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NIR spectroscopy in the petrochemical and refinery industry: The ASTM compliant tool for QC and product screening – Part 2

NIR spectroscopy in the petrochemical and refinery industry: The ASTM compliant tool for QC and product screening – Part 2

Differences between gasoline, diesel, and jet fuel

Gasoline is a fuel made from crude oil and other petroleum-based liquids, containing carbon numbers generally between 4 and 12, and exhibiting boiling points of up to 120 °C. Gasoline is primarily used as a fuel for vehicles. Petroleum refineries and blending facilities produce motor gasoline for sale at gas (or petrol) stations. Most of the gasoline that petroleum refineries produce is unfinished gasoline. This unfinished product requires blending with other liquids to control parameters such as octane rating and volatility to make gasoline meet the basic requirements for fuel that is suitable for use in spark ignition engines.

Diesel fuel is refined from crude oil at petroleum refineries. «Diesel» is the common term for the petroleum distillate fuel oil sold for use in motor vehicles that use the compression ignition engine, invented by the German engineer Rudolf Diesel (1858–1913). He patented his original design in 1892. One of the fuels that Rudolf Diesel originally considered for his engine was vegetable seed oil, an idea that eventually contributed to the biodiesel production process of today. Prior to 2006, most diesel fuel contained high quantities of sulfur. Sulfur emissions from combusting diesel fuel leads to air pollution that is quite harmful to human health. Therefore, the U.S. Environmental Protection Agency issued requirements to reduce the sulfur content of diesel fuel to be as low as 15 mg/L. Diesel fuel contains components with a carbon number range from 8 to 21 (though mainly between 16–20) and is the fraction that boils between 200 °C and 350 °C.

Jet fuels (or aviation fuels) are one of the basic products used by aircraft. Jet fuel is comprised of refined petroleum products with carbon numbers between 10 to 16 (although they can range from 6 to 16), and it boils between 150 °C and 275 °C. This type of fuel is heavily regulated by national and international bodies. There are two main types of jet fuel: Jet A and Jet B. The main difference between the two is the freezing point. Jet B is usually used for military operations and locations with inclement weather. Jet A is mainly used to fuel commercial airplanes.

Near-infrared spectroscopy—an ASTM compliant tool to assess the quality of gasoline, diesel, and jet fuel

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, available turnkey solutions for gasoline, diesel, and jet fuel are outlined which have been developed according the NIRS implementation guidelines of ASTM E1655 (method development), ASTM D6122 (method validation), and ASTM D8340 (results validation). Afterward is a discussion about the return on investment (ROI) of using NIRS as an alternative to the CFR Engine.

Did you miss Part 1 in this series about NIRS as a QC tool for the petrochemical industry? Check it out below!

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

NIRS expedites and simplifies fuel quality control

 Without high quality fuels (e.g., gasoline, diesel, and jet fuel), our daily lives would look much different. At the end of the production process as well as at various steps in the distribution chain, the quality of the product needs to be determined. Typically, key quality parameters such as RON/MON (research and motor octane numbers), cetane index, and flash point are determined in the laboratory by chemical and physical methods. These methods not only incur high running costs but they are also quite time consuming.

NIRS on the other hand requires neither chemicals nor sample preparation. This technique can even be used by non-technical people (no chemistry degree necessary) and it provides results in less than a minute. Furthermore, multiple chemical and physical parameters can be determined simultaneously. The combined benefits of this technology make NIRS the ideal solution for many daily QA/QC measurements or ad-hoc at-line analysis.

Metrohm offers the NIRS DS2500 Petro Analyzer for quality control and routine analysis of fuels and is compliant with ASTM D6122. Resistant to dust, moisture, and vibrations, this instrument is not only suitable for laboratory use, but also use in direct production environments. Learn more on our website

Turnkey solutions: available pre-calibrations for gasoline, diesel, and jet fuel

Table 1 lists all constituents covered by the pre-calibrations for these different fuels. Click on the fuel type in the table to learn more about its pre-calibrations offered by Metrohm.

