Select Page
Ph. Eur. 2.2.48 Raman Spectroscopy: How Raman instruments from Metrohm comply with the 2022 update

Ph. Eur. 2.2.48 Raman Spectroscopy: How Raman instruments from Metrohm comply with the 2022 update

The European Pharmacopoeia (Ph. Eur.) is a single reference work for the quality control of medicines. Ph. Eur. contains norms, suggests analytical methods, and lists many properties that define quality control (QC) during the production of medicines, the raw materials used, and the instruments required to perform such tests. These official standards are legally binding in several countries – not only in Europe, but worldwide.

Raman spectrometers—especially handheld and portable instruments—are increasingly used for QC of medicines and raw materials (RMID). Instrument interfaces are user-friendly, requiring little technical expertise, and they provide flexible sampling options for most sample types with rapid, non-destructive measurements.

Metrohm’s Raman systems exhibit great flexibility—from see-through to standoff to immersion sampling.

An excerpt from the Ph. Eur. 2.2.48 Raman Spectroscopy chapter says:

«Raman spectroscopy is commonly used for qualitative and quantitative applications and can be applied to solid, liquid, and gaseous samples. Raman spectroscopy is a rapid and non-invasive analytical method and can be performed off-line, at-line, on-line, or in-line[…] Raman spectrometers can be situated far from the point of measurement using long-distance optical fibres to collect the Raman signal.»

Technological developments and their increasing adoption in the pharmaceutical industry prompted a revision of Ph. Eur. 2.2.48 which ensures the reliability of Raman results. The updated chapter 2.2.48 was published in the Ph. Eur. Supplement 10.7 (October 2021) and will ultimately take effect in April 2022.

While much of the Ph. Eur. 2.2.48 chapter has remained the same, the latest revision features:

  • new requirements for spectral resolution for qualitative Raman analysis using a suitable reference material
  • updated requirements for the Raman response-intensity scale
  • detailed procedures for the comparison of spectra

We will address these new requirements across our Raman spectroscopy product lines in the rest of this article.

Spectral Resolution

«Spectral resolution is the ability of a spectroscopic system to separate adjacent bands, which makes it possible to characterise complex samples (e.g., brand analysis, crystallinity, polymorphism).

[…] For identity tests, unless otherwise prescribed in a monograph, the spectral resolution must be less than or equal to 15cm-1 (measured in the wavenumber range between 1000cm-1 and 1100cm-1).

The spectral resolution is verified using a suitable reference material. The instrument parameters used for the test, such as laser, slit-width and grating for dispersive instruments and circular aperture […] for FT-instruments, must be the same as those applied for sample measurements. For example record the Raman spectrum of calcium carbonate for equipment qualification CRS, and determine the full width at half height (W1085) of the band located at 1085 cm-1. The spectral resolution (R) using calcium carbonate is then given by the following relation:»

Handheld Raman instruments: MIRA P, MIRA M-3, and NanoRam

All MIRA and NanoRam devices (including both NanoRam and NanoRam-1064) for the pharmaceutical industry are designed and tested to meet stringent resolution requirements. During QC, the resolution of each instrument is tested to be less than 15 cm-1 against a secondary USP (US Pharmacopeia) reference standard of calcium carbonate according to ASTM E2529, which is the same procedure recommended in this newly released Ph. Eur. chapter.

The measured spectral resolution value for each instrument, along with its identifying serial number, is included in the instrument final test report. A certificate or final test report is packaged with the device and sent to the customer. This resolution is fixed by the optical design of the instrument and is stable over time.

Portable Raman instruments: i-Raman series, QTRam, STRam, and PTRam

The instrument resolution for all of Metrohm’s portable Raman instruments from B&W Tek are factory-tested with calcium carbonate and displayed on final instrument test reports. The spectral resolution is dependent on the instrument design and defined for each specific instrument configuration. Depending on the instrument model, the spectral resolution is between 3.5–11 cm-1. Additionally, the instrument control softwares Vision and BWAnalyst have the performance test function that verifies spectral resolution using the 1001.4 cm-1 peak of polystyrene.

Handheld and portable Raman instruments from B&W Tek.

Response-Intensity Scale

«The verification of the response-intensity scale is principally performed for quantitative methods.

Appropriate acceptance criteria will vary with the application. A maximum variation of ± 10 per cent in band intensities compared to the previous instrument qualification is achievable in most cases. Response calibration may involve the use of white-light standards or luminescent glass (e.g., NIST SRM 2241).»

Handheld Raman instruments: MIRA P, MIRA M-3, and NanoRam series

MIRA P, MIRA M-3, and NanoRam systems are designed for qualitative analysis, not for quantitative purposes. Therefore, this criterion is not a strict requirement for handheld Raman products.

However, the relative intensity response of MIRA P and NanoRam series instruments is calibrated with a NIST standard SRM calibration material (SRM 2241, SRM 2242) or NIST SRM 2241-traceable calibration standard to achieve better uniformity from instrument-to-instrument.

The NanoRam series instruments have an acceptance criterion for relative intensity response in the instrument performance validation in alignment with Ph. Eur. 2.2.48 and USP<858>. To pass the performance validation, <10% relative intensity error is required using the factory-supplied polystyrene cap.

Portable Raman instruments: i-Raman series, QTRam, STRam, and PTRam

The relative intensity response of these portable Raman instruments is calibrated using a proper NIST standard SRM calibration material to achieve better uniformity from instrument-to-instrument. Additionally, the Vision instrument control software includes the performance test function that verifies the intensities of several Raman peaks of polystyrene relative to its 1001.4 cm-1 peak, to a maximum variation of ±10% compared to the previous instrument qualification.

Comparison Procedures

For qualitative methods, additional information for identification has been defined.

