Application Note

Materials

Non-Destructive Analysis of
Substrates and Contaminants by FTIR
with Specular Reflectance Interface
Cleanliness-testing of materials using Agilent 4300
handheld FTIR spectrometer to prevent
downstream issues

Author Abstract
Leung Tang
Verifying that substrates are clean before they are bonded to another material or
Agilent Technologies, Inc.
coated with a protective layer is a critical application. Contaminants, such as trace
oils, can compromise a substrate’s surface by negatively affecting the stiction
(static friction) properties of the material. Low stiction adversely affects the bond
strength of glues and coating adhesion for paints, leading to premature wear and the
potential failure of the material.
This study shows that the Agilent 4300 handheld FTIR spectrometer fitted with
the specular reflectance interface can identify substrate materials, evaluate the
presence of contaminants, and quantify contaminants. The instrumentation can also
be used to determine the presence of chemicals and confirm the chemical condition
of surface agents. As a fast, non-destructive technique, the 4300 FTIR enables large
samples to be analyzed in-situ, without any damage to the substrate. Measurement
times are typically less than 30 seconds per result and the results are displayed in a
clear format on the screen of the 4300 handheld FTIR.
Introduction In this study, the 4300 handheld FTIR spectrometer with
specular reflectance interface was used to detect a range
In materials science, the condition and cleanliness of first of contaminants on the surface of a glass-lined vessel.
produced substrates and materials is vitally important, A quantitative method was also developed to predict the
especially if they are to be further bonded to another concentration of a PTFE-based release agent formulation
component or coated with a protective layer. Chemical on aluminum.
adhesives are increasingly used to replace or supplement
mechanical fixing methods as they can provide strong bonds, Experimental
but only if the surfaces of the components are clean and
free of contamination. Compared to mechanical fasteners, Selection of the sampling interface for the handheld FTIR
chemical glues reduce the weight of the assembled parts There are many ways to measure samples using a 4300
and ensure a more uniform distribution of stresses over the handheld FTIR spectrometer. In all cases, the IR light from
bonded area. the spectrometer must interact with the sample and then
In many industrial and engineering processes, extensive be directed to the detector. The IR beam interacts differently
cleaning procedures have been developed for critical bonding with the sample depending on which of the interchangeable
applications. It has been shown that even small deviations in sampling interfaces is used with the 4300 FTIR:
these cleaning procedures can produce substandard bonds.1, 2 – Attenuated total (internal) reflectance (ATR)
To guarantee strong bonding, surfaces should be analytically
– Diamond
tested and confirmed before the application of adhesives to
confirm their cleanliness. A good testing technique should – Germanium
be non-destructive, identify and quantify contaminants, and – Transmission
ideally be field deployable. The technique must also have the
– External reflectance
sensitivity required to measure low levels of contamination
that would adversely affect the bonding between surfaces. – Specular 45° cone half-angle (CHA)
Another application area that requires a high level of – Diffuse
cleanliness includes the coated or uncoated surface – Grazing angle
of reaction vessels used in manufacturing processes.
The wide choice of interchangeable sampling interfaces
Contamination arising from surface coatings such as metals,
available for the 4300 FTIR enables the handheld
alloys, treated metal, or glass lined metals can adversely
spectrometer to examine and measure samples
affect the chemical reaction or yield of the product.
nondestructively and in situ. The 4300 has been used to
Infrared (IR) spectroscopy is a non-destructive method that analyze samples that are atypical for FTIR, such as minerals,
can identify and quantify many substrates, materials, and concrete, and coatings.3
contaminants. Virtually all organic chemicals and many
For the analysis of glass and metal-based substrates, both
inorganic chemicals can be measured by IR. When fitted
the ATR internal reflectance and transmission techniques are
with a specular reflectance interface, IR is sensitive enough
unsuitable. For ATR, it is difficult to establish good contact
to measure contaminants on reflective and non-reflective
between the ATR crystal and the surface of hard or brittle
surfaces at low levels.
substrates, while for transmission, IR light cannot transmit
The Agilent 4300 handheld FTIR spectrometer fitted through opaque materials. Also for ATR, the short penetration
with the specular reflectance interface is capable of the of the IR beam in the substrate results in a high limit of
nondestructive identification and quantification of many detection (LOD).
substrates and contaminants. Before coating or bonding of
The external reflectance interfaces are suitable for the
materials, the 4300 FTIR can be used to analyze components
measurement of various substrates. Figure 1 shows an
of virtually any size. The high sensitivity of the 4300 FTIR
overview of the range of materials that have been measured
provides trace level detection of contaminants at pre-,
by the 4300 FTIR fitted with an external reflectance
mid-, and post-cleaning stages. The fast scan times of the
interface and includes a short list of typical applications of
instrument, typically less than 30 seconds per result, enable
the technique.
multiple positions on the substrate to be analyzed quickly. The
instrument is also designed to be directionally ambivalent and
robust, simplifying its use.

