever the viscosity of the sample,
- Optimises the quantity of the sample introduced in the plasma.
You must stay on the plateau of the curve shown below to avoid any variation in
the signal due to a slight variation in flow.
This comes down to slightly (around 10 %) increasing the flow rate of the nebuli-
zer with respect to its natural flow rate.
In a water solution, the typical value for a concentric nebulizer is 1 ml/min.
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Figure 35: Influence of solution uptake
To select the nebulization pressure, plot the SBR curves (Mg 285) as a function of
the pressure and the Mg ratio as a function of the pressure. The Mg ratio is the ratio
of the net intensities of the Mg 280 nm and Mg 285 nm lines, obtained with the same
high voltage. Take a nebulization pressure such that the Mg ratio is greater than 8
and the SBR (Mg) is the highest possible.
In our example, apply 3 bars.
Figure 36: Influence of aerosol pressure
The optimal nebulizer pressure depends on the type of nebulizer (see section 3.2.1).
4.2.4 Influence of integration time on background and signal
Limit of detection depends on the Signal to Background Ratio (SBR) and on the
relative standard deviation of the background (RSD
0
) (see part 2.2.4).The following
curve shows that when the quantity of photons is too low, means when the inte-
Influence of arosol pressure
20
40
60
80
100
120
140
160
180
1 1,5 2 2,5 3 3,5
Aerosol pressure (bar)
S
B
R

M
g

2
8
5
4
5
6
7
8
9
10
M
g

r
a
t
i
o
Influence of sample uptake
500
550
600
650
700
750
0,2 0,4 0,6 0,8 1 1,2 1,4 1,6 1,8
Sample uptake(mL/min)
V
a
r
i
a
t
i
o
n

o
f

M
g

2
8
5

s
i
g
n
a
l
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48
gration time is too short, the RSD
0
is too high. It reaches a stage when there is enough
light,when the integration time is increase.
Figure 37: Influence of integration time with the relative standard deviation on background
Influence of integration time on background
The value of the integration time for which the RSD
signal
< 1 % depends on
the quantity of light coming on the detector. It depends on the line sensitivi-
ty, the concentration of the elements and the wavelength.
Summary
The table below summarises the optimisation procedure.
Generator power Matrix Ratio (Mg) >7
Matrix constant
Sheath gas Alkaline or not Maximum SBR(Mg 285)=f (sheath)
Salt content of solution Maximum SBR(Na) = f (sheath)
Peristaltic pump speed Nebulizer and capillary tube Curve plateau
Signal (Mg 285) = f(speed)
Parameter Depends on Optimisation criterion
Relative standard deviation of the signal (100 g/l)
vs. Integration time
0
1
2
3
4
5
6
0 2000 4000 6000 8000 10000 12000
Integration Time ms
R
S
D

s
i
g
n
a
l
Mg 280 Mg 285
Relative standard deviation of the background vs. Integration
Time mean of 3 determinations on 10 replicates
0
1
2
3
4
5
6
0 5000 10000 15000 20000 25000 30000 35000
Integration time ms
R
S
D
(
B
)
231 nm
Nebulization pressure Nebulizer Maximum SBR (Mg 285)=f
(pressure)
And Ratio (Mg)> 7
Integration time Concentration of element Plateau RSD = f(time) for each
and each concentration.
Line sensitivity
Wavelength
4.3. Analytical conditions
Depending on the type of application, certain operating conditions should be selec-
ted. Three conditions are indicated below; these correspond to the usual analysis
conditions with water and organic solutions.
Power 1000 W 1200 W 1400 W 1100 W
Cooling gas flow 12 l/min 15 l/min 18 l/min 13 l/min
Auxiliary gas flow 0 l/min 1 l/min 0.6 - 0.8 l/min 0 l/min
Sheath gas flow 0.2 l/min 0.2 l/min 0.4 - 0.6 l/min 0.4 l/min
Nebulization 2.8 - 3.2 bars 2.5 - 3 bars 1 - 1.5 bars 2.8-3.2 bars
pressure
Pump speed 20 15 5 - 10 20
rpm
Except for very specific samples, the default conditions are perfectly appropriate.
For a new solvent, use the procedure described in section 4.4.7.3 concerning igni-
tion of an organic plasma.
4.4. How to perform an analysis ?
An analytical method must be chosen for each application. There is no universal method.
This section gives a few indications on how to choose and optimise the analysis methods.
The purpose of our training programs is to detail and explain the information given below
using concrete examples.
4.4.1. Choice of program and choice of lines
"Water" Oil Solvent Salt
condition condition condition condition
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The flowchart below shows how to select a program in the software. A pro-
gram is the set of elements and their parameters that you wish to determine.
Determining the matrix:
In the software and documentation that we provide, a certain number of matri-
ces are listed. If the matrix for the samples to be analysed is known and lis-
ted, simply select the matrix and create an analysis program based on this
matrix.
If the matrix is not known, you will need to use IMAGE (if you have this
option) or the semi-quantitative program to determine the major elements in
order to deduce a matrix. Caution, when this method is used, no information
concerning the acids or organic substances are given.
Search for lines:
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If none of the programmed matrices are appropriate to the samples, you
must search for the appropriate lines.
You can perform a bibliographic study using the books and journals indica-
ted in the appendix or using the library of wavelengths given in the software.
The tables of wavelengths and spectral interferences are also given in the appen-
dix. All of this data must be verified experimentally. In this respect, the inten-
sities depend on the excitation source (frequencies) and this source is specific
to each manufacturer. The values given in the tables are only indications.
Of course, the interferences depend of course on the resolution of the instru-
ment and it is therefore preferable to establish your own interference tables.
As a general rule, for an element at the trace level (concentration inferior to
100 times the limit of detection), choose the most sensitive wavelength and
and a less sensitive wavelength for major elements. Then, depending on the
matrix, study the possible interferences. To do so, make a scan of the line.
This is the "PROFILE" function in the software.
The "Profile" function will allow you to display what is actually happening.
Make a profile of the various mono-element solutions (elements to be analy-
sed and possible interfering elements) at the various analysis wavelengths.
The choice of analysis wavelengths most appropriate to your analytical pro-
blem is made after you have superposed the profiles.
You do not need to systematically use the wavelength giving the best theore-
tical detection limit. The best compromise for the analytical programme should
be sought between the detection limit, stability, interference and the regrou-
ping of wavelength in a Wavelength Analytical View (WAV). There is no "uni-
versal" line for an element.
The choice of lines is made according to the following criteria:
- Desired sensitivity,
- Absence of interference,
- Regrouping lines in a spectrale range (WAV).
A good choice can enhance the analytic speed. With ACTIVA it is not neces-
sary to take the most sensitive and the more classical lines. The global method
has been optimized for a maximum number of lines and a minimum number
of WAV. This method is an aid for lines choice.
4.4.2. WAV criteria
Four possibilities are offered for defining the WAV.
- Automatic mode
- Min mode
- Max mode
- Custom mode
Automatic mode:
Using the Automatic mode, the software will optimize the choice and the width
of the WAVs according to the wavelengths listed in the method.
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Min Mode:
Using the Min mode, the line and its vicinity is measured (+/- X picometers
around the theoretical wavelength value, the X value in pm is set in the
"Instrumental configuration" section). The size of the spectral window is 100
pm in this case, allowing the simultaneous measurement of the peak and the
background.
Max mode:
When Max mode is selected, the full width of the detector is used and mea-
sured ( i.e. 2047 pixels).
Custom mode:
When Custom mode is selected, it is possible to set manually the start and
final wavelength values of the WAV. Theoretical limits are given by the soft-
ware.
Several modes can be used by the line.
The Automatic mode associated with a good choice of the lines enhance
the analytical speed. It can analyse simultaneously several lines and their back-
ground.
4.4.3. Peaks criteria
Four modes are available:
- Max
- Mean
- Gaussian
- ABC
"Calculate points" correspond to the number of points (number of verti-
cal columns of pixels) taken into account for the intensity measurement,
"Display points" correspond to the number of points displayed on the screen.
One point represents the sum of one column of pixels (whatever the binning).
The peak intensity given by the software is normalized to 1 pixel and one
second.
Using the Max analysis mode, and one calculated point, the peak intensity
given by the software corresponds to the maximum pixel intensity measured
around the experimental wavelength position (determined by the peak search).
If n "Calculate points" are used, the average of the n pixel intensities will be
calculated.
Using the Mean analysis mode, and one calculated point, the peak intensi-
ty given by the software corresponds to the pixel intensity measured at the
experimental wavelength determined after the peak search. If n "Calculate
points" are used, the average of the n pixel intensities will be calculated. Usually,
n is an "odd" number.
Nota: in Max and Mean, the number of calculated points n can be fixed
to cover the peak partially or totally; the number of points varies depending
on the lines because the bandpass by pixel change the wavelength for a given
grating; There is an odd number of points.
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Indicatives values of n in function of the wavelength:
< 200 nm n = 1
200 < < 230 nm n = 3
230 < < 300 nm n = 5
300 < < 500 nm n = 7
500 < n = 9
Using the Gaussian analysis mode, the peak intensity corresponds to the
maximum intensity determined after a Gaussian fitting of the peak. The
number of calculated points corresponds to the number of points used for
the fitting. This number has to be high enough in order to obtain a proper
Gaussian fitting.
Using the ABC (Algorithmic Background Correction) analysis mode, the
intensity and the background are determined after a curve fitting. This fitting
is based on a Gaussian fitting per peak, while a parabolic fitting is used for the
background.
Remarks: the Mean and Max modes with several points of calulation are the
most used with a CCD. The ABC mode can be used for a line on a wing of
another line.
In all cases, the intensity of the peak and the background are measured simul-
taneously.
4.4.3. Choice of analysis method
There are five analysis methods.
Classic method: direct calibration.
Standard addition method.
Internal standard method.
Virtual method.
100% method
To choose an analytical method, refer to the table below or the flowchart.
Standard additions Matrix unknown Preparation of at Biological medium
No reference least 4 solutions
No blank for a sample
Internal standard Better instantaneous Element added in Cements, lubricants,
repeatability each sample to be steels, precious
Better accuracy analysed metal
Analytical method Problem to solve/ Constraint Application examples
Desired improvement
Virtual (*) Better instantaneous All elements must Metallurgy
repeatability be known
Better accuracy.
100 % (*) Better repeatability All elements must Metallurgy
Better accuracy for be known
all elements and measured
Classic calibration All other cases
(*) Only used with " Spark ablation " accessory to analyse conductive solids.
4.4.3.1. Direct calibration
Choice of standards
The choice of standards is essential to obtain an accurate analysis. The
standards matrix must be as near as possible to that of the samples to
be analysed. This covers not only the major elements but also the acids
or traces of organic substances present. If the matrix doesnt match
the original one, the power should be slightly increased to lower the
matrix effects.
Number of standards
From a statistical point of view, at least four points are desirable, if
possible, grouped two-by-two. For a greater number of points, it is bet-
ter to group the concentrations into two point clouds.
Calibration
It is better to use the upper part of the calibration curve. On the other
hand, since the uncertainty is a hyperbola with respect to the calibra-
tion line, do not try to extrapolate the line beyond the concentrations
used.
Analytical method Problem to solve/ Constraint Application examples
Desired improvment
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Figure 39: Limits of confidence for a concentration
Weighting
When the concentration region is large (ex 0 - 500 ppm), it becomes
necessary to weight the intensity values (by the inverse of the root
mean deviation). The weighting forces the regression line to pass more
through the low points than through the higher points. The error on
the low concentrations will be less; on the other hand, the error on the
high concentrations will be more (the choice of the coefficient for weigh-
ting is important to lower the errors over the whole range).
4.4.3.2. Standard addition method
The standard addition method is relatively easy to use and can be the
solution for certain special analytical problems encountered in ICP
analysis:
* No standards.
* Presence of matrices which do not allow good results using the clas-
sic calibration methods.
Example: Biological matrices for which it is very difficult to obtain a
"blank".
In this method, the concentration CX of an unknown sample X is obtai-
ned by analysing a solution of the sample with successive additions of
elements to be determined and for which the concentrations are respec-
tively equal to C, 2C, 3C, etc...
The intensities measured are then plotted on a curve as a function of
the concentration.
With ICP plasma emission, when the standard addition method is used,
it is absolutely necessary to take into account the spectral background
and subtract it from the intensities corresponding to the CX, CX + C,
CX + 2C, etc... solutions; the Intensity/Concentration curve is then defi-
ned as a function of the net intensities (raw intensities less background
intensity).
Though the standard addition method is constraining (preparation of
samples), indirect, and requires the correction of the background, it is
nonetheless the most accurate quantification method and sometimes
very useful in special cases indicated above.
Note: The quality of the results basically depends on the precision of
the background correction and then, of course, on the precision of the
successive additions.
There is no point in using standard additions for a complete series of
samples of the same type. If the standard additions have been perfor-
med with a sample, the sample can be used with these additions to
generate the calibration curve.
Let's take, for example, a series of samples of the same type.