Table 1. Pre-calibrations available for a variety of key quality parameters in gasoline, diesel, and jet fuel.
Fuel type Parameters Range SECV
Gasoline RON 81–100 0.68 0.958
MON 81–88 0.53 0.889
Anti-Knock Index 85–94 0.45 0.948
Aromatics 20–45% 0.011 0.959
Benzene 0.15–0.70 % 0.0004 0.902
Density 0.74–0.76 g/cm3 0.0024 g/cm3 0.797
Olefins 0–25 % 0.013 0.909
Oxygen 0.2–2.0 % 0.00045 0.994
Diesel Cetane index 46–77 0.62 0.987
Cetane number 45–60 0.942 0.942
Density 0.82–0.89 g/cm3 0.0021 g/cm3 0.968
CFPP -22–(+19) °C 2.8 °C 0.963
T95 325–410 °C 7.04 °C 0.799
Flash Point 56–120 °C 2.7 °C 0.97
Viscosity 2–5.5 cSt 0.15 0.91
Kerosene / Jet Fuel Cetane index 36–50 1.1 0.871
API gravity 38–48 ° 0.56 ° 0.931
Aromatics 10–25 % 0.01 0.851
T10 158–200 °C 4.1 °C 0.801
T20 165–205 °C 3.1 °C 0.88
T50 180–220 °C 4.1 °C 0.789
Density 0.78–0.83 g/cm3 0.003 g/cm3 0.936
Flash Point 38–65 °C 4.3 °C 0.62
Freeze Point -65–(-40) °C 3. 5°C 0.576
Hydrogen 13.2–14.2 % 0.0005 0.934
Saturates 75–90 % 0.009 0.888
Viscosity at 20 °C 3–7 cSt 0.33 cSt 0.804

Learn more about the possibilities of petrochemical analysis with Metrohm NIRS DS2500 Analyzers in our free brochure.

Application example: quality control of diesel with the NIRS DS2500 Petro Analyzer

The cetane index (ASTM D613), flash point (ASTM D56), cold filter plugging point (CFPP) (ASTM D6371), D95 (ISO 3405), and viscosity at 40 °C (ISO 3104) are among some of the key parameters to determine the quality of diesel. The primary test methods for these parameters are labor intensive and challenging due to the need for multiple analytical methods.

In this turnkey solution, diesel samples were measured in transmission mode with a NIRS DS2500 Petro Analyzer over the full wavelength range (400–2500 nm). The built-in temperature-controlled sample chamber was set to 40 °C to provide a stable sample environment. For convenience reasons, disposable vials with a pathlength of 8 mm were used (Figure 1), which made a cleaning procedure unnecessary.

Figure 1. Quality control of diesel fuel as performed by the Metrohm NIRS DS2500 Petro Analyzer.

The obtained Vis-NIR spectra (Figure 1) were used to create prediction models for the determination of key diesel parameters. The quality of the prediction models was evaluated using correlation diagrams which display the correlation between Vis-NIR prediction and primary method values. The respective figures of merit (FOM) display the expected precision of a prediction during routine analysis (Figure 2).

Figure 2. Correlation plots and figures of merit (FOM) for the different constituents tested in diesel.

This solution demonstrates that NIRS is excellently suited for the analysis of multiple parameters in diesel fuel, providing results in less than one minute without the need for sample preparation or any chemical reagents.

Want to learn more? Download our free Application Note.

Return on investment: CFR Engine vs. NIRS

Gasoline requires intensive checks on several quality parameters which must be within certain specifications before commercialization. These parameters which can also be controlled by NIRS analysis include the research octane number (ASTM D2699) and motor octane number (ASTM D2700), also known as RON/MON.

The importance of measuring these values precisely is not only to comply with regulations, but also because of the further potential to save costs for manufacturers. As an example, RON values exceeding the stated requirements will still be accepted by the market, but these products will then include a higher amount of lucrative long-chain organic molecules. This so-called «RON giveaway» is estimated at approximately 0.5 RON per barrel, resulting in $2.25 million USD/month in lost revenue for a production process of 100,000 barrels per day.

Figure 3. CFR® F1/F2 Octane Rating Unit Combination Research & Motor Method. (Source: CFR Engines Inc.)

The Combination Cooperative Fuel Research (CFR) octane rating engine (model F1/F2) is used to determine the octane quality of gasoline and fuel blending components. This unit is recognized and approved by ASTM D2699 and D2700. The engine is equipped with a heavy-duty crankcase, variable compression cylinder, carburetor with adjustable fuel to air ratio, and knock measurement equipment (Figure 3).

Ready-to-use NIRS systems are also available for monitoring several gasoline quality parameters which cover varied ranges and their respective precisions (Table 1). Additionally, the manufacturers of NIRS analyzers usually offer application support to extend these ranges or improve upon the precision.

