MIRacle Manual
MIRacle Manual
MIRacle Manual
Jan. 1, 2015
(608) 274-2721
(608) 274-0103
[email protected]
www.piketech.com
Contents
Introduction
MIRacle ATR Accessory
MIRacle Pressure Clamp Options
MIRacle Universal Plate Options
Installation
Accessory Adjustment
Performance Verification
Sampling Procedures
Configuration for Liquid Sampling
Configuration for Solid Sampling
Pressure Clamp Tip Attachments
Micrometer Pressure Clamp
High-Pressure Clamps
High-Pressure Clamp Installation
Crystal Cleaning
ATR Spectrum
ATR Correction
Liquid Samples
Solid Samples
Useful Equations
Materials
Zinc Selenide
Germanium
Silicon
Diamond
Specifications
Effects of Temperature
Precautions
Mirrors
SAFETY
Replacement Parts and Options
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Introduction
The PIKE Technologies MIRacle is a patented Universal Sampling Accessory designed for single- or
multi-reflection attenuated total reflectance (ATR) and specular reflectance measurements with FTIR
spectrometers. The accessory features a unique optical design (US.PAT: 5,965,889 and 6,128,075), which
provides exceptional sensitivity and IR throughput. The single-reflection sampling plate of the accessory
has a 1.8 mm round crystal surface allowing reliable analysis of small samples. Solid materials can be put
into intimate physical contact with the sampling area through high-pressure clamping, yielding highquality, reproducible spectra.
ATR crystal plates come in several configurations, including ZnSe, Ge, Si or diamond. The first three
options are suitable for analysis of liquids, semi-liquid materials and pliable solids. The Si or diamond
configurations should be used when working with reactive samples and/or abrasive solid materials that
need to be pressed hard against the crystal. Single-reflection ATR works very well for the analysis of
relatively strong absorbing substances (e.g. polymers, rubber, paint chips, fibers, etc.). Highly absorbing
samples, such as black rubber, are best analyzed using the Ge plate due to its lower depth of
penetration. Acidic samples are best handled with Ge, Si or diamond crystal plates. For samples with
relatively lower absorption characteristics or when trace elements are present, the 3 reflection ATR
plates are also available in most crystal materials. Also, the MIRacle specular-reflectance plate provides
even more flexibility for 45 specular reflectance work without the need to change the accessory base.
The compact design of the accessory employs a transfer mirror to direct the infrared beam to one end of
an IR transmitting ATR crystal. A second mirror directs the beam emitted from the other end of the
MIRacle plate to the detector built into your FTIR spectrometer. The MIRacle features a universal
sampling plate design that eliminates the need for separate trough and flat plates, such as normally
required in ATR for handling liquid and solid samples, respectively. The accessory can be equipped with
a wide choice of compression clamps including micrometer controlled, high-pressure, rotating high
pressure and digital readout high-pressure. Included as standard are the base optics assembly with
purge tubes specific to your FTIR spectrometer model, purge tubing attachments and adjustment
wrench set. Add to this your choice of MIRacle universal plate(s) and pressure clamp(s), all of which are
easily interchangeable.
Crystal Plate
Sampling Area
Pressure Tip
Figure 1. High-Pressure Clamp
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* The MIRacle base optics assembly has the crystal plate and purge tubes attached to the base. Some
base optics assemblies may appear different (such as adjustment screw locations and mounting scheme).
The purge tubing kit, wrench set, pressure clamp and tips are packed separately in the carrying case. The
purge tubing kit is not included with some models equipped with recognition bases. The flat tip is
attached to the sample clamp assembly, and the flat and swivel tips are included with the packaging.
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High-Pressure Clamp
Micrometer Clamp
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NOTE: Tip of swivel tips and 3 reflection plates for Micrometer clamp are made of
(white) plastic; Swivel tip for High-Pressure clamps are stainless steel. Depending
upon specific clamp, the pressure tips may appear different than the picture.
Installation
The MIRacle accessory has been aligned and tested in the PIKE Technologies facility to ensure that it
performs to specifications. However, some variation in optical alignment can occur from spectrometer
to spectrometer. To allow for this difference, there are four alignment screws provided on the MIRacle
base optics assembly for fine-tuning once the accessory is installed in the spectrometer. The following is
the procedure for accessory installation and final alignment.