First, we search for the Fe, Co, Cr elements. A semi-quantitative analy-
sis gives the concentrations as, respectively: 10 ppb, 1 ppm and 50
ppm.
The additions are made to obtain three other solutions whose concen-
trations are summarised in the table below.
Sample 1 X W Z
Sample 2 X + 10 g/l W + 1 mg/l Z + 25 mg/l
In the method, the following concentrations are entered
Standard 1 0 g/l 0 ppm 0 ppm
Standard 2 10 g/l 1 mg/l 25 mg/l
After the measurement, the ordinate at the origin (BEC) for each ele-
ment corresponds to X, Y and Z (10 ppb, 1 ppm and 50 ppm).
Sample Fe Co Cr
Sample Fe Co Cr
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In the method, the concentrations will then be:
Sample 1 10 g/l 1 mg/l 50 mg/l
This curve could then be used to analyse the other unknown samples
of the same series.
The additions must remain weak to not over-dilute the matrix. If pos-
sible, do not exceed a dilution greater than 5 %.
4.4.3.3. Internal standard method
The internal standard method is used for a higher degree of precision
of the results. The internal standard is an element that is added, at the
same concentration, to the calibration solutions and in the samples to
be analysed.
The typical concentration of the internal standard is 1 to 10 ppm.
Fluctuations due to variations of the plasma (temperature, generator
efficiency, gas, introduction of samples) cause the intensity of the ele-
ments measured to vary in the same proportion as that of the internal
standard. As a result, the ratio of intensities will remain relatively cons-
tant.
The internal standard must be selected according to the following cri-
teria:
- must not be present in solution,
- must not create spectral interference,
- must not add impurities,
- must be chemically compatible with the samples,
- must have a similar behaviour with respect to fluctuations of the
element to be corrected,
- must be analysable, meaning a polychromator slit has been provi-
ded for the line, or can be analysed on the additional monochro-
mator (H20).
This choice is very tricky. There is no universal element that can be
used for all situations. Generally, for lines I (atomic lines), an inter-
nal standard with an analysis line I is chosen. For lines II (ionic lines),
a line II of the internal standard must be analysed.
The concentration of the internal standard and the photomultiplier tube
high voltage adjustment must be such that the ratio of the intensities is
not too far from the value 1 for the major elements.
Fe Co Cr
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Yttrium and Scandium are commonly used elements.
Caution: Correct use of an internal standard will provide a very sharp
improvement in the results (reproducibility improved by a
factor of 2 or 3); an incorrect choice will deteriorate the
results by a similar factor.
4.4.3.4. Virtual method
The virtual method is used when the internal standard does not have a
constant concentration. A curve is defined between the ratio of inten-
sities and the ratio of concentrations (element / standard). However,
this method is only applicable following mineralisation of a solid where
all the elements are found in the solution.
This method is not very frequently used in ICP analysis.
4.4.3.5. 100 % method
This method, like the virtual method, requires total mineralisation of a
solid. There is no internal standard measurement. Here, we simply consi-
der that the sum of the concentrations in percentage should be 100%.
4.4.4. Analytical optimisation.
The analytical optimisation must be carried out for each application, for exam-
ple, to determine the metals present in drinking water or to determine K, Na,
P, S in soils.
To better understand this section, read, or reread, sections 4.2 " Plasma opti-
misation", 4.3 " Analytical conditions ", 4.4.1 " Choice of program, choice of
lines" 4.4.2. " Acquisition mode " and 4.4.3 " Choice of analysis method ".
The table below summarises the various steps.
1 Sample Sample, elements to See 2.3.
preparation determine
2 Sample Matrix See 3.2.3.
introduction
system
3 Generator Matrix See 4.2.
power
4 Cooling gas, Matrix See 4.3.
auxiliary gas
5 Sheath gas Alkaline (or not) element See 4.2.
salinity of solution
6 Peristaltic pump Nebulizer and capillary See. 4.2.
speed
Step Parameter Depends on Optimisation
criterion
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7 Nebulisation Nebuliser See 4.2.
pressure
8 Wavelength Resolution See 4.4.1.
Regrouping of lines
9 Acquisition See 4.4.2.
mode Expected concentration
10 Integration Acquisition mode See. 4.2.
time
11 Analytical Knowledge of matrix, See 4.4.3.
method presence of major element
12 Standard choice Desired accuracy See. 4.4.3.1.
Minimization of uncertainty
on the analytical result
Example: Analysis of certified reference material: NIST 1640.
The table below gives the list of elements to be determined and their concen-
tration.
Ag 0.00762
Al 0.052
As 0.02667
B 0.3011
Ba 0.148
Be 0.03494
Ca 7.045
Cd 0.02279
Co 0.02028
Cr 0.0386
Cu 0.0852
Fe 0.0343
K 0.994
Li 0.0507
Mg 5.819
Mn 0.1215
Mo 0.04675
Na 29.35
Ni 0.0274
Pb 0.02789
Sb 0.01379
Se 0.02196
Si 4.73
Sr 0.1242
V 0.01298
Zn 0.0532
Element Concentration (mg/L)
Step Parameter Depends on Optimisation
criterion
Step 1: Preparation of sample.
The samples do not need any special preparation as they are already in solu-
tion. However, for better stability, a slight acidification is desirable (1 % HNO
3
).
Step 2: Sample introduction system.
The matrix is a water matrix with little salt content. Here, we have decided to
determine the trace and major elements. The most appropriate system for
introducing the sample is the glass concentric nebulizer with a cyclone spray
chamber.
Step 3: Generator power.
The matrix contains little salt. It is constant from one sample to another. A
power of 1000 W is therefore appropriate.
Step 4: Cooling gas and auxiliary gas.
The water analysis uses the classic values, meaning a cooling gas flow of
12 l/min, and no auxiliary gas (water matrix).
Step 5: Sheath gas.
For potassium (K), a strong sheath gas is used (1 l/min). For sodium (Na),
there is no need to use a strong sheath gas since the expected concentrations
are high. For the other elements, a weak sheath gas of 0.1 l/min. is used.
There is no point in increasing this value since the solution has little salt content
and this would result in a loss of sensitivity.
Step 6: Peristaltic pump speed.
Classic speed for a glass concentric nebulizer: around 1 ml/min. (20 rpm).
Step 7: Nebulization pressure.
This is the pressure of the nebulizer used. This does not depend on the appli-
cation. The pressure is determined by plotting the curves, showing the ratio
of Mg and the signal/background ratio of the Mg as a function of the nebu-
lization pressure. Apply a pressure such that the ratio of Mg is greater 6 than
8 and the signal/background ratio is as high as possible. For this type of
nebulizer, the pressure is around 3 bars.
Step 8: Wavelength.
The choice of wavelength is made considering the concentration of each ele-
ment and the regrouping of the wavelength in the WAV.
Several lines per element are used because these lines already belong to the
WAV and it costs no more time and gives more information.
Ag 328.068
Al 167.020
308.215
394.401
396.152
As 188.983
193.695
Element Wavelength (nm)
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B 182.529
208.959
249.678
249.773
Ba 230.424
Be 249.454
Bi 190.178
222.825
223.061
306.772
Ca 315.887
317.933
Cd 214.438
228.802
Co 226.616
238.892
Cr 205.552
206.149
Cu 213.598
324.754
Fe 238.204
239.562
Ga 294.364
Ge 219.873
303.906
Hg 194.163
K 766.490
Li 670.784
Mg 279.079
279.806
Mn 280.106
293.306
Mo 202.030
204.598
Na 588.995
589.592
Ni 231.604
232.003
P 178.229
213.618
214.914
Pb 168.155
220.353
S 180.676
181.978
Sb 217.581
Se 196.026
Si 212.412
221.667
Sn 189.930
Sr 215.284
216.596
Te 214.281
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Ti 323.904
324.199
336.121
Tl 190.800
V 292.402
327.612
W 224.551
Zn 202.551
206.200
Zr 327.305
Step 9: Analysis mode and integration time
Ag 328.068 Automatic 5
Al 167.020 Automatic 3
308.215 Automatic 5
As 188.983 Automatic 3
193.695 Automatic 3
B 182.529 Automatic 3
208.959 Automatic 3
249.678 Automatic 3
249.773 Automatic 3
Ba 230.424 Automatic 3
Be 249.454 Automatic 3
Ca 317.933 Automatic 5
Cd 228.802 Automatic 3
Co 228.616 Automatic 3
238.892 Automatic 3
Cr 205.552 Automatic 3
206.149 Automatic 3
Cu 324.754 Automatic 5
327.396 Automatic 5
Fe 238.204 Automatic 3
239.562 Automatic 3
K 766.490 Automatic 7
Li 670.784 Automatic 7
Mg 279.079 Automatic 2
279.806 Automatic 3
Mn 280.106 Automatic 3
293.306 Automatic 3
Mo 202.030 Automatic 3
Na 588.995 Automatic 7
589.592 Automatic 7
Ni 231.604 Automatic 3
Element Wavelength Acquisition Number of points Integration
(nm) mode for calulation time (s)
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Pb 220.353 Automatic 3
Sb 217.581 Automatic 3
Se 196.026 Automatic 3
Si 212.42 Automatic 3
Sr 216.596 Automatic 3
V 292.402 Automatic 3
327.612 Automatic 5
Zn 206.200 Automatic 3
Step 10: Analytical method.
The matrix is known and reproducible, the simplest method can be used: direct
calibration (standards made in 1 % HNO
3
)
Step 11: Choice of standards.
The concentration ranges are defined in the table below. We will choose to
use 4 calibration points; two with weak concentrations and two with high
concentrations.
4.4.5. Method validation
Various methods can be used to validate an analytical method.
1. Certified reference materials.
2. Participation in inter-laboratory tests.
3. Analysis of control samples.
Validation of a method can be preceded by the validation of the instru-
ment by the " Diagnostic " method.
For more details, refer to "Validation of analysis method" by Max Feinberg
(section 7.1.4.) or come to the HORIBA Jobin Yvon training.
4.7.6. Semi-quantitative analysis
The semi-quantitative analysis allows to determine 38 elements and 69 lines.
No special software is required.
It can be modified for specific applications.
4.7.6.1. Wavelengths
Al 167.020
308.215
394.401
396.152
As 188.983
193.695
B 182.529
208.959
249.678
249.773
Ba 230.424
Be 249.454
Bi 190.178
222.825
223.061
306.772
Ca 315.887
317.933
Cd 214.438
228.802
Co 226.616
238.892
Cr 205.552
206.149
Cu 213.598
324.754
327.396
Fe 238.204
239.562
Ga 294.364
Ge 219.873
303.906
Hg 194.163
K 766.490
Li 670.784
Mg 279.079
279.806
Mn 280.106
293.306
Mo 202.030
204.598
Element Wavelength (nm)
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Na 588.995
589.592
Ni 231.604
232.003
P 178.229
213.618
214.914
Pb 168.155
220.353
S 180.676
181.978
Sb 217.581
Se 196.026
Si 212.412
221.667
Sn 189.930
Sr 215.284
216.596
Te 214.281
Ti 323.904
324.199
336.121
Tl 190.800
V 292.402
327.612
W 224.551
Zn 202.551
206.200
Zr 327.305
The use of several lines for one element allows to enhances the concentra-
tion range useable and to identify some problems (spectral interference, bad
position of the background) in case of the results of two lines are different
for the same element.
4.7.6.2. WAV and measurement mode
The semiquantitative method has 38 elements, 69 lines and 18 WAV. The
Automaticmode is used for all lines. The number of points of calculation
depends on the wavelength:
- 3 points for wavelength below 300 nm
- 5 points for wavelengths between 300 and 500 nm
- 7 points for alkalin elements
The mode use is fast speed with and integration time of 0.3 seconds in case
of high concentration instead of 1 seconde.
Figure 40: Example of WAV
The figure shows a 4.5 mm WAV for the simultaneous analysis of 10
analytical lines and their background.
4.4.7. Analysis of organic substances
4.4.7.1. Preparation of samples
An organic sample must be diluted in a solvent. Various possibilities
exist. Below is the most widely used methodology.
Dilution to 10 % by weight:
Take 10 g of the sample.
Make up to 100 g with solvent.
For the standards.
Weigh the standard to obtain the desired concentration.
Make up to 10 g with base oil (clean oil).
Make up to 100 g with solvent.
The solvent is either a petroleum ether or xylene. Xylene is a better sol-
vent, but toxic and sometimes prohibited in laboratories; it also requi-
res more power and cooling gas.
Caution: The solvent or base oil often contains significant blank levels
particularly in Sulphur. Always measure a blank profile for
all the elements to verify for presence or absence of conta-
mination.
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4.4.7.2. Typical operating conditions
The classic operating conditions of a plasma in an organic medium are
given below:
Generator power 1200 W
Cooling gas flow 15 l/min
Auxiliary gas flow 0.8 - 1.2 l/min
Sheath gas flow 0.2 l/min
Nebulization gas flow 0.8 l/min
Nebulization pressure 2.5 bars
Sample flow 1.5 ml/min
Nebulizer Jobin-Yvon 0.7 mm ou 1 mm
Pump tube :
Solflex tube (translucent yellow) supplied by 12
Viton tube supplied by 4. Stronger tubes, but more costly.