«Several comparison procedures may be used, and the analyst must document and justify the method used and the specific acceptance criteria that allow a conclusion for identification. The spectra can be compared by either overlaying the spectra (in the whole spectral range or in the region of interest specified in the monograph) or by using mathematical calculations of the software. It is possible for example to perform:

  • visual comparison based on band positions and relative intensities unless otherwise specified[…]
  • a statistical determination of the similarity between the spectra of the material to be examined and the reference standard[…]
  • evaluation by chemometric methods[…]»

While an experienced Raman spectroscopist can certainly compare spectra visually and assess sample validity based on peak location, fluorescence, saturation, and signal-to-noise ratio, the widespread implementation of Raman in the real world means that complex analysis must be done by the device and not the user. Statistical comparison methods are used primarily for identification of unknowns through correlation of a sample spectrum with library spectra. The software performs library searches and returns a Hit Quality Index (HQI) value indicating the level of correlation as defined by a user-defined threshold.

Chemometric methods rely on dimensionality-reduction methods that are performed by the software, such as Principal Component Analysis (PCA), where new sample data is compared within a multivariate model created from representative samples. This permits highly accurate verification of known materials according to how well a spectrum fits into the model limits, which are determined by a confidence interval. In the analysis of medicines and raw materials, chemometric methods are used to distinguish the quality and consistency of a material. MIRA P (and its dedicated software, MIRA Cal P) and NanoRam instruments use both statistical and chemometric methods for sample identification and verification based on the needs of the end-user.

For more information, download our free technical and application notes as well as a White Paper below.

Wavenumber accuracy requirements of Ph. Eur. 2.2.48

«Verify the wavenumber scale for Raman shifts using a suitable standard that has characteristic maxima at the wavenumbers under investigation, for example an organic substance such as polystyrene, paracetamol or cyclohexane[..]

A minimum of 3 wavenumbers covering the working range of the instrument intended for measurements should be selected.[…]»

This chapter maintains the same requirements for Raman wavenumber accuracy and is consistent with the USP <858> and JP 2.26. All of Metrohm’s handheld Raman instruments meet these requirements. Users are recommended to run performance validation tests at regular intervals using polystyrene or another ASTM Raman shift calibration material.

Download our free White Paper below to learn more about instrument calibration, system verification, and performance validation.

The Calibrate/Verify Attachment (CVA) shown here is a dual-ended accessory containing a toluene/acetonitrile ASTM standard for calibration/verification of the wavenumber axis and polystyrene for a second wavenumber verification according to Ph. Eur. 2.2.48.
Performance tests for Raman wavenumber accuracy are included the Vision and BWAnalyst softwares for the i-Raman series and other portable Raman products (STRam, QTRam, PTRam), with acceptance criteria in accordance with the pharmacopeial requirements.

Metrohm’s unique way of compliance with Ph. Eur. 2.2.48

Better representation of the material

«When using Raman spectroscopy[…] care must be taken to ensure that the measurement is representative. This can be achieved by, for example rotation of the sample, performing multiple measurements on different preparations of the sample, using orbital raster scanning (ORS), increasing the area of illumination by reducing the magnification, by demagnification of the laser beam or by changing the focal length between measurements to scan at different depths.»

ORS™ is Metrohm Raman’s proprietary method for moving the excitation laser in a pattern over a sample in order to collect more representative data from a larger area of the sample, especially on heterogeneous samples. All MIRA and MISA instruments are equipped with ORS.
Learn more about ORS by downloading the related Application Note.
For more details about how we comply, please check the U.S. Pharmacopeia Raman Chapters Updates page on the B&W Tek website. For more general information, download this General Compliance Statement for MIRA handheld Raman systems
For a more comprehensive look at raw material identification and verification in the pharmaceutical industry, there is a significant amount of information on this topic in our related blog post.

Post written by Dr. Melissa Gelwicks (Technical Writer at Metrohm Raman, Laramie, Wyoming), and Dr. Xiangyu (Max) Ma (Handheld Raman Product Manager) and Dr. Jun Zhao (R&D Director) at B&W Tek, Newark, Delaware.

Green hydrogen generation: A cross-disciplinary challenge rooted in electrochemistry

Green hydrogen generation: A cross-disciplinary challenge rooted in electrochemistry

Green hydrogen, produced from water electrolysis using renewable energy sources, is being explored as a strategy to reduce the dependence on fossil fuels and decarbonize chemical processes. From an environmental standpoint, this approach is extremely attractive given that mild conditions are used during electrolysis and there are no greenhouse gases produced when using the hydrogen in a fuel cell.

However, the economics of electrolysis and fuel cell systems for energy conversion relies heavily on the costs of electricity and of metals like nickel, platinum, iridium, and titanium. Electrolyzer operating expenses must be minimized for green hydrogen to become an economically viable option. The electricity input contributes heavily to cost. Thus, decreasing the cost of renewable energy is a necessary step. Solar panels becoming more efficient and affordable within the past decades is cause for optimism in this regard [1], but there is much more that can be done to increase the success of green hydrogen. More efficient electrolyzers could make better use of the input electricity and the development of cheaper and more durable components can reduce both the capital and operational costs.

Check out our other blog articles about green hydrogen and decarbonization of chemical processes below!

Cross-disciplinary interest in green hydrogen

Electrolyzers are primarily electrochemical devices with electrocatalysts responsible for water splitting (Figure 1). The scientific challenges related to optimizing electrolyzers are attracting the attention of researchers that are not traditionally trained in electrochemistry. The search for efficient HER (Hydrogen Evolution Reaction) and OER (Oxygen Evolution Reaction) electrocatalysts also piques the interest of inorganic chemists and physicists. Development of better membranes calls for expertise in organic and polymer chemistry. Optimization of catalyst inks and their interaction with substrates requires the know-how of a materials scientist. Heat and mass flow management within the fuel cell stack and balance of plant are engineering endeavors. Clearly, the ongoing development of green hydrogen technologies has encouraged the collaboration of scientists and engineers across many disciplines. The result is an influx of creativity and insight, as well as development of exciting new materials and techniques.