1. The MIRacle accessory fits into the sample compartment of the FTIR spectrometer. Your MIRacle is
set to an appropriate configuration to fit the sample compartment of the FTIR instrument you
specified. Before inserting the accessory in the sample compartment, ensure that your spectrometer
is aligned. If the instrument is not aligned, follow the manufacturers instructions for maximizing the
interferogram signal (the IR energy throughput) of your FTIR spectrometer. In order to locate the
accessory in the correct position, simply place the entire accessory into the FTIR sample
compartment with the PIKE MIRacle label facing the front and line up the base plate provided with
the holes/pins in your FTIR Spectrometer.
2. Fasten the accessory onto the FTIR sample compartment base plate using the captive screw(s)
located on the MIRacle base plate (some accessories may have two mounting screws or a mounting
screw/pin combination, depending on spectrometer configuration).
3. Tighten the captive mounting screw (with flat head screwdriver or by hand) to firmly position the
accessory base onto the FTIR sample compartment base plate. The MIRacle accessory is now ready
for optical alignment.
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Accessory Adjustment
The MIRacle accessory may not require any alignment when installed. However, should you choose to
fine-tune the accessory, refer to this figure and follow these steps:
1. Display the live interferogram on the spectrometer monitor and using the thumbscrews on the left
and right side of the accessory (angle adjustment), adjust the mirrors until the highest throughput is
achieved. To do this, turn the screws one at a time slightly and check the signal. If it increases,
reverse turn until the maximum signal is obtained.
2. Insert the enclosed hex wrench in the two height adjustment screws on the top of the accessory.
Adjust the screws one at a time until the highest throughput is obtained.
3. Repeat the entire procedure two or three times to fine-tune the accessory.
NOTE: For some side focus FTIR models, both thumbscrews are located on the right side of the MIRacle
base optics assembly.
This is a one-time alignment procedure that optimizes the MIRacle to work with an individual optical
bench. Once completed, the alignment does not have to be repeated unless the accessory adjustments
have been moved or it has been placed in a different FTIR instrument. You are now ready to verify the
MIRacle optical throughput performance.
Height Adjustment
Angle Adjustment
Figure 4. Fine-tuning the MIRacle accessory
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Performance Verification
1. With the accessory removed from the sample compartment, collect an open beam background
spectrum.
2. Place the MIRacle accessory in the instrument per installation steps described on page 4.
3. Collect a spectrum of the MIRacle ATR using the same collection parameters as used to collect the
background spectrum.
The following are the % transmission values the accessory should achieve with different crystal
configurations at 1000 cm-1 (with the exception of the Si value which is shown at 2000 cm-1).
ZnSe single reflection ATR plate Greater than 22%T
Ge single reflection ATR plate Greater than 25%T
Diamond w/ZnSe lens single reflection ATR plate Greater than 25%T
ZnSe 3 reflection ATR plate Greater than 12%T
Diamond w/ZnSe lens 3 reflection ATR plate Greater than 12%T
Specular-reflectance plate Greater than 20%T
The MIRacle ATR throughput spectra appear different and show different spectral features depending
upon the crystal material. One notable feature is the spectra range cut-off (where IR throughput goes to
zero) at the long wavelength end of the spectrum (near 400 cm-1).
In the spectrum shown for the ZnSe crystal plate the long wavelength cut-off is about 520 cm-1. Also
shown in this spectrum is that the IR throughput is about 32% at 1000 cm-1.
A feature in the diamond ATR crystal plates and present in the spectrum shown on the following page is
known as the diamond phonon broad IR absorbance bands, which appear, between 2600 and 1900 cm-1.
This is a normal absorbance present in all diamond spectra. This feature ratios well in a typical sample
spectrum. It does, however, reduce the signal-to-noise ratio (SNR) in this spectral region.
If your accessory does not meet this minimum transmission level, please contact PIKE Technologies.
Before calling, please record the serial number located on the label on the back of the MIRacle base
optics assembly.
NOTE: IR throughput performance of your accessory will decrease slowly over time as the lens surface is
exposed to the environment and due to normal wear from cleaning the ATR surface. Contact PIKE
Technologies for information about MIRacle Crystal Plate reconditioning services when throughput drops
below a usable level.
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Sampling Procedures
The spectrum of the required sample is obtained by ratioing a scan with a sample in place to a scan with
no sample on the face of the crystal. The crystal mount is located on the base unit. The MIRacle ATR can
be used for all types of samples (liquids, pastes, soft pliable films, powders and solids).