Caution: Never use an argon humidifier.
4.4.7.3. Adjusting an organic plasma.
Plasma ignition
Attempt to ignite the plasma under the conditions detailed in the table
above.
If the plasma blows, proceed as follows:
- Increase the flow of cooling gas to 18-20 l/min.
- Increase the generator power to 1400 W if possible.
- Supply an auxiliary gas at 0.4 l/min.
- Supply a sheath gas at 0.5 l/min.
- Set the sample flow (peristaltic pump speed) for 0.
- Close the nebulization pressure
- Ignite the plasma.
- Gradually increase the sample flow (peristaltic pump) to its rated value.
- Allow the plasma to stabilise for a few minutes.
- Gradually increase the nebulization pressure to its rated value.
- Decrease the flow of auxiliary gas down to its rated value.
- Decrease the sheath gas down to its rated value.
- Decrease the cooling gas flow and power.
If the injector builds up a carbon deposit, proceed as follows:
- Remove the torch and clean it by blowing with compressed air.
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- Ignite the plasma again.
- Readjust the auxiliary and sheath gas flows.
A decrease in sheath gas drives the plasma to the torch.
An increase in the auxiliary gas results in separation of the plasma base
from the inner torch tube.
Adjusting the plasma
The plasma must comply with the diagram below.
For this purpose, mainly optimise the nebulization flow and pressure and
the sheath gas within 0.1 - 0.3 l/min.
Figure 41: Organic plasma
The higher the nebulization flow, the higher the sensitivity.
The lower the sheath gas flow, the higher the sensitivity.
Expected results
With respect to an ICP instrument in a water medium, the BECs and the-
refore the detection limits will be around 3 to 5 times higher.
4.4.8. To ignite a plasma with an unusual solvent (very volatile)
If an "unusual" solvent, mainly an organic solvent, causes the plasma to blow
out when introduced, proceed as follows:
- Increase the cooling gas flow to 18-20 l/min.
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- Increase the generator power to 1400 W if possible.
- Supply an auxiliary gas at 0.4 l/min.
- Supply a sheath gas at 0.5 l/min
- Set the sample flow (peristaltic pump speed ) for 0.
- Close the nebulization pressure.
- Ignite the plasma.
- Gradually increase the sample flow (peristaltic pump) to its rated value, if
possible.
- Gradually increase the nebulization pressure to its rated value, if possible.
- Decrease the auxiliary gas flow down to its rated value.
- Decrease the sheath gas flow down to its rated value.
- Decrease the cooling gas flow and power.
The classic operating conditions of a plasma in an organic medium are given
below:
Generator power 1200 W 1400 W
Plasma gas flow 15 l/min 18 l/min
Auxiliary gas flow 0.8 - 1.2 l/min 0.2 - 0.6 l/min
Sheath gas flow 0.2 l/min 0.4 - 0.5 l/min
Nebulizer gas flow 0.8 l/min 0.2 - 0.4 l/min
Nebulization pressure 2.5 bars 1 bar
Sample flow 1.5 ml/min 0.2 - 0.5 ml/min
Nebulizer Jobin-Yvon 0.7 mm Jobin-Yvon 0.7 mm
or 1 mm or Cross flow or
Meihnard
Pump tube:
Solflex tube (translucent yellow) supplied by 12
Viton tube supplied by 4. Stronger tubes, but more costly.
Caution: Never use an argon humidifier.
If the injector builds up a carbon deposit, proceed as follows:
- Remove the torch and clean it by blowing with compressed air.
- Ignite the plasma again.
- Readjust the auxiliary and sheath gas flows.
A decrease in sheath gas drives the plasma to the torch.
An increase in the auxiliary gas results in separation of the plasma base from
the inner torch tube.
Oil diluted in Volatile solvent
kerosen
5. Accessories
5.1. Classical hydride generator (Other: CMA, see 5.3)
This method consists in forming hydrides of elements such as As, Bi, Hg, Sb, Se,
Sn, Pb which, being volatile, are easily transported by the argon to the plasma. The
increase in sensitivity will be, for these elements, between 5 and 20 %.
The hydrides are created by the reaction of sodium tetraborohydride on hydrochloric
acid.
En+
NaBH
4
+3 H
2
O + HCl ------ H
3
BO
3
+ NaCl + 8H ---------- EHn + H
2
( excess)
Where E corresponds to the analyte.
The system comprises:
- Two peristaltic pumps with one channel (or a two-channel pump),
- A polypropylene Tee,
- A liquid/gas separator,
- A torch.
The last three parts are mounted on a cassette.
The sodium borohydride and the acid solution are pumped and mixed in a Tee where
the reaction takes place. All the products are then sent to the liquid/gas separator.
The argon carries the gaseous substances, hydrogen and hydrides, to the torch while
the drain removes the excess liquid (H
2
O, elements not generating hydrides, etc.).
Installation
1. Carefully remove the cassette from its package since the glass parts are very fra-
gile.
2. Check that the various connections along the liquid path are tight.
Pumping a demineralised water solution for a few minutes can complete this
check.
Tightening the joints can eliminate all leaks. Caution, do not over-tighten the
joints on the glass parts.
3. Assemble the two parts of the gas/liquid separator using the clip supplied.
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4. Connect the assembly to the ICP torch.
Preparation of reagents and samples.
Sodium tetraborohydride III solution (NaBH
4
).
Dissolve solid NaBH
4
in a solution of NaOH 1 M to obtain a final solution of 1 %
by weight (1 g in 100 ml).
The solution should then be filtered. In these conditions, it is stable for about one
day, kept far from any source of heat, then gradually it looses its reducing power.
Samples
The solutions must not contain particles that could obstruct the pump capillary tubes;
we recommend that you filter the solutions through a filter paper.
All the standards, blanks and samples to be analysed must be prepared in an HCl 1
to 6M medium to easily produce hydrides. Other mediums can also be used.
Caution: If the NaBH
4
solution is stored in a plastic bottle, check that the cover
is not too hermetically sealed. This solution breaks down slowly, relea-
sing hydrogen that could cause the bottle to explode. The reagents used
are corrosive and flammable. Be sure to take all the usual precautions
when handling these types of substances.
Cleaning the glassware
The liquid should arrive regularly into the gas/liquid separator. For this purpose, we
recommend that you degrease the separator before use by any detergent solution
used in the laboratory, and rinse with demineralised water. This rinsing should be
repeated if necessary.
Procedure.
1. The gas conditions are as follows:
Cooling gas flow: 12 l/min.
Sheath gas flow: 0.4 l/min.
Carrier gas flow: 0.6 l/min. for a pressure of 1.5 bars.
2. Set up the two solutions: acid solution and reducing solution.
3. Switch on the pumps:
Sample flow: 0.5 to 2 ml/min.
NaBH
4
flow: 0.5 to 1 ml/min.
4. Wait a few moments for the flows to arrive at the mixing chamber.
5. Carefully observe the flows, in particular, formation of bubbles and surplus
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liquid in the gas/liquid separator.
The liquid levels in the two arms of the U-tube should be stable. This indica-
tes a stable flow of liquid to the drain and a stable formation of the gaseous
product.
6. Before igniting the ICP, stop hydride generation (pump and argon flow).
7. After starting, slowly introduce the hydrides until you have obtained stable condi-
tions.
Maintenance.
To obtain good results, appropriate maintenance is required.
Do not forget to regularly change the pump tubes. Since the solutions are corrosi-
ve, the tubes deteriorate rapidly and a variation in their physical properties will have
an impact on the chemical reaction. The tubes can be changed. However, the new
capillary tubes must be thermoformed.
All the glass parts must be regularly cleaned. At the end of each analysis, before stop-
ping the plasma, all the circuits must be rinsed with demineralised water.
Solutions are pumped Check capillary tubes.
Basic signal very noisy Clean glassware and add wetting
agent to NaBH
4
(Brij 35 for example).
No signal 1. No pumping
2. Sample not acidified
3. No liquid in U-tube. Stop carrier gas for
a few moments to fill U-tube again.
Problem Corrective action
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Figure 42: Hydride Generator
To successfully generate hydrides:
- All the elements must be in their lowest state of oxidation. Use a pre-reduction
phase if necessary. As and Sb can be reduced by potassium iodide KI 10 %. The
Se can also be reduced by KI, but in a very acid medium (5M HCl).
- The acid content of the solution is an important factor. The Ge and Sn are only
reduced at concentrations of hydrochloric acid between 0.05 M and 0.1 M. As,
Sb, Se and Bi are reduced over a large range of concentrations (0.5 to 2.0 M).
In general, HCl 3 M or HNO
3
3M are used for the common elements: Hg, As
and Se.
- The nebulization pressure is very important. This is an optimisation parameter.
- Numerous elements can interfere with hydride generation. Each type of sam-
ple requires a feasibility study.
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5.2. " Concomitant Metals Analyzer " CMA
The CMA is a hydride generator used to improve the sensitivity of elements crea-
tingh hydrides and Hg by a factor of 7 to 30 and at the same time analyze "normal"
non hydrides elements.
This system provides the following advantages with respect to a classic hydride gene-
rator.
1. Analysis can be performed in one analytical run of the elements forming hydri-
des and "normal" others.
2. Does not require prior acidification of the samples.
3. No change of cassette.
4. Improve productivity for total analysis time.
Hydrides are created by the reaction of the sodium tetraborohydride on the hydro-
chloric acid.
En+
NaBH
4
+3 H
2
O + HCl ------ H
3
BO
3
+ NaCl + 8H. ---------- EHn + H
2
( in excess)
Where E corresponds to the analyte.
Figure 43: CMA chamber, principle
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The system comprises:
- A specific spray chamber, CMA type,
- Capillary tubing 2.5 m (67 119 033),
- Peristaltic pump tubes
Black-White for drain (46 791 030)
Grey-Grey for reactives (46 791 018)
Black-Black for sample and acid (46 791 022)
- A double head pump.
The sodium borohydride and the acid solution are pumped by a peristaltic pump
and mixed in the chamber where the reaction takes place.
The gaseous products, hydrogen radicals and hydrides, as well as the aerosol, are
driven by the carrier argon to the torch while the excess liquid is evacuated by the
drain.
The integrated pump is used to pump the drain and bring the sample.
Installation
1. Check that the various connections along the liquid path are tight.
This check can be completed by pumping a solution of demineralized water for a
few minutes.
2. Connect the assembly to the ICP torch.
Preparation of reagents and samples
Sodium tetraborohydride III solution (NaBH
4
).
Dissolve solid NaBH
4
in a solution of 0.5 M NaOH to obtain a final solution of
1 % w/v (1 g in 100 ml).
The solution should then be filtered. In these conditions, it is stable for about one
day, kept far from any source of heat, then gradually looses its reducing power.
Note: If kept in a refrigerator, the solution will stay stable longer.
Samples
The solutions must not contain particles which could obstruct the pump capillary
tubes; we recommend that you filter the solutions through a filter paper.
Acid solution
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The optimum concentration is between 0.5 M and 6 M depending on the element.
Hydrochloric acid is the best acid, 2 M HNO
3
can also be used, a loss of signal will
result HNO
3
is an oxidizing agent, so the reduction process may not happen. Avoid
all oxidizing agents if possible. Avoid using H
2
SO
4
and HCLO
4
, these are extreme-
ly strong oxidizing agents and prevent the reduction reaction to proceed. In gene-
ral, 2 M HCl is used.
Caution: If the NaBH
4
solution is stored in a plastic bottle, check that the
cover is not too hermetically sealed. This solution breaks down slo-
wly, releasing hydrogen which could cause the bottle to explode. The
reagents used are corrosive and inflammable. Be sure to take all the
usual precautions when handling these types of substances.
Procedure
1. The gas conditions are as follows:
Plasma gas flow: 12 l/min.
Sheath gas flow: 0.2 l/min.
Carrier gas flow: 0.8 l/min for a pressure of 3 bars. (45 psi)
2. Set up the two solutions: acid solution and NaBH
4
reagent.
3. Switch on the pumps (both ICP and separate pump, respectively 20 rpm and 10
rpm):
Sample flow: 1 ml/min.
NaBH
4
flow: 1.2 ml/min.
Acid flow: 0.6 ml/min
Drain flow: up to 12 ml/min.
4. Wait a few minutes for the flows to reach the mixing chamber and equilibrium
to occur.
5. Carefully observe the flows, in particular for formation of bubbles and surplus
liquid in the lower part of the chamber.
6. Before igniting the ICP, stop the hydride generation (pump and argon flow).
7. After starting up, introduce the hydrides until you have obtained stable condi-
tions.
Maintenance
To obtain good results, appropriate maintenance is required.
Do not forget to regularly change the pump tubes. Since the solutions are corrosi-
ve, the tubes deteriorate rapidly and a variation in their physical properties will have
an impact on the rate of chemical reaction and thus the stability. At the end of each
analysis, before extinguishing the plasma, all sample introduction systems must be
rinsed with deionized water for a few minutes.