Figure 1. Diagram of the electrolysis of water (water splitting) with respective half reactions at the cathode and anode in alkaline and acidic media.

Back to basics

Working in an unfamiliar domain means there is a need for quickly getting up to speed with best practices and learning a new scientific vocabulary. For many institutions, education on electrochemical principles and laboratory skills was not a key focus area until recent years.

In some cases, the deficiency of fundamental electrochemical training has led to inconsistencies in the reporting of important performance indicators. The electrochemical community has taken note of this and called for a more rigorous approach. As a result, experts have stepped up and provided practical guidance for quantifying and reporting in this domain.

When investigating electrocatalyst materials it is necessary to have benchmarks and well-defined performance indicators. In 2013, a comprehensive benchmarking protocol for evaluating and reporting figures of merit for OER electrocatalysts was published.

This JACS article [2] provides practical advice on how to interpret the catalyst surface in terms of roughness and geometric surface area and how to perform and analyze measurements for valid comparisons of electrocatalytic performance.

A common source of confusion and inconsistency in electrochemical measurements is the use of various reference electrodes (RE). Electrocatalytic activity is judged by the overpotential needed for a specified production rate (i.e., the current density for the HER or OER process, Figure 1). A three-electrode setup is needed to measure the potential, and the RE is crucial for situating this potential on a relative scale, allowing comparison of measurements carried out by different groups and in various conditions.

Find out more about reference electrodes and their usage in our free Application Note.

A 2020 Viewpoint article in ACS Energy Letters [3] provides a detailed explanation of how to report the overpotential of an electrocatalyst, focusing on commonly used reference electrodes like Hg/HgO, Hg/Hg2Cl2 (SCE), and Ag/AgCl.

The reversible hydrogen electrode (RHE) is another commonly used RE that is extremely well-suited for HER and OER studies. A recent ACS Catalysis article [4] explains why the RHE is the ideal reference electrode for electrolysis research and explains how to prepare and work with an RHE. By convention, all standard redox potentials are reported versus the standard hydrogen electrode (SHE). The RHE is a pH-dependent extension of the SHE and refers to the reduction of a proton under non-standard conditions as described by the Nernst equation.

Electrolyzers operate under both acidic and alkaline conditions, thus, the HER and OER are studied across the pH scale (Figure 1). The RHE is suitable for use at any pH and it shares the same dependency on pH as the HER and OER.

A common ground to stand on

Finding common language and understanding between these different fields is vital. This JOC synopsis article [5] clarifies electrochemical concepts for organic chemists. The article is highly visual, providing schematics that link concepts like free energy, redox potential, and overpotential. Equilibrium thermodynamics helps to provide a common point of reference that all chemists can relate to.

Thermodynamic analysis is often applied to quantify the energy efficiency of electrolysis cells and stacks. A recent review article in the Journal of Power Sources [6] highlights diverging definitions for the energy efficiency coefficient from academic and industrial literature. The article provides derivations in various conditions and reminds readers that both electricity and heat must be accounted for in the analysis.

Summary

The articles highlighted in this blog post represent just a small fraction of the many resources available for building a common understanding and better collaboration among all researchers working on the improvement of green hydrogen technologies. When the COVID pandemic shut down laboratory work and travel for many people, the research community carried on with enthusiasm.

Online seminars and working groups held openly and without cost have brought scientists together across disciplines and from around the world. For example, the Electrochemical Online Colloquium was started in 2021. This ongoing series of lectures addresses essential topics in electrochemistry by providing educational content alongside the personal perspective of expert speakers.

The electrochemical community is acutely aware of the importance of transitioning to sustainable and climate-safe energy and chemical processes. Energy storage and conversion through green hydrogen is a promising strategy that requires scientific advancement to thrive. Thankfully, researchers from across many disciplines are bringing their skills and creativity to this topic while the electrochemical community continues to drive collaborative efforts and share their core knowledge.

To find out more about associated topics, download these free Application Notes from Metrohm Autolab.

References

[1] Green Hydrogen Cost Reduction: Scaling up Electrolysers to Meet the 1.5°C Climate Goal; International Renewable Energy Agency: Abu Dhabi, 2020.

[2] McCrory, C. C. L.; Jung, S.; Peters, J. C.; et al. Benchmarking Heterogeneous Electrocatalysts for the Oxygen Evolution Reaction. J. Am. Chem. Soc. 2013, 135 (45), 16977–16987. doi:10.1021/ja407115p

[3] Niu, S.; Li, S.; Du, Y.; et al. How to Reliably Report the Overpotential of an Electrocatalyst. ACS Energy Lett. 2020, 5 (4), 1083–1087. doi:10.1021/acsenergylett.0c00321

[4] Jerkiewicz, G. Standard and Reversible Hydrogen Electrodes: Theory, Design, Operation, and Applications. ACS Catal. 2020, 10 (15), 8409–8417. doi:10.1021/acscatal.0c02046

[5] Nutting, J. E.; Gerken, J. B.; Stamoulis, A. G.; et al. “How Should I Think about Voltage? What Is Overpotential?”: Establishing an Organic Chemistry Intuition for Electrochemistry. J. Org. Chem. 2021. doi:10.1021/acs.joc.1c01520

[6] Lamy, C.; Millet, P. A Critical Review on the Definitions Used to Calculate the Energy Efficiency Coefficients of Water Electrolysis Cells Working under near Ambient Temperature Conditions. J. Power Sources 2020, 447, 227350. doi:10.1016/j.jpowsour.2019.227350

Post written by members of the Metrohm Autolab group, Utrecht, The Netherlands.
NIR spectroscopy in the petrochemical and refinery industry: The ASTM compliant tool for QC and product screening – Part 3

NIR spectroscopy in the petrochemical and refinery industry: The ASTM compliant tool for QC and product screening – Part 3

What is Pyrolysis gasoline or «Pygas»?