Liquids Retainer
An optional liquids retainer and volatiles cover are available for quickly evaporating liquid samples. For
volatile liquids, the liquid retainer with volatiles cover reduces the amount of evaporation of the sample
on the surface of the crystal. To use, place the retainer disk over the ATR crystal. Place the U-shaped
bridge over the retainer disk. Apply pressure to the U-shaped bridge using the pressure clamp. Fill the
reservoir of the liquid retainer with the volatile liquid. Slide the volatile cover between the retainer disk
and the U-shaped bridge. Liquids retainer may be used with the high-pressure clamp only.
NOTE: Some crystals used in the accessory are made of fairly brittle materials (such as ZnSe, Si, or Ge).
Scratches on the surface of the crystal will result in a reduction in the throughput of the accessory.
Remove the sample gently with a non-abrasive cotton tissue and rinse with solvent. For more thorough
cleaning, the crystal plate should be cleaned with an appropriate mild solvent such as isopropyl alcohol
or a stronger solvent, such as acetone. Cotton swabs are highly recommended for ease of cleaning
without scratching the soft ATR surface. Sometimes carry over may occur from one sample to another
due to incomplete cleaning of a prior sample from the face of the crystal. Samples should not be left in
contact with the crystal for an extended period of time since some samples may degrade the crystal
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material and discoloration of the metal plate can occur. Once the measurement has been made, remove
the sample from the crystal and clean the surface of the crystal and the surrounding plate area with a
suitable solvent.
NOTE: The MIRacle high-pressure clamps have the ability to swing sideways for ease of accessing the
crystal surface for cleaning.
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Swivel Tip
Flat Tip
Concave Tip
The success of an ATR measurement depends upon the quality of the contact between the sample and
the crystal. Since there is an infinite number of sample shapes and types, a single configuration of the
sample press tip may not be adequate. For this reason, the MIRacle pressure clamp is designed to
accept three different tip attachments, providing the best possible configuration for any given sample.
In addition, the 3 reflection ATR plates are provided with a special plastic swivel tip matching its 6 mm
diameter crystal size.
The swivel tip features an end cap mounted onto a small ball joint. Such design allows the press tip to
move and adjust its position to the shape of the sample and maintain the sample position parallel to the
crystal surface. This tip allows for better positioning and optimal contact of thin materials with the ATR
crystal surface. The swivel tip is used with irregularly shaped samples, films, semi-rigid polymers.
The flat tip attachment is a flat-tipped cone and it is used when analyzing thin films, fibers, small
particles, rubber samples and other elastic polymers. The flat tip may also be used for powdered
samples.
The concave tip was developed specifically to work with granules, large beads and polymer pellets.
The tip features a concave surface, which prevents the sample from escaping from underneath the
press. It also forces the spherical samples to stay in the center of the crystal assuring maximum IR signal
strength. Do not use the concave tip for powdered samples or samples which do not completely protect
the concave edges of the steel tip from pressing against the crystal - this will damage the ATR crystal.
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Pressure (psi)
408
530
693
815
Lighter pressures should be used for soft, flexible samples. Higher pressures are necessary for hard
polymers, bids, granules, etc. (Please see also the note on selection of pressure clamp tips). The
following is a short procedure outlining proper use of the MIRacle micrometer controlled sample clamp
(025-3050):
1. Select the appropriate tip and attach it to the press.
2. Position the sample on the accessory plate.
3. Set the micrometer screw to 2.0.
4. Lower the press barrel with the control knobs, until the edge of the sampling tip touches the lower
brass end of the barrel.
5. Collect the sample spectrum.
Some FTIR spectrometers offer spectrum preview data collection modes. If available, you can
experimentally determine the best pressure for your particular sample by observing the intensity of the
spectrum while adjusting the micrometer screw.
NOTE: The spring in the clamp assembly is not compressed until the micrometer screw is set to 3.5. For
this reason, always keep the micrometer setting between 3.5 and 0.
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High-Pressure Clamps
The high-pressure clamps consist of the base which attaches directly to the accessorys top plate, the
stainless steel pressure tip arm and the pressure control knob with built in slip-clutch mechanism. A
removable anvil is located underneath the pressure module. This anvil is positioned in the center of the
crystal plate and provides direct pressure to the sample. The pressure clamp module rides up and down
on a lead screw located in the clamp column, with its position adjusted by the control knob. The control
knob features a ratchet-type clutch mechanism that controls the maximum allowable pressure and
protects the crystal from over tightening.
Position the clamp on the two dowel pins located on the top plate of the MIRacle accessory.
Please note that the top plate extends approximately 1/4" beyond the MIRacle base. The clamp
mount provides a space to accommodate for this extension. Before the clamp can be fully
mounted on the pins, the plate extension and the groove in the clamp mount must be perfectly
aligned.