An overview of estimated costs for the analysis of RON and MON with a CFR Engine compared to the Metrohm NIRS DS2500 Petro Analyzer is shown in Table 2. The full payback is achieved within two years if considering only 50% of the primary analysis method (CFR Engine) is replaced by NIRS. This calculation is based on 2000 analyses per year (1000 RON + 1000 MON), with total running costs of approximately $32.50 per analysis (chemicals, maintenance, and labor).

Table 2. Cost of ownership CFR engine vs. DS2500 Petro Analyzer.
Total analyses RON + MON per year 2000 2000
Cost of operator per hour $25.00 $25.00
Cost of Analyzer CFR Engine NIRS DS2500 Petro Analyzer
Analyzer $500,000.00 $55,000.00
Total initial costs $0.001 $55,000.00
Running costs consumables / chemicals / maintenance
Chemicals per year (ASTM D2699/D2700) $20,000.00 $0.00
Maintenance cost per year $20,000.00 $1,500.00
Chemicals plus maintenance cost per analysis $20.00 $0.75
Total running costs per year $40,000.00 $1,500.00
Time spent per analysis  30 minutes < 1 minute
Labor cost of 1000 analyses of RON (ASTM D2699) $12,500.00 $416.50
Labor cost of 1000 analyses of MON (ASTM D2700) $12,500.00 $416.50
Labor cost per analysis $12.50 $0.42
Total labor costs per year $25,000.00 $833.00
Total running costs per year $65,000.00 $2,333.00
1Assumption that the instrument had previously been purchased, and therefore this cost is not included in the ROI calculation.

More information about the analysis of RON/MON and other parameters in gasoline can be found in our free Application Notes below.

In this example, RON/MON analysis was used to show cost savings and ROI when using NIRS to supplement a primary method. However, when expanding this to consider other key quality parameters such as the ones indicated in Table 1, the financial incentives for such an investment are even more compelling.

Summary

Near-infrared spectroscopy is very well suited for the analysis of key quality parameters in gasoline, diesel, and jet fuel. Available pre-calibrations are developed and validated in accordance with the ASTM guidelines. 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 gasoline, diesel, and jet fuel 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:

 

  • Pyrolysis gasoline (Pygas)
  • 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.
NIR spectroscopy in the petrochemical and refinery industry: The ASTM compliant tool for QC and product screening – Part 1

NIR spectroscopy in the petrochemical and refinery industry: The ASTM compliant tool for QC and product screening – Part 1

Introduction to the petrochemical and refining industry

Oil and gas for fuel are produced in nearly every corner of the globe, from small private wells generating around 100 barrels a day, to the large bore wells producing upwards of 40 times that volume. Despite this great variation in size, many parts of the refining process are quite similar.

Chemicals derived from petroleum or natural gas, so-called «petrochemicals», are an essential part of the contemporary chemical industry. The field of petrochemistry became increasingly popular around the early 1940’s during the second world war. At that time there was a growing demand for synthetic products which was a great driving force for the development of petrochemical products.

Oil refining aims to provide a defined range of products according to agreed specifications. Simple refineries use a distillation column (Figure 1) to separate crude oil into different fractions based on their chemical properties, and the relative quantities are directly dependent on the crude oil used. Therefore, it is necessary to obtain a range of crudes that can be blended into a suitable feedstock to produce the required quantity and quality of end products.

The basic products from fractional distillation are shown in Figure 1.
Wallace Carothers, inventor of polyamide.
Figure 1. Illustration of a fractionating distillation column used for the purposes of refining crude oil into several desirable end products.
Near-infrared (NIR) spectroscopy is a technique that is particularly suited for making quality control of these end products more efficient and cost-effective for manufacturers. Furthermore, NIRS is recognized and accepted by ASTM as an alternative method to other techniques. Dedicated ASTM methods for method development, method validation, and results validation are presented later in this article.

Read on for a short overview on NIR spectroscopy followed by application examples for the petrochemical and refinery industry to learn how petrochemical producers and refineries alike can benefit from NIRS.

NIR technology: a brief overview

The interaction between light and matter is a well-known process. Light used in spectroscopic methods is typically not described by the applied energy, but in many cases by the wavelength or in wavenumbers.