Pyrolysis gasoline, also known as Pygas, is a byproduct of naphtha cracking during the production of ethylene and propylene. Pyrolysis gasoline is an easily flammable, colorless liquid with high aromatic contents and represents a mixture of light hydrocarbons (Figure 1). It is a high octane number mixture which contains aromatics, olefins, and paraffins ranging from C5 to C12.

Figure 1. Pyrolysis gasoline (or Pygas) shown here is nearly colorless, but extremely flammable.

Because of its high octane number, Pygas has a high potential for blending in various end-user products.  In addition, pyrolysis gasoline can be used as a component separator for benzene, toluene, and xylene. For this purpose, it is used as a component separation additive.

Pygas contains some undesired conjugated diolefins that when present in high quantities makes them unsuitable as a motor fuel. These conjugated diolefins are highly reactive to polymerization and can plug the downstream refining processes causing unwanted shutdowns and high costs for remediation. These compounds also affect the stability of commercial gasoline. Therefore, the conjugated diolefins content must be controlled.

The content of conjugated diolefins is indirectly measured as the «maleic anhydride value» (MAV), or as the «diene value» (DV). This parameter is usually determined by the Diels-Alder wet chemical method (UOP 326). Furthermore, the determination of Bromine Number (ASTM D1159) in pygas is useful as it indicates the degree of aliphatic unsaturation. These determination methods require several hours and must be analyzed by highly trained analysts. In contrast to using primary methods, near-infrared spectroscopy (NIRS) is a cost-efficient and fast alternative solution for the determination of MAV or DV and Bromine Number in pyrolysis gasoline.

Near-infrared spectroscopy—an ASTM compliant tool to assess the quality of pygas

Near-infrared spectroscopy (NIRS) has been an established method for both fast and reliable quality control within the petrochemical industry for more than 30 years. However, many companies still do not consistently consider the implementation of NIRS in their QA/QC labs. The reasons could be either limited experience regarding application possibilities or a general hesitation about implementing new methods.

There are several advantages of using NIRS over other conventional analytical technologies. For one, NIRS is able to measure multiple parameters in just 30 seconds without any sample preparation! The non-invasive light-matter interaction used by NIRS, influenced by physical as well as chemical sample properties, makes it an excellent method for the determination of both property types.

In the remainder of this post, an available solution for the determination of maleic anhydride value (MAV) or diene value (DV) and Bromine number are outlined which have been developed according to the NIRS implementation guidelines of ASTM E1655 (method development), ASTM D6122 (method validation), and ASTM D8340 (results validation).

Did you miss the first parts in this series about NIRS as a QC tool for the petrochemical industry? Find them all below!

Read our previous blog posts to learn more about NIRS as a secondary technique.

Analysis of Diene Value (DV) and Bromine Number (BN) in pygas with the DS2500 Liquid Analyzer

Historically, NIRS analysis of the diene value and Bromine Number in pygas has been considered to be complicated due to the presence of other non-conjugated dienes as well as alkenes that have similar molecular functional groups. In addition, the majority of the samples are a complex mixture of aromatics and alkanes that varies with process conditions in the ethylene production process, as well with as the different feedstocks used to produce ethylene (e.g., alkanes, naphtha, or gas oil). Also, DV is not reliant on one specific conjugated diolefin, but over a dozen different compounds including cyclopentadiene (a ring structure) and straight-chain diolefins with different chain lengths and side chains. As explained earlier, the diene value is usually determined by the Diels-Alder wet chemical method (UOP 326). Bromine Number (BN) is determined by electrochemical titration at 5 °C (ASTM D1159).

Now, spectroscopic analysis of these parameters in such a complicated system is made successful through a combination of stable NIRS measurements with the DS2500 Liquid Analyzer, and the Partial Least-Squares (PLS) modelling capabilities in the Vision Air complete software package.

Learn more about the Metrohm NIRS DS2500 Liquid Analyzer and Vision Air software here!
Results from NIRS analysis are obtained very rapidly, with no sample preparation required aside from the temperature equilibration of the sample prior to scanning. This makes it possible to monitor and control the process, which is simply not possible using other methods. NIRS measurements do not require highly trained analysts—disposable glass vials are the only things needed for the analysis!

Metrohm offers a related application note for the proper use of NIRS for pyrolysis gas analysis (Table 1).

Table 1. Metrohm’s NIRS solutions for pygas including application details and benefits.
Parameter Reference method   Norm NIRS Application Notes  NIRS benefits
Maleic Anhydride Value (MAV) or Diene Value (DV) Reflux / Hydrolysis / Titration UOP 326 AN-NIR-024 MAV or DV measured within one minute, without requiring sample preparation or use of any chemicals.  A major difference compared to 6–7 hours when using the primary reference methods.
Bromine Number (BN) Cooling / Titration ASTM D1159 AN-NIR-094 Bromine Number measured within one minute without needing chemical reagents or sample preparation.
Learn more about the possibilities of petrochemical analysis with Metrohm NIRS DS2500 Analyzers in our free brochure.

Application example: determination of DV and BN in pygas using the NIRS DS2500 Liquid Analyzer

The diene value and Bromine Number are key parameters for the quality control of pygas.  According to UOP 326, the maleic anhydride is refluxed with the sample in boiling toluene for three hours. Any unreacted maleic anhydride is hydrolyzed to maleic acid, extracted from the reaction mixture, and then titrated with sodium hydroxide. This wet chemical method requires several hours to perform by highly trained analysts. 