Solutions are not pumped Check pump capillary tubes and pressure
on pump.
Base signal very noisy Clean glassware and poor drainage.
No signal Check solutions taht are being pumped
Parameters for hydride generation
Oxidation state
All the elements must be in their lowest state of oxidation except Se which must be
in the SeIV state. Use a pre-reduction phase if necessary. As and Sb can be reduced
by potassium iodine KI 10 %. Se can also be reduced by KI, but in a very acid medium
(5M HCl), be careful not to reduce too strongly to SeII.
Acid concentration
The acid content of the solution is an important factor. The Ge and Sn are only redu-
ced at concentrations of hydrochloric acid between 0.5 M and 1 M. As, Sb, Se and
Bi are reduced over a large range of concentrations (0.5 to 2.0 M).
Nebulizer pressure
The nebulization pressure is very important. This is an optimization parameter.
Chemical interference
Numerous elements can interfere with hydride generation. Each type of sample requi-
res a feasibility study, for example, Se cannot be determined in the presence of Cu.
Purity of reagents
All reagents must be of highest quality, contamination will cause errors, and loss of
limit of detection.
Memory effects
Hydride generation uses the previously mentioned chemical reaction. If high concen-
trations are used, memory effects will be encountered. For this reason, for low level
work, use low level standards (ie 50 ppb). If high level work is required (ie up to 5
ppm), allow several minutes before calibration on the blank is performed. Hg is noto-
rious for its memory effect. The storage vessel is very important especially for Hg.
It has been shown that the addition of 10 ppm of Au will decrease the memory
effects of Hg. If used, Au must be added to samples, blank, rinse and standards alike.
Problem Corrective action
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Figure 44: "CMA" chamber
5.3. Argon Humidifier
5.3.1. Principle
The argon humidifier saturates the argon with humidity the gas of nebulization of
the nebulizer. To analyse water solutions with high salt concentration, > 5 g/L, an
argon humidifier is recommended. The humidifier is mounted ahead of the argon
inlet in the nebulizer.
The humidifier strongly reduces the risks of clogging at the nebulizer.
Its operating principle is explained below.
Caution: Do not use for organic solutions.
Figure 45: Argon humidifier, principle
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5.3.2 Filling the humdifier
Unscrew the cap (ref: 90 550 045).
Fill with distilled water.
Screw the cap back into position.
For optimum operation, the membrane should be in water (red line corresponds
to the minimum water level).
An absence of water will not damage the membrane, however the correct func-
tion will not occur and it will not function correctly.
5.3.3. Use
This argon humidifier can be install on all ICP spectrometers.
The connection is direct in the nebulizer gas line with rapid connectors.
Verify regularly the water level, at least once a month.
Take care: the nebuliser pressure shouldnt exceed (72.5 PSI).
Fifure 47: Argon humidifier schematic
5.3.5. Membrane change
The seal (46 000 6378) has to be screwed with care into the body 31 034 269
for a good seal.
Please take care of the tubes and ring mounting as indicated below.
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Figure 47: Membrane change
Take care: respect the way of winding the membrane coil.
Figure 49: Dismounting the membrane
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5.4. Sample handler
A sample handler can be used with our spectrometers. This device makes it possi-
ble to process a large number of samples quickly without operator intervention.
The handler is equiped with USB for more flexibility, and higher speed for various
applications.
It is equipped with a plastic tray with 4 racks chosen among several possibilities.
Several options are available such as the rinsing station.
In case of nocive vapors, an extraction system can be proposed. This sampler and
its tray are anti-corrosion treated.
The ICP ACTIVAnalyst software allows the complete control of the AS 500 sam-
pler connected to the ICP.
Figure 50: Sample handler JY AS 500
Available racks:
Part Number Number of positions External diameters of tubes
44 820 099 21 pos 30 mm
44 820 098 24 pos 25 mm
44 820 040 40 pos 20 mm
44 820 060 60 pos 16 mm
44 820 090 90 pos 13 mm
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These racks are in plastics.
5.5. Dilution system
Principle
This system is used to dilute solutions (generally organic) without them going through
a tube.
The system dilutes the sample where it is picked up.
Figure 51: Dilution system
The pump P1 injects the solvent in the outer tube. The solvent runs through the tube
up to the sample. At this point, the sample is taken up into the inner tube by pump
P2. Pump P2 having a higher flow than pump P1, takes up a certain quantity of
sample with the solvent.
If the flow of pump P2 is D and the flow of pump P1 is d (d < D), the dilution
ratio obtained is:
(D-d)/D
This system can be used with two separate peristaltic pumps, each adjustable in speed.
The system can also be used with a single pump equipped with several heads. In this
case, it is significantly trickier to adjust the dilution ratio as you are required to use
different sizes of pump tubing.
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Figure 52: Diluter needle
"Diluter" needle adjustment procedure
This is a "successive approach" procedure. The aim is to obtain the best intensities
by manual and automatic dilution.
1. Obtaining comparison values with a manual dilution.
- Preparation of samples (base oil and samples) to define dilution factor before-
hand.
- Run the samples for analysis.
Record the relative intensities of the elements in the samples and their instanta-
neous variation coefficients
2. Adjustment of peristaltic pump speeds.
Up to now, the system operates with two peristaltic pumps.
This adjustment is performed in accordance with the defined dilution factor and
the viscosity of the samples.
Example:
Oil Nyco 13 B Used diesel motor oil
Speed (v" 3 cst) (v from 15 to 20 cst)
Solvent pump 50 480
Nebulizer pump 500 540
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3. Adjustment of distance between two ends of internal and external needles ("d")
Figure 53: Dilution needle adjustments
Example:
Dilution to factor 10 of used train motor oil in kerdane.
- For d 2 mm, the kerdane tends to diffuse itself in the sample.
Figure 54: Solvent diffusion
- It is therefore necessary to gradually increased until no more diluent comes out
toward the sample.
- At the same time, check that the mixture of the diluent (colourless) and oil (dark
colour) is roughly uniform in the Teflon capillary tube linking the system to the
nebulizer (slightly transparent).
Avoid the following situation:
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4. Fine adjustment of pump speed and distance d to roughly obtain the same
values for intensity and variation coefficient as in the case of a manual dilution.
5.6. Spark ablation
The ICP is an ideal technique for liquids, but is not suited to direct analysis of
solids. To overcome this drawback, various introduction systems have been develo-
ped. We saw earlier that the "HJY" nebulizer allowed introducing suspended solid
particles in the plasma. For conductive solid samples, a spark ablation device has
been developed.
A spark is created between the sample and a counter-electrode. A gas (argon) car-
ries the particles removed to the plasma torch.
The plasma completes the mineralisation, excites the atoms, and the light emitted is
analysed by the spectrometer.
Direct analysis of solids is therefore possible. The calibration curves are linear.
With spark emission, the calibration curves are rarely linear.
Typical applications: steels, aluminium, copper alloys, iron, brass
Figure 55: Spark ablation
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5.7. Nitrogen generator
Necessary to analyse wavelengths of less than 200 nm.
A nitrogen generator can be used.
A nitrogen generator provides the following features:
- Low-cost production of nitrogen,
- Permanent rinsing of the spectrometer,
- Purity better than 99.999 % for a flow of 1.5 to 6 l/min. depending on the model,
with an outlet pressure of 5 bars,
- Eliminates the need to handle nitrogen bottles that are hazardous.
The system requires: A 220 V, 50 Hz electric power supply.
Models without a built-in compressor:
Compressed air, with constant pressure of 6 to 9 bars, in observance of standard
ISO 8573-1 class 1.2.1., meaning:
Water, dew point: - 40 C.
Oil concentration: less than 0.01 mg/m3.
No particles greater than 0.1 m.
Average flow depending on models, 20 to 120 l/min.
Models with a built-in compressor:
Only an electric power supply is required.
Several models are available. Contact us.
Options and accessories:
Options are available: compressor with higher flow rate, important for purging, and
the possibility for an automatic transition on bottle or gas system in the event of a
problem.
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Figure 56: Nitrogen generator
6. Maintenance
6.1. Correct operation diagnostic
The method described below will allow you to validate correct operation of a sequen-
tial spectrometer by a very fast test. If a problem is detected, the test will indicate
the probable sources.
For more information concerning this method, we recommend that you contact us
for our specific training courses.
The elements used are Ar, Ba, Zn, Mg. The solution used is Ba, Zn, Mg at 5 ppm
in nitric acid 5 %. This solution is stable for several months.
Creating the method.
Create a method using the following lines, the high voltage for each element is
ideally 520 V, gain 2. If saturation occurs, lower the high voltage checking that the
two Mg lines have the same voltage.
Zn 206.191 nm
Ba 233.527 nm
Mg 280.270 nm
Mg 285.213 nm
Ar 404.200 nm
Ba 455.403 nm
Apply the usual operating conditions.
Perform a peak search.
Generate a profile to set a background correction per element.
Using the method
Generate a profile
Perform an analysis of 5 replicas.
Note: Never perform calibration, always work with net intensities.
Interpreting results
The software records all the measurements described in the table below. On the other
hand, the results are processed sequentially, following the logical order described
below. For example, there is no point in verifying the optical transfer if the energy
transfer is not correct.
Ba II 233 nm profile UV Resolution UV Dispersive system
Ba II 455 nm profile Visible Resolution
Mg II 280/Mg I 285 Energy transfer Generator
Background 455 nm/ Dirty optical system Collimation
Background 233 nm
Mg I 285 nm/adjacent Nebulizer efficiency Nebulization
background
Mean of RSDi Nebulizer repeatability
Ba II 233 nm Detection limit ICP system
Zn II 206 nm Detection limit
A result is considered as correct when it fluctuates little with respect to the prece-
ding values. To determine the "correct" values for your spectrometer, perform the
test daily over a period of a month and fill in the table below.
Line and test Measurement Component
tested
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Resolution
Energy transfer
Optical transfer
Nebulizer efficiency
Nebulizer repeatability
Detection limit Zn
Detection limit Ba
The control limits are defined, for example, by the average 2 standard deviations.
Relative standard deviations (RSD %) of less than 10% for the energy transfer, the
optical transfer, and the efficiency of the nebulizer are perfectly acceptable, based
on our experience.
List of main malfunctions
The main malfunctions are listed below. The following flowcharts describe the checks
to be performed in the event of a non-compliant result in order to isolate the cause
of the problem.
Resolution
Change of laboratory temperature.
Change of spectrometer temperature.
Misalignment of an optical component.
Energy transfer
Power setpoint error.
Change in power indication.
Deterioration of generator.
Increase in reflected power.
Variation of coil geometry.
Variation of viewing height.
Change of flow of cooling gas.
Mean Sigma RSD (%) Control limit
Change of flow of sheath gas.
Change of flow of aerosol gas.
Change of position of torch.
Devitrification of torch outer tube.
Partial clogging of injector.
Optical transfer
Deposit on entrance optics.
Viewing through external tube of torch.
Nebulizer efficiency
Partial clogging of nebulizer.
Deterioration of nebulizer tip.
Partial clogging of capillary tube.
Pump capillary tubes in poor condition.
Inappropriate pump speed.
Aerosol gas leak (argon humidifier)
Variation of temperature of spray chamber.
Torch horizontal alignment.
Nebulizer repeatability
Integration time too short.
Pump rollers of poor quality.
Pump tubes in poor condition.
Chamber soiled.
Gas pressure too low.
Photomultiplier tube black current high after passage of an intense signal.
Drain instability.
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Figure 57: Diagnostics: resolution
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Figure 58: Diagnostic: enrgy transfer (1)
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Figure 59: Diagnostic :energy transfer (2)
Figure 60: Diagnostic: optical transfer
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Figure 61: Diagnostics: nebulization system
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6.2. Servicing operations
6.2.1. Main preventive maintenance tasks and frequency
The table below gives the main preventive maintenance tasks to be perfor-
med by the user.
Begining of day Check the pump tubes and change them if
necessary.
Each day Clean the nebulizer using a clean solvent
(acidified demineralised water or organic solvent)
for ten minutes before switching off the plasma,
then pass air to dry capillary tube.
After shut down Cancel the pressure on the pump capillary tube.
Each week Clean the torch.
Every 50 hours Clean the nebulizer, spray chamber and injector.
Every 3 months Verify the drain circuit.
Every 6 months Verify the torch o-rings and replace them if
necessary.
6.2.2. Maintenance of glass concentric nebulizer
The glass concentric nebulizer is the most frequently used. It provides high
sensitivity but its weak point is that it clogs frequently with samples contai-
ning particles.
Utilisation conditions:
If the solutions precipitate slightly, filter the solutions or adjust the pH. Particles
and polar colloids, such as silica, peptides and heavy metal hydroxides
tend to agglomerate on the polar surface of the glass resulting in obstructions.
Carefully rinse the nebulizer between each solution or at least before stop-
ping the plasma.
Rinse with low pH after passing a solution with low pH.
Rinse with high pH after passing a solution with high pH
Do not use an ultrasonic cleaning method. Vibrations can occur in the capilla-
ry tube, resulting in sintering of the end of the nebulizer and reduced effi-
ciency.