2
 Metal and alloys Glass and ceramics Composites and hybrids

Polymer and elastomers Textiles and fabrics Concrete and minerals

Contamination
Degree of cure
Coatings
Composition
Degradation
Oxide thickness
Wood and laminates
Figure 1. Types of substrates that have been measured by Agilent 4300 FTIR fitted with an external reflectance interface and a summary list of
typical applications of the technique.

Specular reflectance interface

In this study, the 4300 handheld FTIR was fitted with the
45° specular reflectance sampling interface (Figure 2). The 45° Specular
technique is suited to the analysis of a wide range of surfaces reflectance
with moderate-to-high reflectivity such as glass and metal,
but also carbon fiber reinforced polymer (CFRP), which has
low‑to-moderate reflectivity. Figure 3 shows example spectra
obtained using the instrumentation for CFRP, amorphous
silicon on stainless steel, functionalized silicon oxide on
stainless steel, stainless steel, and aluminum.
The specular reflectance interface is a "point and shoot" S D
technique that does not require any force to be applied
between the interface and sample during data acquisition. Figure 2. Left: the 45° specular reflectance interface with nonmarking
Spectral quality is not affected by poor contact with the clear fluorinated ethylene propylene (FEP) coated orange silicone O-ring.
Right: schematic showing the principles of the technique, often referred
sample, unlike ATR. The front clear-coated orange O-ring to as infrared reflection-absorption spectroscopy (IRRAS); S=Source and
ensures the correct distance to the sample. D=Detector.

3
 Results and discussion
Identification of contaminants
The 4300 FTIR fitted with the specular reflectance sampling
interface was used to analyze the surface of the clean
glass‑lined vessel and each of the lubricants added to the
surface of the vessel. Each measurement (64 scans) took
16 seconds at 8 cm–1 resolution. Figure 4 shows the averaged
spectra for the clean glass-lined vessel and for each of the six
lubricants applied to the surface of the vessel. The spectra
show that the method can easily detect the presence and
type of contaminants (in this case, lubricant/release agent) on
Figure 3. Spectra collected using an Agilent 4300 handheld FTIR the surface of the glass-lined vessel.
spectrometer fitted with the 45° specular reflectance sampling interface
shown in Figure 2. a) Carbon fiber reinforced polymer (CFRP), b) amorphous
silicon on stainless steel, (c) functionalized silicon oxide on stainless steel,
(d) stainless steel, (e) aluminum, and (f) mirror background cap for the
4300 handheld FTIR (part number G8180-67562).

When reflective surfaces are analyzed by IR, the typical

measurement configuration is known as infrared reflection-
absorption spectroscopy (IRRAS). Using IRRAS, the light from
the spectrometer passes once through the sample, reflects
off the reflective or semi-reflective surface, and then passes
through the sample a second time, before being collected by
the detector (Figure 2, right). Since the 4300 handheld FTIR
is a Fourier transform instrument, scans can be co-added to
Figure 4. Agilent 4300 FTIR specular reflectance spectra for a) clean glass
both improve the signal-to-noise (SNR) and the LOD of the vessel, b) adhesive lubricant, c) multipurpose lubricant, d) PTFE aerosol,
measurements. The penetration of IR light into the sample e) silicone oil, f) white mineral oil, and g) multipurpose 3-in-1 lubricant.
depends on the material being tested.
There are many differences in the spectra (Figure 4),
Samples especially in the CH stretching mode-region, around 3,000
For the qualitative study (identification of the presence of to 2,800 cm–1, as well as in the fingerprint region. If needed,
contaminants), a clean glass lined vessel was lightly smeared it would be quick and simple to construct a library search
with lubricant. A few milligrams of lubricant were spread of the spectra to identify the compounds or formulations.
thinly over an area of the vessel until it was no longer visible. This would provide a qualitative answer for the presence
To simulate potential contaminants, a range of different or absence of contamination. For successful quantitative
lubricants and release agents were added in turn to the analysis of contaminants on substrates by FTIR, the
clean vessel. The lubricants included an adhesive lubricant, a instrument needs to provide sufficient sensitivity and
multipurpose lubricant, a PTFE aerosol mold-release agent, selectivity, as required by industry. To demonstrate the
silicone oil, white mineral oil, and a 3-in-1 product. quantitative capabilities of the 4300 FTIR, two quantitative
For the quantitative contamination study, varying amounts models were created for the analysis of PTFE-contaminated
of the PTFE aerosol mold-release agent, carefully weighed Al coupons.
to 0.01 mg on a 5-digit balance, were applied to aluminum Quantitative measurements
(Al) coupons, as detailed in Table 1. All coupons were 40.85 ×
The 4300 FTIR fitted with the specular reflectance sampling
50.80 mm. A clean, blank Al coupon was also prepared. The
interface acquired multiple measurements (replicate
clean coupon was cleaned using three wet wipes and an
number >10 for each sample) of the blank (clean) Al coupon
ethanol wash, and then dried with a lint free tissue.
(sample 7) and six PTFE-contaminated Al coupons (samples
1 to 6). The contamination levels of PTFE on the Al coupons
were calculated as shown in Table 1.