For the determination of the Bromine Number according to ASTM D1159, the sample must be cooled down below 5 °C to minimize side reactions like oxidation or substitution.

In contrast to primary methods, near-infrared spectroscopy (NIRS) is a cost-efficient and fast analytical solution for the determination of DV and BN in pyrolysis gasoline.

Figure 2. Quality control of pygas as performed by the Metrohm NIRS DS2500 Liquid Analyzer.

The obtained Vis-NIR spectra (Figure 2) were used to create a prediction model for the determination of DV and BN. The quality of the prediction model was evaluated using a correlation diagram, which displays the correlation between the Vis-NIR prediction and primary method value. The respective figures of merit (FOM) display the expected precision of a prediction during routine analysis (Figure 3).

Figure 3. Correlation plots and figures of merit (FOM) for DV and Bromine Number in pygas.

This solution demonstrates that NIR spectroscopy is excellently suited for the analysis of diene value or maleic anhydride value in pygas in less than one minute without sample preparation or using any chemical reagents. In comparison to the wet chemical method in UOP 326, the time to result is a major advantage of using NIRS since a single measurement is performed within one minute instead of taking 6–7 hours with the primary method. Additionally, Bromine Number is easy to measure with NIRS without requiring any chemicals or sample preparation (such as cooling) as mentioned in ASTM D1159.

Want to learn more? Download our free Application Notes.

Summary

Near-infrared spectroscopy is an excellent choice for measuring MV / DV and BN in pygas. A simple feasibility study using your own pyrolysis gasoline samples will quickly indicate if the NIR spectra will be able to be correlated to the primary method values.  Positive aspects of using NIRS as an alternative technology are the short time to result (less than one minute), no chemicals or other expensive equipment needed, and ease of handling so that even shift workers and non-chemists can perform these analyses in a safe manner.

Future installments in this series

This blog article was dedicated to the topic of pyrolysis gasoline (pygas) and how NIR spectroscopy can be used as the ideal QC tool for the petrochemical / refinery industry. Future installments will be dedicated to other important applications in this industry. These topics will include:

 

  •  Lubricants
  • ASTM Norms

For more information

About spectroscopy solutions provided by Metrohm, visit our website!

We offer NIRS for lab, NIRS for process, as well as Raman solutions

Post written by Wim Guns, International Sales Support Spectroscopy at Metrohm International Headquarters, Herisau, Switzerland.
Guide to online and inline surface finishing analysis

Guide to online and inline surface finishing analysis

What is surface finishing?

Surface finishing is a series of industrial processes with the main goal to alter the surface of a certain workpiece in order to obtain specific properties. This can be performed chemically, mechanically, or even electronically with the aim of removing, altering, adding or reshaping the material that is being treated.

Industries that use surface finishing techniques

Surface finishing techniques are used by most industries that manufacture industrial parts (e.g., metals, wafers, tools, and more). The use of surface finishing processes has been on the rise globally and is expected to grow further. An article published by Grand View Research (2019) predicted that the market size for metal finishing chemicals is expected to grow to $13.52 billion USD by 2025.

People mostly think about polishing and sanding when surface finishing is brought up, but it is much more than that. Several industries use different processes to treat surfaces with the main objective of obtaining the highest product quality. According to Grand View Research, the top three industries with the biggest market share for metal surface chemicals are automotive and aerospace, semiconductors, and the metal industry (e.g., industrial machinery, construction).

Figure 1 shows that surface finishing is mainly used in the automotive industry. Here, electroplating and electroless plating are the main processes used to protect against corrosion. The electroplating process consists of using electricity to coat a material (e.g. copper) with a thin layer of another material (e.g. nickel). Electroless plating is accomplished with chemical processes that reduce metal cations in a bath and deposit them as an even layer, even on non-conductive surfaces.

Next is the semiconductor industry, which includes the manufacturing and cleaning surface process of electrical and electronic parts as well as silicon wafers. This industry involves plating processes (e.g., electroless plating) as well as chemical cleaning baths. Chemical cleaning baths are used here to remove any contaminants from the wafer surfaces.

Figure 1. Diagram with top five industrial applications that incorporate surface finishing techniques (graphic repurposed from Metal Finishing Chemicals Market Global Forecast to 2021). (Click image to enlarge.)
Finally comes the metal industry, responsible for creating the infrastructure that our modern world depends on. Here, the process of galvanization is used to make metal corrosion- and heat-resistant. Galvanization is an anti-corrosive measure taken with iron and steel (as well as other metals) by applying a protective zinc coating which does not allow oxidation to occur. The zinc also acts as a sacrificial anode which still protects the underlying metal in the event of a scratch in the galvanized surface. Pickling baths are another common surface finishing process for this industry. These acidic baths are used to remove the oxide layer which formed on the surface during the hot strip mill. If the base steel is over-pickled, it can result in pitting of the metal surface, leading to an undesirable rough, blistered coating in the subsequent galvanizing steps and also excessively consumes the pickling acid (e.g. HCl).

Much more than just decorative coatings

Do appearances matter? When talking about products, absolutely! One of the reasons product surfaces are treated is so they have a more pleasant appearance for consumers, but also for more technical reasons that go beyond looks. Since surface finishing processes are used in a broad range of industries, they serve different purposes depending on the uses of the final products.

In the semiconductor industry, any defect on the components (e.g., silicon wafers, microelectronics, printed circuit boards (PCB), etc.) can impact the performance of the final product. Therefore, maintaining the proper concentrations of all components in the chemical cleaning bath ensures a repeatable etching process, which for this purpose means the elimination of surface defects.