A NIR spectrometer such as the Metrohm NIRS DS2500 Petro Analyzer measures this light-matter interaction to generate spectra such as those displayed in Figure 2. NIRS is especially sensitive to the presence of certain functional groups like -CH, -NH, -OH, and -SH. Therefore, NIR spectroscopy is an ideal method to quantify different QC parameters like water content (moisture), cetane index, RON/MON (research and motor octane numbers), flash point, and cold filter plugging point (CFPP), just to name a few. Furthermore, the interaction is also dependent upon the matrix of the sample itself, which also allows the detection of physical and rheological parameters like density and viscosity.

Figure 2. Diesel spectra resulting from the interaction of NIR light with the respective samples.
All of this information is contained in a single spectrum, making this method suitable for quick multiparameter analysis. Liquid samples such as oils are secured within an appropriate container or vial (Figure 3), then placed as-is on the smart vial holder.
Figure 3. Liquid sample placement for NIR spectra measurement on the smart vial holder from Metrohm.
The measuring mode is referred to as «transmission», generally an appropriate procedure for analyzing liquids. For transmission measurement (Figure 4), the NIR light will travel through the sample while being absorbed. Unabsorbed NIR light passes to the detector. In less than 60 seconds the measurement is completed and the results are displayed.
Figure 4. A. Measurements of liquids are typically done with disposable vials. B. The NIRS measurement mode is known as transmission, where light travels through the sample while being absorbed (from left to right in the illustration).
The procedure to obtain NIR spectra already highlights two major advantages of NIR spectroscopy compared to other analytical techniques: simplicity regarding sample measurement, and speed:

  • Fast technique with results in less than a minute.
  • No sample preparation required – measure samples as-is.
  • Low cost per sample – no chemicals or solvents needed.
  • Environmentally friendly technique – no waste generated.
  • Non-destructive – precious samples can be reused after analysis.
  • Easy to operate – inexperienced users are immediately successful.

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

Where can NIRS be used in the refining process?

The refining process can be divided into three different segments:

  • Upstream
  • Midstream
  • Downstream

Upstream describes the process of converting crude oil into intermediate products. Refineries are usually very large complexes with several hazardous explosive areas. Therefore, operators are reluctant to transport samples from the different processes to the laboratory. Even the process of obtaining samples for analysis at external QC laboratories is laborious and can require significant paperwork and certified transport services. For obvious reasons, in most cases inline measurements are preferred. These types of measurements are typically done by process NIRS analyzers.

Read more about the difference between atline, online, and inline analyses in our blog post.
Curious about NIRS analyzers for inline process measurements, even in explosive areas? Visit our website to learn more.
Midstream, shown here in Figure 5, offers many more opportunities for the Metrohm DS2500 Petro Analyzer to assist in quality control.
Figure 5. Flowchart of how crude oil becomes gasoline at the local gas station, and where NIRS can perform quality checks during the process.
Fuel is constantly checked for quality when it is received as well as supplied, and in addition to this many terminals also test fuel quality prior to offloading the trucks. The total time for receiving and offloading fuel into a storage tank is approximately 30 minutes, so a fast analysis technique like NIRS is very advantageous.

Downstream at fuel depots and gas stations, the regulatory agencies require measurement of many of the same quality parameters as in the production of gasoline and diesel, and this can also be accomplished with NIRS. There is a significant advantage if the analysis can be done on-site using fresh samples and without the hassle of needing to transport them to testing laboratories.

Mobile NIRS fuel testing using the Metrohm NIRS XDS RapidLiquid Analyzer (XDS-RLA) has been successfully implemented in a number of countries where they enjoy the benefits of having instantaneous on-site results for gasoline and diesel testing. The calibrations developed on the XDS-RLA are easily transferrable to the DS2500 Petro Analyzer. The DS2500 Petro Analyzer does not require trained analysts, and the calibrations do not require constant maintenance, making this an ideal way to monitor different fuels at service stations and more.
Figure 6. Examples of mobile fuel testing with the Metrohm DS2500 Petro Analyzer.
Learn more about the possibilities of petrochemical analysis with Metrohm DS2500 Analyzers in our free brochure.

NIRS as an ASTM compliant tool for QC

Method development

ASTM E1655: Standard Practices for Infrared Multivariate Quantitative Analysis

«These practices cover a guide for the multivariate calibration of infrared spectrometers used in determining the physical or chemical characteristics of materials. These practices are applicable to analyses conducted in the near infrared (NIR) spectral region (roughly 780 to 2500 nm) through the mid infrared (MIR) spectral region (roughly 4000 to 400 cm-1).»