2.
Press the clamp down until the pins fully engage. Using a flat head screwdriver, tighten the captive
screws so the clamp is firmly attached to the accessory base.
3.
As with the micrometer pressure clamp, the high-pressure clamps are provided with three
pressure tips; swivel, flat and concave. However, the swivel tip for the high-pressure clamp is
made of metal vs. white plastic due to the higher sampling forces involved.
4.
The high-pressure clamp models are able to swing to the side for ease of cleaning. The slip clutch knob is
used for applying pressure to the sample without over tightening. A detent holds the pressure clamp tip
in place directly over the crystal.
Crystal Cleaning
The solvent used for cleaning your crystal is dependent on the sample that has been analyzed. In all
cases it is best to attempt to clean the crystal with the mildest solvent possible. For most cases, the
preferred solvent is isopropyl alcohol. If a stronger solvent is required, acetone may be used. In all cases
when using solvents, inspect the materials safety data sheet associated with the solvent you are using
and comply with any recommended handling procedures. Apply the solvent to the crystal with a cotton
swab and gently remove using a cotton swab or non-abrasive wipe. Repeat this procedure until all traces
of the sample have been removed. Under no circumstances should the softer crystal materials (ZnSe,
Ge) be rubbed with paper products such as Kleenex or Kimwipes. Many paper products are abrasive
and could cause scratching of the softer crystal surfaces.
CAUTION: Do not submerge the crystal plate or allow liquid to flow over the top of the crystal plate. This
will damage sensitive optics.
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Figure 7. Thick polymer sample FTIR spectrum collected by ATR and transmission
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ATR Correction
If an ATR spectrum representative of a transmission spectrum is desired, the ATR spectrum must be
processed with the ATR correction program available on your spectrometer software. An example of the
effect of this correction on a spectrum is shown in the following example for polystyrene. The middle
spectrum is the original ATR spectrum of polystyrene. The lower spectrum is the transmission spectrum
of polystyrene. Clearly the IR bands around 3000 cm-1 in the ATR spectrum are weaker relative to the IR
bands at longer wavelength.
However, in the upper red spectrum after ATR correction, the relative IR band intensities are very similar
to those from the polystyrene run by transmission.
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Liquid Samples
One minute, 4 cm-1 resolution spectra of a dilute detergent solution and distilled water were collected
using the MIRacle with diamond crystal. These samples were simply applied directly onto the MIRacle
diamond ATR crystal for analysis.
The red spectrum is the detergent solution and the blue spectrum is that for distilled water. A spectral
subtraction can be applied to obtain the spectrum of the detergent component.
Detergent Solution
Distilled H20
Solid Samples
For the analysis of solid samples the pressure clamp of the MIRacle is required. The sample is placed
face down onto the diamond crystal and force is applied to make intimate contact onto the ATR crystal.
The MIRacle accessory enables to position the sample to a feature area to ensure that the spectrum
collected is taken from the desired location on the sample.
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Useful Equations
The depth of penetration gives us a relative measure of the intensity of the resulting spectrum and is
expressed by the following equation:
dp =
2
2 ( n1 sin2 n 22 ) 1/2
Where is the wavelength of light, n1 is the refractive index of the crystal, n2 is the refractive index of
the sample and is the effective angle of incidence.
Depth of penetration in microns as a function of crystal material is shown in the table below. The
penetration depth is calculated for a sample with a refractive index of 1.5 at 1000 cm-1. Also the safe pH
range of samples for use with each material is listed.
Materials
MIRacle
Crystal Plate
Application
Hardness
2
kg/mm
Cuttoff cm ,
Spectral Range
Refractive
Index @
-1
1000 cm
Depth of
Penetration
@ 45,
pH Range
of Sample
-1
Diamond/ZnSe
5700
525
2.4
2.00
114
Ge
550
575
4.0
0.66
114
Si
1150
8900-1500,
475-40
3.4
0.85
112
120
520
2.4
2.00
5-9
ZnSe
NOTE: Quoted spectral range also depends upon the FT-IR spectrometer configuration of source,
beamsplitter, detector and other components.
Zinc Selenide
ZnSe is the preferred replacement for KRS-5 for all routine applications. Its useful spectral range is less
at the low frequency end than that of KRS-5, but the mechanical strength of this rigid, hard crystalline
material is superior. Although a general-purpose material, it has limited use with strong acids and
alkalies. The surface becomes etched during prolonged exposure to extremes of pH (the acceptable pH
range is 5-9).