Another example includes phosphating baths, which are used to improve corrosion resistance of the product parts used in the automotive and aerospace industry. This process is performed prior to any painting to protect the body structure from environmental factors. Phosphating baths also need to be kept consistent to guarantee the correct (and identical) thickness of the protective layer in each of the products subjected to this process.

Check out our free webinar about how Process Analytical Technology (PAT) brings analytical measurements directly to the process for real-time decision-making, ensuring a high level of control for coating and finishing baths and eliminating unnecessary risk to plant personnel. Learn about real-world case studies and field-tested applications that demonstrate the advantages of optimized bath chemistry and PAT in the surface treatment industry. 

Challenges in surface finishing processes: daily bath maintenance

Like any process, surface finishing has day to day challenges which can be improved upon. Improvement can only come from knowing the bath composition and how it affects the final product. Generally, monitoring the concentration of chemical baths is done via manual sampling and titration in a laboratory on site (in some cases, by a contract lab offsite). While this method works, it can lead to long waiting times from the moment the sample is taken until the final result—therefore the results are no longer representative of the current process conditions. Because of this delay,  bath replenishment can be impaired by over- or under- dosing components, leading to suboptimal bath composition and resulting product quality (Figure 2).

Figure 2. A jagged graph such as this denotes bath quality that suffers from suboptimal conditions. A relatively flat line would suggest a stable bath composition over time, resulting in reproducible high quality surface finishing.
Manual bath analysis and chemical dosage based on old data directly influences the company’s bottom line since the manufacturer loses money either by overusing bath chemicals or producing subpar products. The larger the plating bath volume, the greater the cost of chemicals utilized. Surface finishing baths can be as large as 3500 L (1,000 gallons) or more. Thus, it is extremely important to optimize chemical dosing to reduce unnecessary costs and waste while still providing maximum quality.

If the baths are overdosed, more chemicals are used than necessary which increases overall operational costs. However, if the baths are underdosed based on old data, then the final products may be defective, which results in increased operational costs as well.

Additionally, surface finishing processes involve many hazardous substances. When carrying out any risk assessment, the first resort is the use of personal protective equipment (PPE), and any potential exposure risks should ideally be engineered out of any process.

Automated analysis of the bath components with an online or inline process analyzer completely eliminates the risk of exposure by plant personnel to the hazards associated with the chemicals used, as well as taking care of the sample preconditioning and sampling itself. With a closed loop control, quick measurements are obtained which lead to fast results and response times for optimized process adjustments.

The solution: operate more safely and efficiently with automated process analysis

Process analysis by manual titration typically takes several steps: sample collection, sample preconditioning, volumetric manipulations, calculation, logging and checking results, and finally sending feedback to the process. All of these can be totally eliminated by using online and inline analysis.

The benefits of this are very clear. By limiting the manual handling steps, any risk of exposure to hazardous chemicals is removed. Sampling error, volumetric errors, and end point ambiguity from analyst to analyst are no longer an issue. Furthermore, sampling can be carried out on a timed basis and can be programmed to occur more frequently than possible with manual methods, giving much greater process control.

The analyzer can be used to fully control a process with direct feedback of results for the correct dosage of chemicals to aging baths. Data is automatically recorded and calculated. On-screen plots and signals can warn about deviating process conditions along with alarm outputs to notify operators of bath issues. The user interface is programmed by simple intuitive operation, and can be performed even by non-chemists.

Benefits of online and inline analysis in surface finishing processes:
  • Decrease manual labor – save time and money
  • Safer working environment – avoid contact with hazardous chemicals
  • Faster response time to process changes – better product quality
  • Optimized chemical consumption – less waste, reduced costs
Learn about the differences between inline, online, atline, and offline measurements in our previous blog post.
Metrohm Process Analytics has more than 50 years of experience in process analysis and optimization. The following examples show our expertise with configuring inline and online process analyzers for different surface finishing processes.

Automated monitoring of clean and etch baths

Metal surfaces can have scratches, impurities, and other imperfections which may interfere with further manufacturing processes (e.g., plating or painting). Therefore, clean and etch baths are a key step to obtain clean, polished, and undamaged surfaces.
Figure 3. Trend chart of NH3 and H2O2 concentrations in an SC1 bath. Note the spiking of the baths to maintain their concentrations.
Traditionally, these bath chemicals are measured offline in the lab after taking a sample from the process. However, as mentioned earlier, manual laboratory methods result in long response times in case of process changes (e.g., reaction mixture, moisture levels, …), and the sample preparation can also introduce errors, altering the precision of the analysis. Additionally, it can be quite cumbersome since different operating procedures need to be implemented to analyze multiple parameters including alkalinity, ammonium hydroxide, hydrogen peroxide, and more.
Figure 4. The Metrohm Process Analytics NIRS XDS Process Analyzer is shown here with a diagram of the inline near-infrared spectroscopy (NIRS) system configuration for cleaning bath analysis.
Another example of cleaning baths are mixed acid baths, generally comprised of sulfuric acid, hydrofluoric acid, and nitric acid. Titration only provides the acid value of the sample analyzed; therefore, it is not possible to know how much of a specific acid is present in the baths. However, near infrared spectroscopy (NIRS) is the perfect analytical technique to monitor each acid individually.
Reagent-free NIRS XDS Process Analyzers enable comparison of real-time spectral data from the process to a primary method (e.g. titration) to create a simple, yet indispensable model for process optimization. NIRS is economical and fast, enabling qualitative and quantitative analyses that are noninvasive and nondestructive. Integration of inline spectroscopic techniques allows operators to gain more control over the production process and increase overall safety.

In addition to NIRS process analyzers, Metrohm Process Analytics can design and customize flow-through cells (Figure 5). These clamp on to tubing already present onsite for easy installation with no need to modify the existing setup.

Figure 5. PTFE single fiber clamp-on flow cell from Metrohm Process Analytics.