Multivariate analysis of petroleum products

ASTM D8321: Standard Practice for Development and Validation of Multivariate Analyses for Use in Predicting Properties of Petroleum Products, Liquid Fuels, and Lubricants based on Spectroscopic Measurements

«This practice covers a guide for the multivariate calibration of infrared (IR) spectrophotometers and Raman spectrometers used in determining the physical, chemical, and performance properties of petroleum products, liquid fuels including biofuels, and lubricants. This practice is applicable to analyses conducted in the near infrared (NIR) spectral region (roughly 780 nm to 2500 nm) through the mid infrared (MIR) spectral region (roughly 4000 cm-1 to 40  cm-1).»

Method validation

ASTM D6122: Standard Practice for Validation of the Performance of Multivariate Online, At-Line, Field and Laboratory Infrared Spectrophotometer, and Raman Spectrometer Based Analyzer Systems

«This practice covers requirements for the validation of measurements made by laboratory, field, or process (online or at-line) infrared (near- or mid-infrared analyzers, or both), and Raman analyzers, used in the calculation of physical, chemical, or quality parameters (that is, properties) of liquid petroleum products and fuels.»

Results validation

ASTM D8340: Standard Practice for Performance-Based Qualification of Spectroscopic Analyzer Systems

«This practice covers requirements for establishing performance-based qualification of vibrational spectroscopic analyzer systems intended to be used to predict the test result of a material that would be produced by a Primary Test Method (PTM) if the same material is tested by the PTM.»

Typical NIRS applications and parameters for the petrochemical and refinery industry

Petrochemicals are subject to standardized test methods to determine their chemical, physical, and tribological properties. Laboratory testing is an indispensable part of both research and development and quality control in the production of petrochemicals. The following test parameters are typically important to measure in the petrochemical and refinery industry (Table 1).

Table 1. Examples for use of NIRS for selected petrochemical QC parameters.
Specific Gravity (API) Gravity meter ASTM D298

AN-NIR-022

AN-NIR-024

AN-NIR-025

AN-NIR-041

AN-NIR-053

AN-NIR-071

AN-NIR-075

AN-NIR-080

AN-NIR-086

AN-PAN-1052

Boiling Point Distillation ASTM D2887
Cold Filter Plugging Point (CFPP) Standardized filter device ASTM D6371
Pour Point Pour Point analyzer ASTM D97
Cloud Point Cloud Point analyzer ASTM D2500
Flash Point Flash Point tester ASTM D93
Viscosity Viscometer ASTM D445
Color Colorimeter ASTM D1500
Density Densimeter ASTM D792
Fatty Acid Methyl Ester (FAME) FTIR ASTM D7806
Reid Vapor Pressure RVP analyzer ASTM D323
PIANO (Paraffins, Isoparaffins, Aromatics, Naphthenes, Olefins) Gas chromatograph ASTM D6729
Octane Number (RON/MON) CFR Engine ASTM D2699

ASTM D2700

Cetane Number CFR Engine ASTM D613
Diene value / MAV index Titration UOP 327-17
Parameter Conventional method ASTM method Relevant NIRS Application Notes

Future installments in this series

This article is a general overview of the use of NIR spectroscopy as the ideal QC tool for the petrochemical / refinery industry. Future installments will be dedicated to the most important applications and will include much more detailed information. Don’t miss our next blogs on the topics of:

 

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.
NIR spectroscopy in the polymer industry: The ideal tool for QC and product screening – Part 5

NIR spectroscopy in the polymer industry: The ideal tool for QC and product screening – Part 5

The history of polyurethanes

In 1937, the German chemist Dr. Otto Bayer (1902–1982) invented the versatile class of plastics we call polyurethanes. Polyurethanes are available in myriad forms—they are used in numerous products, from coatings and adhesives to shoe soles, mattresses, and foam insulation. Despite the variety in their characteristics, the underlying chemistry of these different forms is strikingly similar.

During World War II, the use of polyurethanes became popular as a replacement for rubber, which at the time was expensive and hard to obtain. Around the 1950s, polyurethanes began to be used in adhesives, elastomers, rigid foams, and flexible cushioning foams such as those used today.

Wallace Carothers, inventor of polyamide.
Dr. Otto Bayer was credited with inventing polyurethanes in 1937.

Nowadays, a life without polyurethane is difficult to imagine, as you can easily find it everywhere around you.

How is polyurethane created?

