X-Ray Presentation
X-Ray Products By Shimadzu
XRF: X-Ray Fluorescence
EDXRF: Energy Dispersive XRF
EDX: Energy Dispersive X-Ray
XRF: Interchangeable with EDX
Shimadzu EDX-720/800/900/GP
Shimadzu uEDX-1200/1300/1400
WDXRF: Wavelength Dispersive XRF
XRF: Wavelength Dispersive X-Ray
Shimadzu XRF-1800 (Call Marketing)
XRD: X-Ray Diffraction
Shimadzu XRD-6000/7000
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© 2007 SHIMADZU
XRF Analysis
EDX & XRF
SAMPLE
(solid, liquid, film)
1. Elements Present
2. Quantitative Analysis
3. Film Thickness
1. Elements Present: Copper, Zinc, Gold, etc.
2. Quantitative: Cu: 25%, Zn: 15%, Au: 60%
3. Film Thickness of Gold on a Copper base.
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© 2007 SHIMADZU
XRD Measures 4 Parameters
1. Phase ID
1. a-Al2O3 vs. g-Al2O3
2. Quantitative
3. Structural information
1. Crystallite size
2. Lattice stress & strain
4. % Crystallinity
XRD
POLYCRYSTALLINE
SAMPLE
Phase ID: Three of the 5 forms or Titanium (TiO2)
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Anatase
Rutile
Brookite
© 2007 SHIMADZU
XRD: Quantitative Analysis & Crystal Structure
Quantitative Analysis:
65% ZnO, 35% MgO
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Crystal Structures:
© 2007 SHIMADZU
Crystalline vs Amorphous
Solid matter is:
Amorphous (random)
Crystalline (regular pattern)
Smallest volume is a unit cell
The Crystal Lattice – La2O3 (cubic)
1 unit cell
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© 2007 SHIMADZU
Percent Crystallinity of Sample
Crystalline and non-crystalline
(amorphous) samples scatter x-rays
differently so the percent of each can be
measured.
Drugs in the crystalline from may be
effective for the problem, but in the noncrystalline from may be ineffective.
What effective does temperature have on
crystallinity? High temp breaks down
crystal? Room temperature vs body temp.
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© 2007 SHIMADZU
Principal of X-Rays
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Excitation of Electrons: X-Ray vs UV-Vis-IR
X-Ray: Excitation of
Inner Shell Electrons
UV-Vis-IR: Excitation of
Outer Shell Electrons
Ionization
E2
E1
Excitation state
E0
Light of frequency v
Electron
Atom ic nuclei
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© 2007 SHIMADZU
Spectra: Wavelength & Electron Volts (eV)
WAVELENGTH SCALE
ENERGY SCALE
0.7
0.7
0.6
0.6
0.5
0.5
0.4
0.4
Absorban
ce
Absorbance
0.3
0.3
0.2
0.2
0.1
0.1
0
300.0
320.0
340.0
360.0
Wavelength (nm)
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380.0
400.0
RawData ...
0
3.100 3.300 3.500 3.700 3.900 4.100
eV
© 2007 SHIMADZU
Types of X-Rays for EDX
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EDX Series
EDX-GP
EDX & mEDX
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EDX Schematic
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Components of EDX-720/800/900
Liquid N2 Dewar (720/800)
Sample Chamber
Detector and MCA
X-ray tube
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© 2007 SHIMADZU
Question 1a: What Elements Need to be Measured?
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Question 1b: What Level Need to be Measured?
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Question 2: Will Viewing Area of Sample
Change? Picture Required?
Collimator:
1, 3, 5, & 10 mm Spots
Shown by Green
Rings
CCD Camera
Save Picture of
Sample Area
Easy Position of
Sample
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© 2007 SHIMADZU
Question 3: Autosampler Required?
Requires Turret Drive
Unit (212-22685-91)
4 Types of Turrets
16 Sample Solid (32
mm)
16 Sample Liquid (32
mm)
8 Sample Solid (52
mm
8 Sample Solid
w/Spinner for nonhomogenous samples
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© 2007 SHIMADZU
Question 4: Analysis Light Elements
(2nd or 3rd Row in Period Table)
Solids
Vacuum Unit
212-22460-00
Increase Sensitivity of
Light Elements
NOT for uses with
water, oils, or
powders
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Liquids & Powders
Helium Purge Kit
212-22495-01
Increase Sensitivity of
Light Elements
USED with water,
oils, & powders
© 2007 SHIMADZU
Vacuum & He Purge for 6C to 17Cl
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© 2007 SHIMADZU
Questions 5-7: Other Accessories
5) Does customer need Precision stage?
X-Y stage for fine
positioning of sample
Requires CCD Camera
& Collimator
6) Liquid Nitrogen Start Up Required?
Gloves, Dewar, & Transfer Tube
7) Standards Required?
Mostly for RoHS Application
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© 2007 SHIMADZU
EDX Configurator to do a Quote
www.ssi.shimadzu.com and select “Product
Gateway”, then “X-ray Instruments” and click on
the “EDX Configurator”
All part numbers for main body and accessories
will be provided
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Select The EDX Model
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EDX-GP for RoHS
Similar to EDX-720 (13Al to 92U)
Standard: CCD and Collimator
No: Vacuum, Helium Purge, or Autosampler
Square Sample Compartment
RoHS (Restriction of Hazardous Substances
Electronics Industry
Pb, Hg, Cd, Cr, Br (more to be added in future)
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No Destructive Acceptance Test
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EDX-GP Schematic
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EDX-GP Includes Special RoHS Software
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Select the Proper uEDX
Feature
uEDX-1200
uEDX-1300
uEDX-1400
Element Range
13Al-92U
11Na-92U
13Al-92U
Detector
Si(Li)
Si(Li)
Si-Drift
Detector Window
Beryllium
Polycarbonate
Beryllium
Detector Cooling
Liquid N2
Liquid N2
Peltier
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Detector Types and Features
Si (Li)
Excellent energy resolution
Good count rates
Requires liquid nitrogen (or Peltier cooling)
Si-drift
Good energy resolution
Excellent count rates
No liquid nitrogen
PIN Diode
Poor energy resolution
Good count rates
No liquid nitrogen
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Detector Signal Processing
Detector current pulses  Counts or “cps”
Pulses are segregated into channels
according to energy via the MCA (MultiChannel Analyser).