Cleaning the nebulizer
Frequency:
Every day, clean the nebulizer without disassembling.
Frequency Task
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Every week, disassemble and clean the nebulizer.
Each time you wish to analyse traces after analysing majors, disassemble and
clean the nebulizer.
When so required by the " Diagnostic " test, disassemble and fully clean the
nebulizer.
Materials required:
Solvent: nitric acid 5 % v/v or any other solvent.
Very thin wire.
Procedure:
Cleaning without disassembly of nebulizer.
At the end of the day, nebulise using a solution of nitric acid at 5 % v/v or
the solvent.
Rinse with demineralised water (in water medium).
Cleaning with nebulizer disassembled
If a particle is stuck in one of the conduits, perform the various steps as
may be required:
a) Carefully tap the nebulizer against a wooden surface (or against another
material with comparable hardness) to move the particle toward the wider
section.
Move the particle to one of the inlet openings and drive it out.
Position the nebulizer so that gravity acts when expelling the particle.
b) Apply a gas pressure (about 1 bar) at the orifice using a hose. With a fin-
ger, intermittently cover the inlet to create overpressure in the contaminated
conduit. Here again, position the nebulizer so that gravity acts in expelling
the particle.
c) Immerse the nebulizer nozzle in a solvent. Or, a solvent can be added in
the lateral conduit using a pipette to fill the capillary tube and the concentric.
Blank the nozzle with your finger to prevent draining. Wear a glove if a cor-
rosive solvent is used.
Apply pressurised gas through the inlet of the conduit containing the parti-
cle so that the particle and liquid are both propelled toward the increasing sec-
tion to the nebulizer outlet. You must know the exact location of the particle
to avoid accidentally fixing it by propelling it in the direction of the decrea-
sing section.
Solid deposit in sample capillary tube
Based on the last analysis performed, try to guess the chemical nature of the
deposit. Then, chose the most appropriate solvent to dissolve it and intro-
duce it through the orifice to fill the part of the capillary tube near the depo-
sit. Run the solvent over the deposit. Rinse and purge with gas.
If a particle is solidly stuck in the capillary tube
Insert a very thin wire (0.02mm) in the outlet orifice of the capillary in the
direction of the increasing section. Carefully probe the capillary tube to dis-
lodge the particle. Avoid twisting the wire and damaging the end of the capilla-
ry tube and the external cone. Be very careful when using this method. It should
only be applied when all other methods have failed.
6.2.3. Maintenance of HJY nebulizer
6.2.3.1. Nebulizer characteristics
The nebulizer is composed ofv a body on which a needle and nozzle
are mounted.
Two types of needles are used:
- Needle with diameter 0.7 mm, made of platinum.
- Needle witha diameter of 1 mm made of stainless steel.
The needle is mounted on a holder for fast installation and adjustment
of the elements.
Two types of nozzles are used:
- Nozzle for diameter 0.7 mm needle made of zirconium.
- Nozzle for diameter 1 mm needle made of zirconium.
6.2.3.2. Periodicity
Everyday, clean the nebulizer without disassembling
Every week, disassemble and clean the nebulizer.
Each time you wish to analyse traces after having analysed majors, dis-
assemble and clean the nebulizer.
When so required by the " Diagnostic " test, disassemble and fully clean
the nebulizer.
6.2.3.3. Material required
Solvent : nitric acid 5 % v/v or any other solvent.
Very thin wire
Vacuum grease or Vaseline
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6.2.3.4. Adjusting the nebulizer
Principle of adjustment
This procedure consists in adjusting the position of the needle with
respect to the nozzle to obtain maximum nebulizer efficiency.
Adjustment procedure
To move the needle, simply screw or unscrew the holder (11). This
operation must be performed with great care to avoid damaging to the
nozzle or needle.
The needle tip must be tangential to the surface of the nozzle and should
never bear on the nozzle (risk of damaging to both these essential com-
ponents).
If this is the first time you use your nebulizer:
Remove the mandrel located inside. Set it aside.
The nebulizer which you have been supplied is tested and preset with
the following parameters:
for a nebulizer with a metal nozzle and a diameter 0.7 mm needle:
pressure: 2.5 to 3 bars
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flow: 0.3 to 0.5 l/min. (instrument without automatic control
function) 1 l/min (automated instrument)
Medium: water
for a nebulizer with a metal nozzle and a 1 mm diameter needle:
pressure: 2. 5 to 3 bars
flow: 0.35 to 0.5 l/min. (instrument without automatic control func-
tion) 1 l/min. (automated instrument)
Medium: kerosene or xylene
In general, there is no need to repeat this adjustment.
However, proceeding as follows can perform a finer adjustment:
Loosen the locknut (9)
Open the argon and pressurise the nebulizer.
Insert the capillary tube in the solvent (water, xylene)
Slowly turn the needle holder (11) to the right to decrease the argon
flow (monitor the evolution of the flow on a flowmeter). The flow
decreases when the needle moves forward toward the nozzle. Never
go below a flow of 0.25 l/min.
Turn the needle holder (11) to the left to increase the argon flow
When the optimum flow is obtained, tighten the locknut (9).
Replacing the nozzle or needle
Disassemble the nebulizer as follows:
Cut off the argon.
Loosen the clamping ring (3).
Remove the nozzle.
Loosen the locknut.
Unscrew the needle holder (11) so that the needle does not advan-
ce by more than 3 mm from the body.
Replacing the needle
After removing the needle and the nozzle, reassemble the needle hol-
der.
A centring ring (6) is mounted in the lower part of the body to ensure
the best possible centring of the needle with respect to the nozzle. It is
therefore preferable to insert the needle in the central hole of this ring.
To facilitate this operation, use the mandrel supplied with the nebulizer
or, if unavailable, use a metal wire which can be inserted in the needle
and which will serve as a guide.
We also recommend that you lightly lubricate the external wall of the
needle using a vacuum grease or Vaseline to facilitate sliding through the
centring device (remove the lubricant at the end of the operation).
Screw on the holder until the needle just slightly touches the base of
the body (the needle should not project by more than 3 mm).
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Reinstall the appropriate nozzle without forgetting the o-ring.
Connect the argon.
Adjust the Teflon capillary tube on the needle.
Adjust the position of the needle by screwing in the needle holder. This
operation should be performed by plunging the capillary tube in the
solvent until you have obtained the desired pressure and flow, produ-
cing a good aerosol that is correctly centred.
Note: After performing an operation of this type, we recommend
that you perform an argon leak test. To do so, pressurise the
nebulizer, blank the orifice of the nozzle with your finger
and immerse the assembly in water to check for any possible
leaks.
Replacing the nozzle
Disassemble the nozzle to be replaced.
Unscrew the needle holder (11) and proceed as above for the adjust-
ment.
Reminder: All of these operations must be performed with great care.
Any damage to the nebulizer resulting from a false manoeu-
vre or incorrect use will not be covered by warranty.
6.2.3.5. Practical tips
Nebulizer clogged
Check the needle entry.
Fibre or particles (suspended in solutions) can form a plug.
Remove your Teflon capillary tube.
Using a cutter (do not use scissors) or a razor blade, cut off 1 cm of
capillary tube.
Readjust the capillary tube on the needle.
Needle clogged
Run the mandrel (supplied with nebulizer) or, if not available, a metal
wire through the needle, nozzle side, toward the capillary tube.
Solution has too much salt
The salts crystallise in the nebulizer. Dilute the solutions or use the argon
humidifier.
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Spray jet not in axis
The impact of this apparent defect is negligible if as the spray jet is
properly oriented and regular.
Nebulizer sputters and spray is not regular
Is the nebulizer in the same position as that used in the torch compart-
ment?
Check if the nozzle and needle are compatible (diameter).
Check that there are no machining burrs remaining in the nozzle.
Check the argon pressure and flow.
At the end of the day, nebulise using a solution of nitric acid at 5 % v/v
6.2.4. Maintenance of parallel-flow nebulizer
The parallel-flow nebulizer can be used to introduce all types of samples in
the plasma. This nebulizer is easy to maintain.
Utilisation tip
The nebulizer is entirely made of Teflon. The Teflon does not wet, thus
resulting in a light pulsation of the aerosol. This pulsation has no damaging
effect on the results. Attempting to eliminate pulsation by introducing a sur-
face active agent can have an unwanted effect on correct operation. This would
result in a high sensitivity to solutions with high salt concentration and fre-
quent clogging.
The nebulizer is fragile. Do not allow it to drop. Dropping it can result in per-
manent damage.
Caution: The gas inlet orifice is at the end of the nebulizer. Touching this end
with your finger, a piece of paper or anything else will result in immediate
destruction of the nebulizer.
The nebulizer is sensitive to temperature. Avoid any abrupt changes in tem-
perature. Keep the sample compartment door closed.
Cleaning the nebulizer
Frequency:
Every day, clean the nebulizer without disassembling it.
Each time you wish to analyse traces after having analysed majors, clean the
nebulizer without disassembling.
When so required by the " Diagnostic " test, clean the nebulizer, without dis-
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101
assembling it.
Materials required:
Solvent: nitric gas 5 % v/v or organic solvent.
Procedure:
At the end of the day, nebulise using a solution of nitric acid at 5 % v/v or
the organic solvent if working in an organic medium.
Changing the sample capillary tube
Though the nebulizer will not clog, the sample inlet capillary tube can clog. In
general, the capillary tube clogs between the pump tube and the capillary
tube. Simply cut the end of the clogged capillary tube and reconnect it to the
pump tube. If clogging occurs at another location in the tube, the tube must
be replaced.
Carefully pull the capillary tube to remove it.
Take a new tube (outside diameter 1.09 mm, inside diameter 0.38 mm). Take
the desired length (around 38 cm).
Roll about 10 cm of one end between your fingers and stretch it out to about
half of its original diameter.
Insert the stretched part in the nebulizer until it goes past the nebulizer end.
Use the stretched part to pull the non-stretched part toward the nebulizer
end.
Cut the stretched part.
Carefully pull the tubing back so that it comes in by around 0.6 cm from the
nebulizer tip. The distance is not critical. It should be 0.6 cm or more.
6.2.5. Cleaning of glass spray chambers
Purpose:
The Scott or cyclone chambers become soiled due to the different solutions
nebulised.
Frequency:
Every day, clean the chambers without disassembling them.
Every week, fully clean the chambers without disassembling them.
Each time you wish to analyse traces after having analysed majors, clean the
chambers without disassembling them.
When so required by the " Diagnostic " test, disassemble and fully clean the
chambers.
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Materials required
Solvent: nitric acid 5 % v/v or organic solvent.
KOH tablet.
Procedure
1. Cleaning the spray chamber without disassembling it.
At the end of the day, nebulise using a solution of nitric acid at 5 % v/v
or organic solvent if working in an organic medium.
2. Cleaning with disassembly of spray chamber.
Fill the chamber with demineralised water.
Dissolve 2 or 3 KOH tablets in the chamber.
Agitate for 1 minute.
Empty and rinse with demineralised water. Allow to dry.
6.2.6. Cleaning the torch
6.2.6.1. Cleaning the torch tubes
Purpose
The torch tubes become soiled with the nebulised substances. They beco-
me soiled even faster when the solution has a high salt content. Even if
it is possible to perform analysis with soiled tubes, it is better to clean
them regularly before the products attack them and become irrecove-
rable.
Frequency
Every week, disassemble and clean fully.
Each time you wish to analyse traces after having analysed majors, clean
the tubes without disassembling, or clean them if they appear soiled.
When required by the " Diagnostic " test, disassemble and clean the
tubes.
Materials required
Solvent: nitric acid or aqua regia or HF.
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Procedure
Once the plasma is stopped, wait at least 15 minutes for the tubes to
cool.
Remove the tubes by turning them.
Soak the tubes:
If not too dirty, in pure nitric acid or in aqua regia.
If very dirty, soak the tubes for a few seconds in hydrofluoric acid, then
in nitric acid.
Caution: gloves and protective goggles should be worn when hand-
ling acids.
6.2.6.2. Cleaning the torch
Purpose
The torch does not become very soiled. However, deposits can occur
in the injector if a too weak sheath gas is used. It is best to regularly
check the o-rings which, over time, can become attacked by the acid
vapours. A deposit of carbon or other materials can occur on the quartz
tubes (intermediate or outer) and in the injector when using an organic
solvent.
Frequency:
Weekly, disassemble and clean fully.
Each time you wish to analyse solutions with high salt content.
When required by the " Diagnostic " test, disassemble and clean.
Tools required:
Silicon grease.
Sulfochromic mixture.
Procedure
The plasma must be off, the argon closed and the peristaltic pumps off.
Once the plasma is out, wait at least fifteen minutes for the tubes to
cool down.
Remove the torch by disconnecting the quick couplings.
Remove the two outer tubes and the intermediate tube by slightly tur-
ning and carefully pulling them with respect to the torch body . Be
careful not to break them by clasping them too tightly.
Also remove the injector that is force-fit and clean it if clogged, or repla-
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104
ce it if damaged.