 

Polyurethanes are formed by reacting polyols (i.e., alcohols containing more than two reactive hydroxyl groups in each molecule) with di-isocyanates or polymeric isocyanates. Suitable catalysts and additives are used wherever necessary. Since both a variety of di-isocyanates and a wide range of polyols can be used to produce polyurethane, a large spectrum of polyurethane materials can be produced to meet the specific requirements for different applications. Polyurethanes can appear in a variety of forms including rigid foams, flexible foams, specialty adhesives, chemical-resistant coatings, sealants, and elastomers.

Figure 1. Molecular structures of isocyanates, polyols, and polyurethane.

Physical and chemical properties of polyurethanes

The properties of polyurethanes are highly dependent on their production process. When the polyol chain (Figure 1) is long and flexible, the final product will be soft and elastic. On the other hand, if the extent of cross-linking is very high, the final polyurethane product will be tough and rigid. The cross-linked structure of polyurethanes generally consists of three-dimensional networks which result in very high molecular weights. This structure also accounts for the thermosetting nature of the polymer since polyurethane typically does not soften or melt when exposed to heat.

One of the most popular forms of polyurethane is foam. This form is created by facilitating the production of carbon dioxide gas during the urethane polymerization process.

Typical applications of polyurethane

The primary application of polyurethane is in the production of foams (rigid and flexible). Other important applications and uses of polyurethane are listed below.

 

  • Low-density, flexible polyurethane foams are widely used in mattresses and automobile seats.
  • Bathroom and kitchen sponges are commonly made from polyurethane. It is also used in the manufacturing process of seat cushions and couches.
  • Polyurethane is also used to produce textiles used in some clothing and upholstery.
  • Due to its good insulating properties, polyurethane materials are commonly used in construction work.
  • Polyurethane moldings are also used in columns and door frames.
  • Flexible polyurethane is used in the manufacture of partially elastic straps and bands.
  • The low-density elastomers of polyurethane are widely used in the footwear industry.

In Table 1 a variety of polyurethane properties are compared to other conventional materials like rubber, metal, and plastic.

Table 1. Polyurethane in comparison with rubber, metal, and plastic.

PU vs. Rubber

PU vs. Metal

PU vs. Plastic

High abrasion resistance

Lightweight

High impact resistance

High cut and tear resistance

Noise reduction

Elastic memory

Superior load bearing

Abrasion resistance

Abrasion resistance

Thick section molding

Less expensive fabrication

Noise reduction

Colorability

Corrosion resistance

Variable coefficient of friction

Oil resistance

Resilience

Resilience

Ozone resistance

Impact resistance

Thick section molding

Radiation resistance

Flexibility

Lower cost tooling

Broader hardness range

Easily moldable

Low temperature resistance

Castable nature

Non-conductive

Cold flow resistance

Low pressure tooling

Non-sparking

Radiation resistance

Near-infrared spectroscopy as a tool to assess the quality of polyurethanes

Near-infrared spectroscopy (NIRS) has been an established method for both fast and reliable quality control within the polyurethane 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, a short overview of polyurethane applications is presented, followed by available turnkey solutions for polyurethane analysis developed according the NIRS implementations guidelines of ASTM E1655-17.

Did you miss the first parts in this series? Find them here!

For more detailed information about NIRS as a secondary technique, read our previous blog posts on this subject.

Applications and parameters for polyurethanes with NIRS

When producing different types of polyurethanes, it is important to check certain parameters to guarantee the quality of the finished products. Typical parameters include hydroxyl number, acid number, moisture, and color in polyols as well as the NCO (isocyanates) content, (total) acid number, and moisture content in polyurethanes. The most relevant applications for NIRS analysis in polyurethane production are listed later in this article in in Table 2.

Where can NIRS be used in the polyurethane production process?

Figure 2 shows the individual steps from plastic producer via plastic compounder and plastic converter to plastic parts and foam producer.

Figure 2. Illustration of the production chain for polyurethanes.

Easy implementation of NIR spectroscopy for plastic producers

Metrohm has extensive expertise with analysis of polyamides and offers a turnkey solution in the form of the DS2500 Polyol Analyzer. This instrument is a ready-to-use solution for the determination of multiple quality parameters in polyols and polyurethanes. For the analysis of polyurethane pellets and parts, the Metrohm DS2500 Solid Analyzer is recommended.

Figure 3. Turnkey solution for polyurethane analysis with the Metrohm DS2500 Polyol Analyzer.