Automated monitoring of phosphatizing baths

The phosphatizing process produces a hard, electrically non-conducting surface coating that adheres tightly to the underlying metal. This layer protects against corrosion and improves the adhesion of paints and organic finishes to be subsequently applied.

Phosphatization consists of two parts: an etching reaction with phosphoric acid which increases the surface roughness, and a second reaction at the surface between the alkali phosphates and the previously generated metal ions. This coating is quite thin and offers only basic corrosion protection. The addition of metal cations (such as zinc, manganese, and calcium) to the phosphatizing bath results in the formation of very resistant zinc phosphates with a coating thickness between 7–15 times thicker, perfectly suited for outdoor use.

Figure 6. Schematic diagram of the various process stages and baths used in the phosphatizing process. (Click image to enlarge.)

In the cleaning, degreasing, and rinsing baths, and also in the phosphatizing bath itself (Figure 6), the various parameters involved in the process must be kept stable. Conductivity, pH value, free alkalinity, and total alkalinity are among the main parameters that must be determined in the degreasing and rinsing baths. Free and total acids, accelerator, zinc, and fluoride are monitored in phosphatizing baths. The 2060 Process Analyzer from Metrohm Process Analytics (Figure 7) monitors, records, and documents all of these critical parameters at the same time. The combination of different analytical methods within one system as well as the intuitive handling via the well-arranged user interface ensure easy and reliable monitoring of the entire process.

Check out our free related Process Application Note to learn more.

Figure 7. The 2060 Process Analyzer from Metrohm Process Analytics is an ideal solution for online phosphating bath applications.
To sum up, online and inline process analyzers from Metrohm Process Analytics are the ideal solution to automate the analysis of surface finishing processes because of the comprehensive benefits they provide:
  • No manual sampling needed, thus less exposure of personnel to dangerous chemicals
  • Extended bath life by tightening process windows (less chemicals required)
  • Minimize risk of downtime with faster and more precise data
  • Easier compliance with final product requirements by process automation

If you want to learn more about all the applications that we have to offer, download our free application e-book based on 45 years of global installations.

Read what our customers have to say!

We have supported customers even in the most unlikely of places⁠—from the production floor to the desert and even on active ships!
Post written by Andrea Ferreira, Technical Writer at Metrohm Applikon, Schiedam, The Netherlands.
The evolution of handheld 785 nm Raman spectroscopy: Raman extraction from fluorescence interference

The evolution of handheld 785 nm Raman spectroscopy: Raman extraction from fluorescence interference

MIRA DS (Metrohm Instant Raman Analyzer) is a handheld Raman system that identifies materials using 785 nm laser excitation. The advantages of using 785 nm Raman are well understood. Excitation with shorter wavelengths produces strong Raman scattering with short acquisition times. This results in a high signal-to-noise ratio and provides excellent spectral resolution with lower power draw. These are just some of the reasons that handheld Raman has become so popular over the last two decades.

The sensitivity of Raman at 785 nm also means that lower laser powers can be used. Lower laser powers help to protect sensitive samples from burning or ignition. The silicon detectors used at shorter wavelengths do not need to be cooled, further extending battery lifetimes. The net result is that 785 nm systems can be very small and still provide fast and accurate material identification for long hours in the field.

Learn more about how MIRA became mobile in our previous blog post.
However, while this is considered the «sweet spot» for both a strong signal and fluorescence mitigation among possible wavelengths, approximately 10% of Raman active materials fluoresce under interrogation with 785 nm Raman systems [1]. For example, Gum Arabic is a widely used filler and binding agent. When sampled with 785 nm systems, its fluorescence overwhelms the Raman signal (more on this subject later). Similarly, cutting agents (e.g., sucrose found in street drugs) fluoresce and can prevent positive identification of the target substance. Dyes can be problematic in the analysis of tablets, foodstuffs, art, and plastics as well. Often, weak Raman features can still be observed in fluorescent materials with 785 nm interrogation, but fluorescence mitigation is crucial for library matching.

Previous recommendations to overcome fluorescence

When fluorescence is an issue, 1064 nm laser excitation is often recommended. The tradeoffs include higher laser power, increased sample heating, longer interrogation times, and low Raman scattering efficiency. Often, this means larger instruments with shorter battery lifetimes. Instruments from some manufacturers require longer acquisition times that slow down sampling and can potentially damage the sample.

Is there a better way?

In a word, yes. SSE (Sequentially Shifted Excitation) can be used to remove fluorescent contributions to a Raman spectrum by using a laser that shifts the excitation wavelength as a function of the laser temperature. The result is a very large «handheld» system with a shoulder strap and a high price tag, partly due to the expensive laser used. Aside from the bulk and the cost, another issue with these systems is that the constant temperature cycling of the laser causes the system’s battery to have a short lifetime.

A Metrohm solution

Metrohm Raman has designed a fluorescence rejection system based on its compact MIRA DS package using an IPS single-mode 785 nm laser. The system is capable of producing excellent spectral resolution and flat baseline data with low laser power, short acquisition times, and all of the other excellent functionalities that users have come to expect from MIRA DS.

This fluorescence rejection system is built upon a MIRA DS platform, preserving all of its unique capabilities:

MIRA XTR DS

MIRA XTR DS is the evolution of Raman spectroscopy. It combines the smaller size, higher resolution, and lower power consumption of a 785 nm Raman instrument with patent-pending advanced algorithms to eXTRact Raman data, even from spectra that have strong fluorescence!
Figure 1. Comparison of Raman spectra of Gum Arabic powder measured by 1064 nm, 785 nm (MIRA DS), and XTR® (MIRA XTR DS).
Figure 1 contains Raman spectra from a fluorescent material, Gum Arabic powder, with traditional 785 nm and 1064 nm laser excitation, in addition to MIRA XTR DS. The improvement in resolution with XTR is obvious. Notice the very flat (uncorrected) baseline in the XTR spectrum on the bottom. This is crucial for library matching with a Pearson correlation, where the dot product between spectra and non-zero baselines contribute strongly to the correlation.