4
Table 1. Reference samples of PTFE contaminated The spectral features can be modeled univariately using
Al coupons. the MicroLab PC software or by multivariate analysis (MVA)
using Agilent MicroLab Expert software. MVA produces better
ID mg mg/cm2 ug/cm2
LODs and the MicroLab Expert software provides a wider
1 10.28 0.495422 495.4217
range of statistical testing options, so MVA was used in this
2 3.40 0.163855 163.8554
study. (Results obtained using the univariate model diverged
3 1.92 0.09253 92.53012
significantly from Beer-lambert assumptions and were not
4 0.69 0.033253 33.25301
applicable to the IRRAS technique.)
5 0.18 0.008675 8.674699

6 0.08 0.003855 3.855422 Using the partial least squares (PLS1) MVA in MicroLab
7 0 0 0
Expert with a 4:1 split in the training data for calibration
and validation, two models were created: one global model
The averaged spectra obtained by FTIR for each (Figure 6) and a model for the lower concentration range of
PTFE‑concentration level are shown in Figure 5. Because PTFE contamination (Figure 7).
stacking the spectra compresses the data’s Y-axis, overlaid
spectra of Al coupons 5, 6, and 7 are shown in the lower y = 0.9825x + 0.0012
R2 = 0.9911
graph. The features present in the clean Al coupon (sample 7)
are due to physisorbed (physical adsorption) water and the
native aluminum oxide.

Figure 6. PLS1 MVA model based on samples 1 to 7 (low to high range

model). The calibration data are shown by the black circles and validation
spectra by the blue diamonds. The green square is the region of the lower
range model.

When the analyte level spans a large range, a discrete low

range model is often beneficial. Using all the spectra from
samples 4, 5, 6, and 7, a second model was created using the
MicroLab Expert software, as shown in Figure 7.

Figure 5. Agilent 4300 handheld FTIR spectra of varying concentrations of

PTFE on aluminum. Top: Samples 1 to 7 stacked. Bottom: Samples 5, 6, and
7 overlaid. Sample 7 is the clean Al coupon.

5
 – Automatically apply the correct model (if there is more
y = 0.9874x + 0.0001 than one), and when several models are available,
R2 = 0.9868
the software can be directed to show the most
appropriate result.
– Display the results using a user definable traffic light
system, enabling quick and easy interpretation of the data.
For a closer inspection of the predicted values of PTFE on Al,
a table of all the spectra collected for PTFE samples 4 to 7
that have been reprocessed by the lower range PLS1 model
(Table 2). Although the method was approaching the limits
of the 5-digit balance, the model can clearly still predict the
lowest standards. The boxplot in Figure 8, which displays
each spectral result with the statistical boxplot, confirms the
effectiveness of the method for the quantification of PTFE
on aluminum.
Figure 7. Lower range PLS1 model for PTFE on Al (based on spectra Table 2. Predicted values for each spectra of PTFE on Al coupons 4, 5, 6,
acquired for samples 4, 5, 6, and 7). The calibration data are shown by the and 7.
black circles and validation spectra by the blue diamonds.
Coupon 7 Coupon 6 Coupon 5 Coupon 4
Both these models can be implemented into a single method Actual 0 0.003855 0.008675 0.033253
to predict the level of PTFE lubricant on aluminum. There are –0.00032 0.00395 0.00641 0.03460
three types of analytical methods that can be selected in the –0.00010 0.00369 0.00865 0.03699
MicroLab PC software: 0.00048 0.00396 0.01180 0.03170
–0.00121 0.00295 0.00596 0.03511
– Spectral Collection: data collection of spectra.
–0.00058 0.00363 0.01099 0.03430
– Qualitative Search: where the spectral data are checked
–0.00131 0.00541 0.00663 0.03042
against a spectral library for identification of compounds
0.00089 0.00511 0.01033 0.03250
or formulations.
–0.00064 0.00169 0.00808 0.03374
– Components: an interrogation of the spectra by any one –0.00067 0.00510 0.00717 0.03275
Predicted
or combination of peak area, peak height, peak ratio, SNR, 0.00107 0.00484 0.00872 0.03409
center of gravity, and also application of a wide range of 0.00066 0.00575 0.00904 0.03634
mathematical models ranging from Beer-Lambert type N/A N/A 0.00854 0.03360
basic models to PLS1-MVA modeling. A well-trained N/A N/A N/A 0.03403
and validated model enables the software to predict the N/A N/A N/A 0.03368
level of a measured quantity of the analyte, providing N/A N/A N/A 0.03291
quantitative data. More than one trained model can be N/A N/A N/A 0.03125
queried in a single method. N/A N/A N/A 0.02885