At the same time, check that all the o-rings in the torch body are in
good condition and replace them if necessary. Apply a light coat of sili-
con grease to new o-rings before fitting them.
Reinstall the injector by pushing it in fully and ensure that the centring
spacer is properly in place at the upper level of the torch body.
Then, install the new intermediate tube followed by the outer tube. To
facilitate the positioning, apply a light coat of silicon grease at the base
and push them in while turning them slightly similar to the procedure.
Check that they are perfectly pushed into the body of the torch and
that the torch, thus reassembled, looks like it did before the interven-
tion.
Correct operation of the torch highly depends on the condition of the
tubes and their proper positioning with respect to the induction coil.
The end of the injector should be situated at the end of the interme-
diate tube or 1.5 mm below. It should not, under any circumstances,
project beyond the tube.
Reinstall the torch checking that it is properly engaged on the sheath
device. Reinstall the clip.
Check that the torch is properly centred with respect to the induction
coil windings.
In the torch body, successively fit:
- The sheath device.
- The injector.
- The Teflon centring device.
- The inner tube (still called intermediate tube).
- The outer tube.
Before assembling, check the position of the o-rings. Lightly lubricate
the sockets of the auxiliary and outer tubes. Gradually insert the tubes
while turning them. Be sure to place the tubes fully.
Once you have completed the assembly, check that the top of the injec-
tor tube is 1.5 mm below the top of the auxiliary tube.
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105
6.2.7. Replacement of pump capillary tubes
Purpose:
Wear due to the corrosive effect of the solutions on one hand, and the conti-
nuous tension of the pump to which they are subjected on the other, cause
the tubes to loose their elasticity.
Materials required:
For water solutions, tygon capillary tubes are used (white, translucent colour).
For strong acids, oils, aromatic solvents up to 200 C, solflex capillary tubes
(yellow translucent colour) are used. Stronger, Viton tubes can also be used
(black colour).
Procedure: The plasma must be off.
Remove and replace the defective capillary tubes. Be careful with the pump
rotation direction.
Do not over-tighten the tube.
Adjust the tube so that the natural suction of the Meinhard, for example, is
similar to that of the capillary tube when tensioned.
6.2.8. Cleaning the entrance window
This operation should only be performed by persons qualified by a
HORIBA Jobin Yvon maintenance training course.
Purpose:
The entrance window of the spectrometer is made of MgF
2
and can be affec-
ted by chemical products which go to the torch. A dirty window lowers the
signal of low wavelength and then of the total range.
Frequency:
Every year, for use in a water medium with lateral viewing.
Every month, for use in an organic medium.,
Every week, for use with spark ablation.
When required by the " Diagnostic " test.
Materials required:
Lens paper or cotton swab.
Anhydrous acetone.
Procedure
1. Disassembly of optical gun.
Dismount the front panel, the one with the ACTIVA logo.
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106
Figure 62: Dismountong of the optical channel
Figure63: Optical gun
The window holder (7) appears on the fixed part of the gun. Unscrew
it.
Figure 64: Window holder
2. Cleaning
The window is made of MgF
2
. Water will irremdiably destroy it.
Clean the lens with acetone using a cotton swab, or better, a lens
paper.
3. Reassembly of optical gun.
Perform the disassembly procedure in reverse order.
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107
6.3. In the event of a problem
6.3.1. Absence of signal or low signal
The signal for the elements in the solution is absent or very low regardless of
the wavelength.
Check that the nebulizer is not clogged.
Nebulise a solution of Yttrium at 1 g/l.
If the plasma becomes coloured, nebulization is correct.
If the plasma does not become coloured, the nebulizer is clogged and needs to
be cleaned.
Figure 65: Plasma with Y 1 g/L solution
6.3.2 Bad instantaneous stability
If the RSDs are bad:
Check the analytical conditions (analysis mode, increment between two points,
integration time).
Check the peristaltic pump rollers.
Check the temperature in the sample compartment.
If necessary, change the Interface board as it may lose data if defective.
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108
Check the torch and the capillary tubes.
If the instantaneous RSDs are randomly bad on the low point :
Carefully rinse before measuring the low point (at least 10 min).
If necessary, replace the Interface board as it may lose data if defective.
Aspirate " Brij 35 ".
If the instantaneous RSDs are systematically bad on the low point:
Add a surface active agent, for example Brij 35, to the rinsing solution. Wait
10 minutes, then repeat the measurements.
If the results improve, either add a surface active agent to the rinsing liquid,
or clean the chamber, or replace the chamber.
If the results do not improve, install the reference nebulizer, then the cham-
ber, and finally the reference burner.
Check that there are no leaks in the gas circuits (nebulization, sheath, argon
humidifier).
If the instantaneous RSDs are bad on the high point for certain ele-
ments:
In Gaussian analysis mode, check the increments between the two measure-
ment points.
In direct analysis mode, check that the peaks do not change.
6.3.3. Loss of reference line or zero order
6.3.4. Spectralink reinitialisation.
If an electronic problem occurs, for example a micro-cutoff, the
Spectralink can "crash". Reinitialise the Spectralink and perform a zero
order search, then continue the analysis. If the cutoff is short, there is
no need to recalibrate.
6.4. Periodic verification of spectrometers.
To ensure the compliance of the results with respect to the initial specifications of
your instrument, proceed as follows. In accordance with standard ISO 10012 rela-
tive to control of inspection, measurement and test instruments, all analysis values
must be confirmed metrologically.
As a manufacturer, we can provide this service in accordance with the type of main-
tenance contract that you have signed.
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109
The tests last 8 hours and are conducted independently of the annual inspection pro-
vided by the standard service contract. The tests are completed over the period of
one day.
These tests comprise the Final Control tests for the instrument, covering such aspects
as resolution, detection limits, short and long-term stability, the generator and the
fluid control function.
A specimen copy of the Verification Certificate is given below.
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110
Figure 66: Verification certificate (1)
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111
Figure 67: Verification certificate (2)
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112
6.5. Spare parts
6.5.1. How to order
We highly recommend that you use HORIBA Jobin Yvon consumables to
obtain a constant analysis quality with your spectrometer. We decline any respon-
sibility regarding performance when HORIBA Jobin Yvon consumables are
not used.
Price quotations can be obtained by telephone or better by writing (fax, mail).
Our references are detailed in the spare parts catalogue.
Our prices do not include tax. The costs for packaging and transportation are
added and depend on the method of shipping.
All orders must be confirmed in writing and carry an order number.
To order :
Contact your supplyer or
HORIBA Jobin Yvon or www.jobinyvon.fr
Ligne Emission emission
Service Aprs-Vente alliance
16-18 rue du Canal
91165 Longjumeau Cedex
Tel.: 01 64 54 13 28
Fax : 01 69 09 17 27
6.5.2. Minimum recommended stock
We recommende you to have:
- a nebulizer (to be tested at reception in order to use it when needed)
- an external torch tube
- an internal torch tube
- an injector tube
- capillary for nebulizer
- pump tubes
- eventually a torch body
- a nebulizer spray chamber
- a sheath device
- a fuse
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113
7. ANNEXES
7.1. Bibliography
7.1.1. General works
Les applications analytiques des plasmas hautes frquences
C. Trassy, J.M. Mermet
1987
Technique et documentation
Lavoisier
11, rue Lavoisier
75384 PARIS CEDEX 08
Handbook of inductively coupled plasma spectrometry
M . Thompson, J.N. Walsh
1988, 2nd edition
Blachie USA Chapman and Hall NEW YORK
Inductively coupled plasma emission spectroscopy
En deux volumes
Vol 1 : Methodology, instrumentation and performance
Vol 2 : Applications and fundamentals
PW JM Boumans
Wiley, Interscience publication, 1987
Inductively coupled plasmas in analytical atomic spectrometry (2 nd edition)
A Montaser, DW Golightly
VCH Publishers
7.1.2. Sample introduction
Sample introduction system
J. Sneddar,
Elsevier, 1990
7.1.3. Detector
Scientific Charge Coupled Devices
James R. janesick
SPIE Press, 2001
7.1.4. Sample preparation
Sample pretreatement and separation
R. Anderson
Analytical Chemistry by open learning, 1987
John Wiley and Sons.
.
7.1.4. Statistics applied to analytical chemistry
Activa User Manual
114
La validation des mthodes d'analyse
Max Feinberg
Masson,1996
Applied regression analysis, second edition
N. Draper, H. Smith
1996
John Wiley and Sons.
Statistics for analytical chemistry
2nd edition
JC Miller, JN Miller
1988,
Ellis Horwood Limited
Probabilities data reduction and error analysis in the physical sciences
D. Taupin
1988
Les Editions de Physiques
Chemometrics : a textbook
DL Massart, BGM Vandeginste, SN Deming, Y. Michotte, L. Kaufman
1988
Elsevier
Prcision des dosages de traces
M. Neuilly
1996
Cetama
7.1.6. Journals
Journal of analytical atomic spectrometry
Royal society of Chemistry
University Park
Nottingham- NG72RD, UK
Spectrochimica Acta - Part B : atomic spectroscopy
Pergamon Press Plc
Headmington Hill Hall
Oxford OX3 OCW, UK
7.1.7. Wavelength and interference tables
Tables of Spectral Lines
AN Zaidel, VK Prokof'ev
1970
Library IFI/ Plenum-New York- London
Line coincidence tables for inductively coupled plasma atomic emission spec-
troscopy
P. Boumans
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115
1980
Pergamon Press
Inductively coupled plasma atomic emission spectroscopy
Spectral information atlas
R. Winge, V. Fassel
1985
Elsevier
Wavelength table MIT
G. Harrison
1969
en deux volumes
The MIT Press Cambridge, Massachusettes, London
Lambda III
J. Burgener
1992
Technical Solutions unLimited, Canada
7.2. Wavelengths as a function of matrices
Indicated below in the tables are the wavelengths to be used as a function of
the matrix.