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5 Filters as Standard
No Filter
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Al Filter
© 2007 SHIMADZU
Applications of EDX 1
Electrical & Electronic Components
Regulated Substances, Thin Films, Defects
Chemical Industry
Organic & Inorganic Material, Catalyst,
Paints, Pigments, Rubbers, & Plastics
Petroleum & Petrochemical
Ni, V, S in Oils, Dopants & Contaminants
Building & Construction
Ceramic, Cements, Glasses, Bricks, & Clays
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Applications of EDX 2
Agriculture & Food Products
Soils, Fertilizers, Foods
Iron, Steel, & Nonferrous Metals
Impurities in Raw Material, Alloys, Solders,
Precious Metal
Machinery & Automobiles
End of Life Vehicle (ELV)
Environmental
Analysis of Soil, Effluent, Ashes, and Filters
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Applications of uEX
Electronic Material& Components
Composition & Thickness of films, plating
Chemical Engineering & Chemicals
Catalyst, Scale & Sediment, Cosmetic, Dyes
Oil and Coal
Petroleum, Oils, Coal, Coke
Ceramics
Pharmaceutical, Food, Agriculture
Paper & Pulp (Coated Paper, Talc, Toner)
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XRD-6000 and XRD-7000
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© 2007 SHIMADZU
Principals of XRD
Bragg’s law is a simplistic model to
understand what conditions are required for
diffraction.
  2d hkl sin 
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

dhkl dhkl
Wavelength from X-Ray tube type.
Angle from where peaks are located.
D is space which is matched to
standards or databases.
© 2007 SHIMADZU
Example of XRD-6000 Design: Theta/2 Theta
Sample and Detector move in 1:2 ratio with respect to distance
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© 2007 SHIMADZU
Example of XRD-7000 Design: Theta/Theta
X-Ray Source and Detector move in 1:1 ratio with respect to distance
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XRD-6000 & XRD-7000 Specs
XRD-6000
185 mm
sample to
detector
±0.001º
degrees
resolution
XRD-7000
200-275 mm
sample to
detector
±0.0002º
degrees
resolution
Sales
185 mm sample to detec
distance
20:1 – 6K vs 7K
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© 2007 SHIMADZU
XRD-7000 Theta/Theta
/ geometry
Sample fixed
horizontal
Adjustable radius
Improved
resolution
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© 2007 SHIMADZU
XRD Most Commonly Used in w/RED DOT
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X-Ray Tubes
X-Ray Tube Elements: Usually Cu
Other: Co, Fe, Cr, Mo, W (Substitutes Before PO)
X-Ray Tube Spot Size (Substitutes Before PO)
Normal Focus (NF)
Long Fine Focus (LFF)
Fine Focus (FF)
Broad Focus (BF)
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© 2007 SHIMADZU
Qualitative Analysis: Counter Monochromator
Allows only K(alpha) Rays to
Detector
Eliminates K(beta) and
Continuous X-Rays
Increase S/N ratio
Sold with almost every XRD
Counter Monochromator must
match X-ray tube (Cu, Co, Fe,
Cr)
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© 2007 SHIMADZU
Qualitative Analysis: Software
Shimadzu’s Auto Search (Standard)
Very Limited Database
ICDD’s PDF Series (Most Popular)
PDF 2: Size 219,000 records
PDF 4/Organics: 371,000
PDF2 Search Software used w/PDF 2 & 4
MDI’s JADE (Not Recommend)
Pattern Processing, ID, & Quantification
Can Access PDF files,
Training is in CA, USA only (customer pays)
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© 2007 SHIMADZU
Quantitative Analysis: Rotational Stage
RS-1001
Rotates Sample
Minimizes Scatter
Eliminates Crystalline
Orientation
Improves Precision
No Rotation
Rotation 90
Degrees
Rotation 45, 90,
135 Degrees
Rotation Full
360 Degrees
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© 2007 SHIMADZU
Quantitative Analysis: Environmental Analysis
RS-2001
Environmental Stage
Filter Holder
Software
Asbestos Analysis
Similar to Rotation
Stage
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© 2007 SHIMADZU
Automatic Analysis
ASC-1001
Auto 5 Position
Sample Changer
Sample Rotation like
RS-1001
Optional Environmental
Stage Holders like RS2001
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© 2007 SHIMADZU
Thin Film Analysis
THA-1101
Thin Film Sample Stage
Monochromator
Suction Pump to hold
samples in place
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© 2007 SHIMADZU
Heating or Cooling Samples
TTK-450
Heat Sample During
Diffraction
Observe the
Crystalline Structure
Heating: +450 C
Cooling: - 180C
Air, Inert Gas, or
Vacuum
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© 2007 SHIMADZU
Sample Holders (Optional)
1.
2.
3.
4.
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Standard with XRD – Use if need extras
No Metal Interference
No Metal Interference, Limit Sample
No Interferences
© 2007 SHIMADZU