Once established, the method and its model or models can N/A N/A N/A 0.03117

then be transferred to the MicroLab Mobile software of the Average –0.00016 0.00419 0.00853 0.03322

4300 handheld FTIR (and/or still be used from the MicroLab Standard
0.00079 0.00115 0.00176 0.00198
Deviation
PC software with a laptop). Both MicroLab Mobile software or
MicroLab PC software will both provide step-by-step graphical
instructions, and can be tailored to:
– Check that the 4300 is fitted with the correct interface, as
required by the method.
– Warn of poor alignment to the surface.

6
 Spectra
A quantitative method was also developed using the
0.04 Max PTFE-based aerosol release agent deposited on aluminum
3rd Quartile coupons. By analyzing accurately weighed amounts of PTFE
Median line
Average (box) by FTIR, the Agilent MicroLab Expert software and a PLS1
Min 1st Quartile
0.03
multivariate analysis (MVA) modeling technique was used
to create a quantitative method. Two MVA models were
mg/cm2 PTFE

0.02
developed based on spitting the model training set spectra
into roughly three-quarters calibration and one-quarter
validation. Both models were implemented and incorporated
0.01 into a single method for the handheld 4300 FTIR.
This method could be used to directly measure PTFE release
0
agent on a coupon in a force-free and non-destructive
manner. Each measured position would lead to a discrete
predicted value that can be color-coded to suit the user's
-0.01 requirements for cleanliness. The method could also be used
7 6 5 4
to check the presence and chemical condition of PTFE in
Figure 8. The boxplot and values of PTFE on Al coupons 4, 5, 6, and 7. a mold.
The efficacy of cleaning procedures can now be performed
A previous study was done on the quantification of a
at-site or on-site using the sensitive 4300 FTIR spectrometer.
silicone‑based release agent on the surface of a CFRP
The handheld 4300 weighs ~2 kg with batteries, so is portable
substrate, where the substrate was a cured epoxy-based
and easy to handle, and a simplified graphical user interface
carbon composite.2 That study required more intense
ensures its ease-of-use by nonexpert operators.
pre‑processing of the data to enable model compensation
of variances in the resin:fiber ratio. The same level of The study has shown that the 4300 FTIR coupled with the
pre‑processing was not required for the PFTE on Al data. specular reflectance interface provides a highly tailorable
and flexible solution for on-site cleanliness testing of a wide
Both the full range and the low range PTFE on Al models
variety of substrates. The system can be used for qualitative
required minimal pre-processing of the model training data to
testing of contaminants or models can be trained to quantify
provide excellent model statistics. Industrial uses of metals
for a specific contaminant or multiple contaminants,
bonded to glass fiber reinforced polymer (GFRP) or CFRP are
providing quality assurance for critical bonding applications.
increasing, as they provide a good balance of strength and
weight. For these applications, the cleanliness of the metal
(typically Al because of its lightweight properties) before
References
application of the GFRP or CFRP layer is critical. 1. Extended Non-Destructive Testing of Composite Bonds
(ENCOMB), FP7, CORDIS, European Commission
Conclusion (europa.eu), accessed April 2023, https://cordis.europa.
eu/project/id/266226/reporting
The Agilent 4300 handheld FTIR spectrometer fitted with a
specular reflectance sampling interface was used for the 2. Tang, P. L.; Rein, A. Quantification of Release Agent on a
qualitative study of a variety of substrates and common Carbon-Fiber-Reinforced Polymer using a Handheld FTIR,
lubricant and aerosol release agents. Spectra were all Agilent Technologies application note, publication number
collected from the samples at multiple sites and orientations 5991-5595EN, 2018.
and all samples were shown to be spectrally distinct. 3. Tang, P. L., Comparison of Portable FTIR Interface
Technologies for the Analysis of Paints, Minerals
& Concrete, Agilent Technologies application note,
publication number 5991‑8359EN, 2017.

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Printed in the USA, May 24, 2023
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