Matrices:
Ag
Al 10 g/l
Cement
Co 20 g/l
Cu 10 g/l
Water
Fe 10 g/l
Fe/Ni/Cr
Geology
Ir
Kerosene
Mn
Nb
Ni 10 g/l
NiSO
4
, 6H
2
O 100 g/l
Paint
Pt
Pt/Rh
Ru
Brine
Sb 24 g/l
Soils
Ta 10 g/l
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Verre
W 10 g/l
Xylene
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Ag 328,068 X X
Ag 338,289 X X
Al 167,020 X X
Al 237,312
Al 394,401 X X X
Al 396,152 X X X
As 189,042 X X X X X X X
As 193,696 X X
As 200,334
As 228,812
Au 197,819 X X
Au 242,795 X
Au 267,595 X X
B 182,640 X X
B 208,959 X
B 249,773 X X X X
Ba 233,527 X X
Ba 455,403 X X
Be 234,861 X X
Be 313,107 X X
Bi 206,170 X X
Bi 222,825
Bi 223,061 X X X
Bi 289,798 X X
Bi 306,772 X X
Ca 315,897 X X
Ca 317,933 X X
Ca 393,366 X X X X X X
Ca 396,847 X X
Ca 422,673
Ce 456,236 X X
Cd 214,438 X X X X X X
Cd 226,502 X X
Cd 228,802 X X
Co 228,616 X X X X
Co 238,892 X X X X X
Cr 205,552 X X X
Cr 206,149
Cr 267,716 X X X X X X X
Cr 283,563 X X
Cr 284,325
Cr 357,869
Cr 425,434
Cu 213,598 X X
Cu 217,894 X X
Cu 223,008 X X
Cu 224,700 X X
Cu 324,754 X X X X X X
Cu 327,396
Matrix Water Co 20g/l NiSO
4
,6H
2
O Sb24 g/l Niobium Ni 10g/l Cu10g/l Al10g/l
Element (nm) 100g/l
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Fe 234,349
Fe 238,204 X X X X
Fe 239,562 X X
Fe 240,488
Fe 259,940 X X X X X X X
Fe 273,955 X X
Fe 371,993
Ga 294,364 X X
Ge 417,206 X X
Ge 209,406 X X
Hf 282,022 X X
Hg 184,890 X X X
Hg 194,227 X
I 178,218
In 230,606 X X X
In 303,936 X X
In 325,609 X X X
Ir 205,222 X
Ir 212,681 X
Ir 215,268 X X
Ir 224,268 X
Ir 322,078
K 766,491 X X X
La 398,852 X X
La 408,672 X X
Li 670,784 X X X
Mg 279,553 X X X X X X
Mg 280,270 X X
Mn 257,610 X X X X X X X
Mn 259,373 X X
Mn 260,569 X X X
Mn 403,076
Mo 202,030 X X X
Mo 204,598 X X
Mo 281,615
Mo 284,823
Mo 313,259 X X
Mo 379,825
Mo 386,411
Na 588,995 X X X X
Na 589,592 X X
Nb 269,706
Nb 309,418 X X
Nb 313,079
Nb 316,340 X X X
Nb 319,498 X X
Ni 216,556 X X X
Ni 221,647 X X
Ni 231,604 X X X X
Ni 232,003 X X
Ni 341,476
Ni 349,295
Ni 351,505 X X
Ni 352,454 X X
4
,6H
2
Element (nm) 100g/l
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119
Os 228,226
P 178,225 X X X X X
Pb 168,100 X X X X
Pb 220,353 X X X X X X
Pb 261,418
Pb 283,306 X X X X X
Pb 405,783 X X X X X X X
Pd 324,270 X X
Pd 340,458 X
Pd 342,124
Pd 360,955 X
Pt 214,423 X
Pt 224,552
Pt 265,945 X X
Pt 299,797 X
Rh 233,477
Rh 339,685
Rh 343,489 X X
Rh 369,236 X
Ru 240,272 X
Ru 245,657
Ru 267,876 X
Ru 372,803 X
S 180,676 X X X
S 181,978 X X
Sb 206,833 X X X X
Sb 217,581 X X X
Sb 231,147 X X
Sc 361,384 X X X
Se 196,090 X X X
Si 212,412 X X
Si 251,610 X X X X
Si 252,851 X X
Si 288,158 X X X
Sm 359,260
Sn 189,989 X X X X X X X
Sn 235,484 X X
Sn 242,170 X X
Sn 242,949 X X
Sn 283,999
Sr 407,771 X X X X X
Ta 263,558 X X X
Te 214,281 X X X
Te 225,904 X
Te 238,578 X X
Ti 323,657
Ti 334,941 X X X
Ti 336,121 X X
Ti 337,280 X X X
Ti 338,376 X X
Tl 190,864 X X
4
,6H
2
O Sb24 g/l NiobiumNi 10g/l Cu10g/l Al10g/l
Element (nm) 100g/l
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V 290,882 X X
V 292,402 X X X X
V 310,230 X X
V 311,071
V 311,838 X X
W 207,911 X X X
W 209,475 X X
W 218,936
W 239,709 X X
Y 360,073 X X
Y 371,030 X
Y 378,870
Zn 206,202 X X X X
Zn 213,856 X X X
Zn 334,502 X X
Zr 257,139
Zr 339,198 X X
Zr 343,823 X X X
Zr 349,621 X X
4
,6H
2
Element (nm) 100g/l
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Ag 328,068 X X X
Ag 338,289 X X X
Al 167,020 X
Al 237,312 X
Al 394,401 X X
Al 396,152 X X X X X X
As 189,042 X X
As 193,696
As 200,334 X
As 228,812 X
Au 197,819 X
Au 242,795 X X X
Au 267,595 X X X X X
B 182,640 X X
B 208,959 X X X
B 249,773 X X X X
Ba 233,527
Ba 455,403 X X X
Be 234,861 X
Be 313,107
Bi 206,170
Bi 222,825 X
Bi 223,061 X X X
Bi 289,798
Bi 306,772 X
Ca 315,887
Ca 317,933 X X X
Ca 393,366 X X X X
Ca 396,847 X X
Ca 422,673 X
Ce 456,236 X
Cd 214,438 X
Cd 226,502 X X X X
Cd 228,802 X X X
Co 228,616 X X X X X
Co 238,892 X X X X
Cr 205,552 X X
Cr 206,149 X
Cr 267,716 X X X X
Cr 283,563 X
Cr 284,325 X
Cr 357,869 X
Cr 425,434 X X
Cu 213,598
Cu 217,894
Cu 223,008
Cu 224,700 X
Cu 324,754 X X X X X X X
Cu 327,396 X
Fe 10g/l Ta 10g/l W 10 g/l Mn Ag Pt Pt/Rh Ir Ru
Element (nm)
Fe 234,349 X
Fe 238,204 X X
Fe 239,562 X
Fe 240,488 X
Fe 259,940 X X X X
Fe 273,955
Fe 371,993 X
Ga 294,364 X
Ge 417,206
Ge 209,406 X
Hf 282,022
Hg 184,890 X
Hg 194,227
I 178,218 X
In 230,606
In 303,936 X
In 325,609
Ir 205,222
Ir 212,681 X
Ir 215,268
Ir 224,268 X X X X
Ir 322,078 X
K 766,491 X X
La 398,852
La 408,672
Li 670,784 X X X
Mg 279,553 X X X X X X X X
Mg 280,270
Mn 257,610 X X X
Mn 259,373
Mn 260,569 X X
Mn 403,076 X
Mo 202,030 X
Mo 204,598 X
Mo 281,615 X
Mo 284,823 X
Mo 313,259
Mo 379,825 X
Mo 386,411 X
Na 588,995 X X
Na 589,592 X X X
Nb 269,706 X
Nb 309,418
Nb 313,079 X
Nb 316,340 X
Nb 319,498
Ni 216,556 X X
Ni 221,647 X
Ni 231,604 X X X X X
Ni 232,003
Ni 341,476 X
Ni 349,295 X X
Ni 351,505
Ni 352,454
Element (nm) X
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Os 228,226 X X
P 178,225 X X
Pb 168,100
Pb 220,353 X X X X X
Pb 261,418 X
Pb 283,306 X
Pb 405,783
Pd 324,270
Pd 340,458 X X X X X
Pd 342,124 X
Pd 360,955
Pt 214,423 X
Pt 224,552 X
Pt 265,945 X X
Pt 299,797
Rh 233,477 X
Rh 339,685 X
Rh 343,489 X X X
Rh 369,236
Ru 240,272 X
Ru 245,657 X
Ru 267,876 X
Ru 372,803 X
S 180,676
S 181,978 X
Sb 206,833 X X X X
Sb 217,581 X
Sb 231,147 X
Sc 361,384 X
Se 196,090
Si 212,412
Si 251,610 X X
Si 252,851
Si 288,158 x X
Sm 359,260 X
Sn 189,989 X X X X X X
Sn 235,484
Sn 242,170
Sn 242,949
Sn 283,999 X X
Sr 407,771 X X X X
Ta 263,558
Te 214,281 X
Te 225,904 x
Te 238,578
Ti 323,657 X
Ti 334,941 X X X
Ti 336,121 X
Ti 337,280
Ti 338,376
Tl 190,864
Element (nm)
V 290,882 X
V 292,402 X X
V 310,230 X
V 311,071 X
V 311,838
W 207,911 X X X
W 209,475 X
W 218,936 X
W 239,709
Y 360,073
Y 371,030
Y 378,870 X
Zn 206,202 X
Zn 213,856 X X X X X X X X
Zn 334,502
Zr 257,139 X X
Zr 339,198 X X
Zr 343,823 X X X
Zr 349,621
Element (nm)
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Ag 328,068 X Eau X
Ag 338,289
Al 167,020
Al 237,312
Al 308,215 X X X X
Al 394,401 X
Al 396,152 X X
As 189,042 X X X
As 193,696 X
As 200,334
As 228,812
Au 197,819
Au 242,795
Au 267,595
B 182,580 X
B 182,640
B 208,959 X
B 249,773
Ba 233,527 X X X X
Ba 455,403 X
Be 234,831
Be 313,107
Bi 206,170
Bi 222,825
Bi 223,061
Bi 289,798
Bi 306,772
Ca 315,887
Ca 317,933 X X X
Ca 393,366
Ca 396,847
Ca 422,673 X
Ce 456,236 X
Cd 214,438 X
Cd 226,502 X X
Cd 228,802 X X
Ce 413,765 X
Co 228,616 X X
Co 238,892 X
Cr 205,552 X
Cr 206,149
Cr 267,716 X X X X
Cr 283,563
Cr 284,325 X
Cr 357,869
Cr 425,434
Cu 213,598
Cu 217,894
Cu 223,008
Cu 224,700
Cu 324,754 X X X X
Cu 327,396
Geology Soils Cement Glass Paint Saumur Kerosen Fe/ni/Cr
Element (nm) Xylen
Dy 353,170 X
Er 390,631 X
Eu 318,967 X
Fe 234,349
Fe 238,204
Fe 239,562
Fe 240,488
Fe 259,940 X X X X X
Fe 273,955
Fe 371,993
Ga 294,364
Gd 342,247 X
Ge 417,206
Ge 209,406
Hf 264,141 X
Hf 282,022
Hg 184,890 X
Hg 194,227 X X
Ho 345,600 X
I 178,218
In 230,606
In 303,936
In 325,609
Ir 205,222
Ir 212,681
Ir 215,268
Ir 224,268
Ir 322,078
K 766,491 X X X X
La 398,852 X
La 408,672
Li 670,784 X
Lu 261,542 X
Mg 279,079 X X
Mg 279,553
Mg 279,806 X
Mg 280,270 X
Mg 285,213 X
Mn 257,610 X X X X
Mn 259,373
Mn 260,569
Mn 403,076
Mo 202,030 X X X
Mo 204,698
Mo 281,615
Mo 284,823
Mo 313,259
Mo 379,825
Mo 386,411
Na 588,995 X
Na 589,592 X X X
Element (nm) Xylen
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Nb 269,706
Nb 309,418
Nb 313,079
Nb 316,340 X X
Nb 319,498
Nd 406,109 X
Ni 216,556
Ni 221,647 X
Ni 231,604 X X X
Ni 232,003
Ni 341,476
Ni 349,295
Ni 351,505
Ni 352,454
Os 228,226
P 178,225 X X X X X
Pb 168,100
Pb 220,353 X X X X X X X
Pb 261,418
Pb 283,306
Pb 405,783
Pd 324,270
Pd 340,458
Pd 342,124
Pd 360,955
Pr 414,311 X
Pt 214,423
Pt 224,552
Pt 265,945
Pt 299,797
Rh 233,477
Rh 339,685
Rh 343,489
Rh 369,236
Ru 240,272
Ru 245,657
Ru 267,876
Ru 372,803
S 180,676 X
S 181,978 X X X CIE
Sb 206,833 X
Sb 217,581
Sb 231,147
Sc 361,384 X
Se 196,090 X X
Si 212,412
Si 251,610 X X
Si 252,851
Si 288,158 X X X
Sm 359,260 X
Sm 359,260 X
Element (nm) Xylen
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128
Sn 189,989 X X
Sn 235,484 X
Sn 242,170
Sn 242,949
Sn 283,999
Sr 407,771 X
Ta 263,558
Tb 350,917 X
Te 214,281
Te 225,904
Te 238,578
Ti 323,657
Ti 334,941 X
Ti 336,121
Ti 337,280 X X X X
Ti 338,376
Tl 190,864 X X
Tm 313,126 X
V 290,882 X
V 292,402
V 310,230 X
V 310,252 X
V 311,071
V 311,838
W 207,911 X
W 209,475
W 218,936
W 239,709
Y 360,073
Y 371,030 X
Y 378,870
Yb 328,937 X
Zn 206,202
Zn 213,856 X X X X
Zn 334,502 X
Zr 257,139
Zr 339,198
Zr 343,823 X X
Zr 349,621
Element (nm) Xylen
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129
7.3. Training
General training courses are organised at HORIBA Jobin Yvon. The programs and
dates will be sent to you each year.
In addition to these training courses, we can provide training courses on site to
meet your specific needs. These training courses can be registered under your conti-
nuing training budget.
For example, we propose:
Assistance in optimizing a specific analysis method.
Analytical training over one to three days on a subject of your choice.
Software and first-time user training.
Complete training of 3 to 5 days.
7.4. Optical system supplement
The optical system comprises two parts:
The illumination system
The dispersive system
7.4.1. Illumination system
The illumination system carries the light emitted by the plasma to the disper-
sive system.
The Achromatic Entrance Imager was designed to optimize photon collec-
tion, optical aberrations, resolution, stray light and the 6 mm slit height of the
Czerny-Turner optical system. It allows viewing of the entire 6 mm Normal
Analytical Zone of the plasma. This view is imaged through the spectrome-
ter onto the full height of the 2048 x 512 pixel detector. This collected light
is vertically spread over 512 pixels gaining the full well capacity of each pixel
without the penalty of readout noise.
Compared to the use of a single lens for focusing, the Achromatic Entrance
Imager uses 2 mirrors: one concave and one plane. The concave mirror is inhe-
rently free of chromatic aberrations across the spectrum, rather than at one
wavelength, and the plane mirror directs the light into the optical system. The
achromatic imager uses a MgF
2
window.
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130
Figure 68: Illumination system
7.4.2. Dispersive system
ACTIVA incorporates a new innovative design featuring a 0.64 m Czerny-
Turner optical system. This design integrates an Achromatic Entrance Imager
entrance optic for optimized imaging from the entrance slit onto the solid state
detector of the best analytical zone of the plasma. The ACTIVA dispersive
system features a design with a low number of optical surfaces, negligible
stray light and free of optical aberrations.
This entrance optic associated with large Czerny-Turner optical components
featuring 80 mm x 110 mm dual gratings, provides the highest optical lumi-
nosity from the far UV to the near infrared.