Learn more about MIRA XTR DS on our website.

Applications for MIRA XTR DS include Sensitive Site Exploitation / Intelligence Surveillance Reconnaissance (SSE/ISR) of clandestine labs and determination of synthetic routes to illicit products. MIRA XTR DS is designed for real world scenarios like the analysis of methamphetamine lab residues and identification of narcotics in street drug samples. This includes ID of narcotics, despite cutting agents that fluoresce and fail analysis at 785 nm. ORS™ combined with fluorescence rejection means that MIRA XTR DS can also delicately interrogate sensitive materials like colored explosive compounds.

Download our free White Paper below to find out more about the capabilities of MIRA XTR DS.

Classic applications improved with MIRA XTR DS

Lidocaine [2] is a local anesthetic that can also be used to cut cocaine because it enhances the immediate numbing sensation that many cocaine users associate with a high quality product. Since cocaine is typically present at only ~30% in street samples, its signal can be occluded by other components in the mixture. However, positive identification of common cutting agents like lidocaine can lead to further investigation of a suspect sample.

Traditionally, lidocaine was an issue for 785 nm Raman systems, as its fluorescence prevented both positive identification of lidocaine and detection of cocaine. MIRA XTR DS produces an excellent, fluorescence-free, resolved spectrum of lidocaine (Figure 2).

Figure 2. Comparison of Raman spectra of lidocaine hydrochloride measured by 1064 nm, 785 nm (MIRA DS), and XTR (MIRA XTR DS).
Diphenhydramine is another example of a common OTC drug that, when detected, may suggest darker dealings. It can be abused on its own, but it is also a potential precursor in the synthesis of methamphetamine. Diphenhydramine exhibits some fluorescence when interrogated with 785 nm Raman (Figure 3), but it is also typically present in mixtures with inert ingredients that fluoresce. For this type of analysis, SERS can be used to detect trace amounts of a substance. This is an excellent showcase for MIRA XTR DS, because it can perform both 785 nm Raman and SERS tests, while most 1064 nm systems currently on the market cannot be used for SERS analysis.
Figure 3. Left: MIRA XTR DS used for no-contact testing. Right: Comparison of Raman spectra of Diphenhydramine measured by 1064 nm SERS, 785 nm SERS (MIRA DS), and XTR SERS (MIRA XTR DS).
What’s the difference between Raman and SERS? Read our blog article to find out!

But MIRA XTR DS can do more!

With fluorescence mitigation, 785 nm Raman can be used more generally for material identification and chemical analyses.

Microcrystalline Cellulose

Microcrystalline cellulose (MCC) is another inert excipient that is commonly used in food production and the pharmaceutical industry. When interrogated with 785 nm Raman, its fluorescence can overwhelm the Raman signal and prevent identification and mixture matching (Figure 4).

Figure 4. Comparison of Raman spectra of MCC measured by 1064 nm, 785 nm (MIRA DS), and XTR (MIRA XTR DS).
Ketchup

Measurement of analytes in ketchup is a particularly interesting application, as it is a highly colored, complex mixture. With 785 nm testing, it shows fluorescence—with 1064 nm testing, it burns. But XTR analysis carries the added benefit of signal enhancement, returning a spectrum that clearly indicates the presence of trace lycopene in ketchup—the chemical that contributes its red color (Figure 5).

Figure 5. Comparison of Raman spectra of ketchup measured by 1064 nm, 785 nm (MIRA DS), and XTR (MIRA XTR DS).
Another important application demonstrates how MIRA XTR DS can distinguish imitation honey from the pure, unadulterated form in the pursuit of fraudulent food products, and that it shows promise for quantitative analysis. MIRA XTR DS extracts Raman spectra from materials that typically show fluorescence with 785 nm excitation, this time with sufficient resolution to detect different ratios of mixtures (Figure 6).
Figure 6. Comparison of Raman spectra of pure honey (left) and imitation honey (center) measured by 1064 nm, 785 nm (MIRA DS), and XTR (MIRA XTR DS). Right: Determination of the ratio of different mixtures of pure honey with adulterants using MIRA XTR DS. (Click image to enlarge.)

A powerful laboratory in the palm of your hand

Historically, Raman users dealt with fluorescence by using instruments with a 1064 nm laser. MIRA XTR DS combines the smaller size, higher resolution, and lower power consumption of a 785 nm laser with revolutionary machine learning to eXTRact Raman from fluorescent samples. The benefits are considerable!
  • Low power 785 nm laser interrogates sensitive samples without risk of ignition or burning.
  • Compact, pocket-sized design enables true single-handed operation of the device
  • The low power consumption means longer battery life for extended field use

MIRA XTR DS: all the best of handheld Raman with virtually unlimited applications.

Find out more about MIRA XTR DS

Download free white papers and learn more on our website.

References

[1] Christesen, S. D.; Guicheteau, J. A.; Curtiss, J. M.; Fountain, A. W. Handheld Dual-Wavelength Raman Instrument for the Detection of Chemical Agents and Explosives. Opt. Eng. 2016, 55 (7), 074103. DOI:10.1117/1.OE.55.7.074103

[2] Barat, S. A.; Abdel-Rahman, M. S. Cocaine and Lidocaine in Combination Are Synergistic Convulsants. Brain Res. 1996, 742 (1), 157–162. DOI:10.1016/S0006-8993(96)01004-9

Post written by Dr. Melissa Gelwicks, Technical Writer at Metrohm Raman, Laramie, Wyoming (USA).