Note: Complexing agents, such as ammonia and EDTA, will also erode its surface because of the
formation of complexes.
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Germanium
Germanium (Ge) has been used extensively in the past as a higher refractive index material for samples
that have a high refractive index, such as carbon filled samples. The down side of using Ge is the high
refractive index produces a relatively weaker spectral absorbance compared to ZnSe or diamond.
Silicon
Silicon is hard and brittle. It is chemically inert and only strong oxidizers affect it. Silicon is well suited for
applications requiring temperature changes as it withstands thermal shocks better than other ATR
materials. It also is the hardest crystal material offered except for diamond, which makes it well suited
for abrasive samples that might otherwise scratch softer crystal materials. Typically, Silicon crystal is
totally absorbing below 1500 cm-1 making its usefulness in the mid-IR range limited.
Diamond
Diamond is one of the most rugged optical materials. It can be used for analysis of a wide range of
samples, including acids, bases, and oxidizing agents. Diamond is also scratch and abrasion resistant. Its
disadvantage is the cost and the intrinsic absorption from approximately 2300 to 1800 cm-1, which limits
its usefulness in this region (5% transmission).
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Specifications
ATR Crystal Choices
Stainless steel
Angle of Incidence
45 degrees, nominal
1.8 mm
Pressure Device
Maximum Pressure
10,000 psi
Sample Access
Heating Options
Accuracy
+/- 0.5%
Sensor Type
Temperature Control
Input Voltage
Operating Voltage
Accessory Dimensions (W x D x H)
Effects of Temperature
The PIKE Technologies MIRacle utilizes a metallic gasket to seal the crystal to its mount. This sealing
mechanism allows some flexibility and hot samples may be placed on the crystal without damaging the
crystal or seal. However, it is recommended that the temperature difference between the sample and
the crystal be no more than 30 C. So for a crystal at room temperature, the sample may be at a
temperature of up to 50 C. Do not exceed sample temperature greater than 60 C when using the
single reflection diamond MIRacle ATR crystal. Apply only room temperature samples to MIRacle
3 reflection ATR plates. Please contact PIKE Technologies if you wish to place samples of a higher
temperature on the crystal surface. Heated MIRacle plates are also available and can be heated up to
130 C (60 C for diamond).
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Precautions
Mirrors
In order to provide the maximum transmission in the infrared, with the minimum spectral interferences,
the mirrors used in this device are uncoated (bare) aluminum on a glass substrate. Since the coatings are
soft, care must be taken to avoid damage. Normally, these mirrors will not need cleaning, since they are
contained within the housing of the accessory. If they do need cleaning, they may be gently wiped with
a lint-free, abrasive-free cloth, such as lens tissue, or with a camel hairbrush. Under no circumstances
should the mirrors be rubbed with paper products such as Kleenex since this will scratch the mirror
surface resulting in reduced IR throughput.
SAFETY
Caution should be used when handling and using ATR crystals since some of the materials can be
hazardous. Specifically, zinc selenide is a heavy metal material and should be handled with this in mind.
If the crystal is broken or pulverized, the dust may be harmful by inhalation, ingestion or skin
absorption.
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NOTE: To use this option please call PIKE Technologies to get a return material authorization (RMA)
number to send your existing crystal plate to us for restoration to like new condition.
HEATED CRYSTAL PLATES
025-4018
025-4058
025-4108
NOTE: ZnSe and Ge heated plates may be operated to 130 C. Diamond has limited range to 60 C.
Heated plates require PIKE Temperature Controller.
LIQUID JACKETED CRYSTAL PLATES
025-2014
025-2054
025-2094
025-2104
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PRESSURE CLAMPS
025-3020
025-3035
025-3050
076-6025
OTHER
025-3053
025-3099
025-3098
026-5012
026-5013
026-3051
026-5010
Figure 10. The high pressure, Sealed Sample Chamber Clamp for the MIRacle Single Reflection ATR accessory allows
the clamp/crystal plate assembly to be removed from the MIRacle base mounted in the spectrometer to a protective
environment for sample loading and handling. Typical applications include studies of toxic or chemically aggressive
solids and powders. Dedicated Sealed Sample Chamber Clamp crystal plates, available in diamond, ZnSe or Ge, must
be ordered separately.
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6125 Cottonwood Drive Madison, WI 53719-5120 (608) 274-2721 (TEL) (608) 274-0103 (FAX)
[email protected] www.piketech.com