ACTIVA operates with several nm wide spectral windows called Wavelength
Analytical Views (WAV). The width is given by the reciprocal linear disper-
sion (RLD) of the grating multiplied by the detector pixel size and the num-
ber of pixels. The aberration free, JY holographic gratings combined with the
2048 pixel wide CCD detector result in two WAV sizes: up to 8 and 16 nano-
meters. The two gratings are used back-to-back to provide first order light from
165 to 800 nm. The use of first order light eliminates order hopping resulting
from overlapping orders typically seen in echelle grating spectrometers and
results in a constant intensity across the WAV.
7.4.2.1. Properties
The purpose of the dispersive system is to separate the lines in order
to obtain better detection limits and facilitate analysis by avoiding cor-
rective calculations.
The core of the system is the grating.
How the gratings are produced will be explained subsequently.
A grating is a surface on which a large number of narrow, parallel,
equal and equidistant grooves have been formed. A grating breaks down
the light into coloured spectra. This enables separation of the various
wavelengths emitted by the sample being analysed.
Different laws govern the dispersive systems.
Figure 69: Diffraction
The normal is the perpendicular to the flat slope of the grating before
machining. When an incident beam with an incident angle illuminates
the grating , a portion of the light is diffracted with an angle ,
which is the angle of diffraction.
The fundamental equation of diffraction is as follows:
nk = sin + sin
wavelength
n number of grating lines (constant)
k order of diffraction
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132
incident angle with respect to normal of grating
diffracted angle with respect to normal of grating
In the lines below, we will demonstrate the relation with a simplified case
in order to introduce the principle of order.
Figure 670: The difference of functioning
Here, we will assume a reflecting grating and an incident beam perpen-
dicular to the grating.
In the direction, the difference of functioning, difference of length of
paths between directions 2 and 1 is:
d
2
- d
1
= l'H =
= l'lH
sin = l'H / ll' = l'H / a with a grating step
so the difference of length path becomes
= a sin
This represents the difference of functioning between direction 1 and
2 but also between directions 2 and 3; it is the difference of functioning
between two consecutive vibrations.
All of these vibrations give a maximum amount of light when = k with
k Z.
k = 0 sin = 0 pour tout
ou = 0 pour tout
This is the zero order; the grating behaves as a mirror, reflecting the light
in only one direction.
k = 1 depends on
This is the first order spectrum.
k = 2
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134
This is the second order spectrum.
The figure below represents the spectra of the first two orders.
Figure 71: Two orders
For ACTIVA
The entrance and exit slits are fixed. The angle - is thus a
constant of the system.
Figure 72 : ACTIVAdispersive system
LINEAR DISPERSION
Dispersion is an important principle. It is represented by the linear disper-
sion (mm/nm) or by the reciprocal linear dispersion (nm/mm) or by the
angular dispersion. It represents the scatter of the spectrum in the image
plane.
The monochromator allows us to define the movement of the grating
required to access the desired line.
The angular dispersion is defined by:
d = n
d d cos
The reciprocal linear dispersion is defined by:
d = d cos
dx nF
where F is the focal distance of the spectrometer (distance between entry
slit - grating or grating - exit slit).
It can also be represented by:
d = cos = cos
dx (sin + sin ) F F n K
The angular dispersion thus depends on the angle of incidence and dif-
fraction. It is not constant at all points of the focal plane.
The table below represents the linear dispersion as a function of the
wavelength for the ACTIVA.
170 31.06 0.307
200 35.20 0.293
300 50.39 0.229
400 70.72 0.118
500 46.53 0.447
In addition, for a higher dispersion, large angles and a long focal dis-
tance is required.
RESOLUTION
The experimental width of the line depends on:
- the physical width of the line
- the instrumental width
Wavelength Angle Linear dispersion
(nm) () nm/mm
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135
It is represented by:
exp
= (
phys
+
ins
)
1/2
The physical width of the line is between 1.5 and 6 pm.
The instrumental width must be less than 1.5 pm in order to not be a
limiting factor.
The instrumental width is due to:
theoretical resolution (optical system)
bandpass (width of slits)
aberrations (mirrors, alignment)
Theoretical resolution
The theoretical resolution power is used to evaluate the degree to which
two near emission lines can be separated. This principle represents the
effect of diffraction without considering the effect of the slits.
We assume that two lines with the same intensity are separated when
the maximum level of one corresponds to the minimum level of the
other (Rayleigh criterion).
The resolution power R is represented by:
R = = kN = W
d
Where k: spectral order
N : Total number of useful lines of grating
W : Width of illuminated grating
The resolution power will proportionally increase with the size of the
grating and the significance of the spectral order.
Aberrations
The theoretical resolution power is deteriorated by aberrations (astig-
matism, coma).
However, our spectrometers (distance between slits, width of gratings,
etc.) have been optimised to overcome these problems.
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136
Practical resolution
To determine the practical resolution of an instrument, the width at mid-
height (LDH) of a line is calculated. In this respect, we consider that
two lines are separated when the minimum intensity of one corresponds
to the maximum intensity of the other (Rayleigh criterion).
The LDH is calculated graphically after recording the line.
The LDH depends on the specific length of the line itself and the instru-
ment.
7.4.2.2. Grating
White light is the sum of all wavelengths (ultraviolet, blue, , red,
infrared).
A grating is an optical device used to break down the light into its com-
ponents.
This function used to be performed using prisms.
Schematically, a grating is a support that is identical in shape and dimen-
sions to a mirror on which very closely spaced lines have been traced
(20 to 3600 lines/mm).
The optical phenomenon used by the gratings is diffraction, unlike prisms,
which obey the refraction principle.
Gratings have the advantage over prisms of being more dispersive,
thus making it possible to build larger instruments. They also have the
advantage of being used across a much wider spectral range (far ultra-
violet to far infrared, meaning the widest range of colours).
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138
Figure 73: Diffraction : grating and prism
The elements forming the material around us stop certain wavelengths
and allow others to pass.
By analysing the light passing through a material, it is possible to iden-
tify the components.
Similarly, with emission, the elements excited by a source of energy
(Plasma, ICP, Spark, ) emit their characteristic wavelengths.
Gratings are used in spectroscopy instruments applied to industrial
analysis (ACTIVA, U1000, monochromators), medical analysis (spec-
trophotometers), and scientific research (U 1000, THR, satellite-carried
experiments). In all of these instruments, the grating ensures the main
functions and forms the core of the instrument.
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139
Figure 74: Gratings manufacture
Three very different technologies are used to manufacture gratings:
Engraving
The engraving is done on a grating machine: the lines are traced by a
diamond, shaped like a boat hull, in a layer of aluminium deposited by
vacuum evaporation.
The grating machines are very high-precision machines implementing
interferometer control and operating in a thermostat-controlled room
to more or less one or two hundredths of a degree.
HORIBAJobin Yvon manufactures all of the HORIBAJobin Yvon gra-
ting machines.
For this technique, the grating lines are traced one after the other and
can take several weeks.
Figure 75: Engraving machine
Figure 76: Grating engraving
Holographic recording
A polished support covered with photosensitive resin is exposed in a
field of interference fringes, then developed chemically. All of the lines
of the grating are simultaneously recorded.
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140
Figure 77 :Holographic record
HORIBA Jobin Yvon developed the holographic gratings and is the
world's foremost manufacturer of this type of grating.
To obtain satisfactory grating operation, the error in positioning the lines
with respect to the theoretical position must be very low. The mean error
is two thousandths of a micron for a holographic grating.
For the grating to achieve a good luminous efficiency, the profile of the
lines must have a well-defined shape. The shape of the lines must the-
refore be carefully controlled.
Figure 78: Grating profil
In the ultraviolet and visible ranges, holographic gratings provide per-
formance that is superior to that of engraved gratings.
Depending on the instrument, the grating used will either be an "origi-
nal" grating engraved on a machine or holographically recorded, or a
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141
replica of the original grating.
Ionic machining
To improve their efficiency even further, the holographic gratings can
be ionically machined.
Properties of gratings depending on their technology
Engeaved grating
Very high efficiency of 80 to 95 %
High stray light
Holographic grating
Mean efficiency of 30 to 40 %
No stray light
Machined holographic grating
Efficiency of 60 to 80 %
No stray light
Production of gratings
HORIBA Jobin Yvon produces all the gratings used in its instruments
and also sells gratings to laboratories and other instrument manufactu-
rers throughout the world.
Up to now, the gratings were nearly always used for spectroscopy. At
this time, systems implementing gratings (grating multiplexers) are cur-
rently being evaluated for optical fibre telecommunications applications.
Such systems could provide a new market outlet for the grating tech-
nology in addition to their use in spectroscopy.
Wavelength range of a grating
The number of lines of the grating determines the wavelength range of
a grating.
The highest values for incidence and diffraction angles are 90 C.
The equation
nK
limite
= sin + sin
becomes:
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142
nK
limite
= 1 + 1 = 2
hence:
limite
= 2
nK
Since analysis are never performed at grazing incidence, the practical
limits are below the theoretical limits.
The table below gives examples of spectral ranges.
2400 1 830 780
4320 1 460 450
Resume: mains features
- Simultaneous SimShot analysis of multiple elements at multiple wavelengths
and background within a Wavelength Analytical View (WAV).
- Achromatic Entrance Imager for optimized imaging of the entrance slit onto
the solid state detector.
- High luminosity, 0.64 m Czerny-Turner dispersive system with few reflecti-
ve surfaces.
- 6 mm large entrance slit increases light throughput.
- Dual holographic gratings provide first order wavelength coverage from
165 to 800 nm.
- High speeed WAV of 16 nm with optical resolution < 10 pm.
- Super Flat Field position of the solid state detector allows constant resolu-
tion and constant intensity within a WAV.
- Wavelength stabilization, through use of user selected wavelength referen-
cing, provides excellent stability.
7.4.3 Detector
ACTIVA ICP-OES uses a Back Illuminated (BI), high performance Advanced
Inverted Mode Operation, Charge Couplet Device (CCD) detector optimi-
zed for UV and visible spectroscopy, with high quantum efficiency, very low
noise levels and high linear range. Back illumination technology, in combina-
tion with an extremely low noise amplifier makes the device well suited to the
most demanding spectroscopy applications. With a relatively constant respon-
se and an average Quantum Efficiency (QE) of 60% between 165 nm and
800 nm, this detector is ideal for elemental analysis by ICP-OES. The detec-
tor operates in Advanced Inverted Mode (AIMO), also known as Multi-Pinned
Phase (MPP), and offers a reduction by 100 in dark current with a minimum
reduction in full well capacity, increasing dynamic range.
Number of lines of Order Theoretical Practical
grating limit limit
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143
An alternative to front side illumination, where incident UV photons are
trapped in the electrode gate structure and the insulating layer, is backside
illumination, which is the process for illumination from the reverse side. Back
thinning occurs with the elimination of the substrate to allow the photons to
directly reach the epitaxy silicon layer. This back thinning process is usually
achieved with chemical etching, together with surface passivation and an optio-
nal UV anti-reflection coating. Back-thinned devices have a much higher quan-
tum efficiency than standard (front illuminated) devices. UV wavelengths
back-thinning will provide the highest quantum efficiency of any technology
available today.
Figure 79: CCD with back illumination
(a) (b)
Figure 80: Quntum efficienty front illumination (a) back illumination (b)
Advanced Inverted Mode Operation (AIMO) is an improved inverted mode
device structure created to achieve peak signal levels higher than any available
with the basic IMO device featuring additional implants to allow integration
with all clock phases at zero and the whole surface inverted, thereby achie-
ving very low levels of dark signal. AIMO provides a decreased dark signal
without effecting the full well capacity.
The ACTIVA CCD offers 13.5 m x 13.5 m pixel size, well suited for high-
resolution spectroscopy. Associated with the high resolution is ACTIVAs high
luminosity dispersive optic, the optical resolution is as low as 10 pm. The chip
is rectangular shaped 2048 wide x 512 pixels high, well adapted to detect 6
mm of the plasma with large WAVs (Wavelength Analytical View).
The selection of pixel size is a balance between basic performance parame-
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144
ters. Smaller pixels will give increased resolution, assuming that resolution is
not limited elsewhere in the system. Typically, as the pixel size decreases, well
capacity (the amount of charge that can be stored in a pixel) and the overall
dynamic range decrease. However, when the detector is combined with a
light rich, high-resolution dispersion system with a large 6 mm entrance slit
height, the full column of 512 pixels can be used and the dynamic range is
actually increased to five orders of magnitude.
In addition, the binning of the entire 512 pixels allows the on chip summa-
tion of the pixel charges for increased signal without the penalty of increa-
sing readout noise.
Features
- 13.5 m x 13.5 m pixel size
- Image area 27.6 mm x 6.9 mm
- Back illuminated format for enhanced quantum efficiency (QE)
- Average quantum efficiency of 60% from 165 nm to 800 nm
- Advanced Inverted Mode Operation (AIMO)
- Ideally suited for spectroscopy applications
- High performance STE cooling provides ultra low dark current
- Excellent dynamic range of 5 orders of magnitude
- High speed processing of 1 MHz
- Extremely low readout noise of 3 electrons RMS
- Full binning capability increases speed and reduces noise
- Blooming protection is provided through individual pixel column protec-
tion and readout registers
- Full well capacity of 100,000 electrons
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145

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