Learn more about the possibilities of polymer analysis with Metrohm DS2500 Analyzers in our free brochure.

Application example:

Pre-calibrations and starter model for the PU industry on the DS2500 Polyol Analyzer

The determination of the parameters listed below in Table 2 is a lengthy and challenging process with conventional laboratory methods. To measure them all, several different techniques are required which takes a significant amount of time, not only to analyze the sample, but also for the instrument management and upkeep.

Table 2. Primary method vs. NIRS for the determination of various quality parameters in PU samples.
Parameter Primary method Time to result (primary method) Relevant NIRS Application Notes NIRS benefits
Hydroxyl number in Polyols

Titration

90 min. preparation + 1 min. Viscometer

AN-NIR-068

AN-NIR-065

AN-NIR-035

AN-NIR-007

All three parameters are measured simultaneously within a minute, without sample preparation or the need of any chemical reagents
NCO (Isocyanate) content in PU HPLC 20 min. preparation + 20 min. HPLC
Moisture content

Karl Fischer Titration

25 min. preparation + 5 min. KF Titration

 

The NIRS prediction models created for polyols are based on a large collection of real product spectra and are developed in accordance with ASTM E1655-17 Standard practices for Infrared Multivariate Quantitative Analysis. For more detailed information on this topic, download the free white paper.

To learn more about pre-calibrations for polyols, download our brochure and visit our website.

One example of a dedicated ASTM standard referring to NIRS is ASTM D6342-12 Standard Practice for Polyurethane Raw Materials: Determining Hydroxyl Number of Polyols by Near Infrared (NIR) Spectroscopy. The following application example demonstrates that the DS2500 Polyol Analyzer operating in the visible and near-infrared spectral region (Vis-NIR) provides a cost-efficient and fast solution for the determination of the hydroxyl number in polyols and the NCO (isocyanate) content in polyurethanes. With no sample preparation or chemicals required, Vis-NIR spectroscopy allows analysis of all three quality parameters listed in Table 2 in less than a minute. The results are shown in Figure 4 and Figure 5.

Figure 4. Turnkey solution for determination of hydroxyl number in polyols using the Metrohm DS2500 Polyol Analyzer. A: Sampling and analysis of polyols. B: NIRS results compared to a primary laboratory method along with the Figures of Merit (FOM).
Figure 5. Turnkey solution for determination of NCO content (Isocyanates) in polyurethane using the Metrohm DS2500 Polyol Analyzer. A: Sampling and analysis of polyurethane. B: NIRS results compared to a primary laboratory method along with the Figures of Merit (FOM).

This application example demonstrates that NIR spectroscopy is excellently suited for the analysis of multiple parameters in polyols and polyurethanes in less than one minute without sample preparation or using any chemical reagents. Visit our website to learn more about our variety of analytical solutions for the polymer industry!

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.

NIR spectroscopy in the polymer industry: The ideal tool for QC and product screening – Part 4

NIR spectroscopy in the polymer industry: The ideal tool for QC and product screening – Part 4

Polyamide (Nylon): A brief introduction

Wallace Carothers (1896–1937), the creator of polyamide.

Polyamide, more commonly known as Nylon, was first synthesized by Wallace Hume Carothers, an American organic chemist working for the DuPont chemical company. In 1935, he developed the formula known as PA66, or Nylon 66.

Just a few years later in 1938, Paul Schlack, a German chemist working at IG Farben, developed PA6 (also known as Nylon 6), a different molecule based on the organic compound caprolactam. Both types of polyamides are well-suited for many kinds of applications. The use of PA6 or PA66 depends on the technical requirements needed as well as the economical constraints.

The two most widely used polyamides are by far PA66 and PA6. These polyamides are most often manufactured into fibers for the textile industry or blown into films used for the packaging industry. Polyamides are also used to produce parts for numerous industries.

Polyamides with the highest performances are PPA (Polyphthalamide or high-performance polyamide) and PA46. Polyamides with these qualities are often used as a replacement for metal materials or for very specific applications where the polymer is exposed to extreme conditions, e.g. automotive structural parts or safety helmets.

Differences between Polyamide 6 (PA6 / Nylon 6) and Polyamide 66 (PA66 / Nylon 66)

Polyamide 6 (PA6) is also known as Nylon 6 or Polycaprolactam. It is one of the most commonly used compounds in the polyamide family. PA6 is synthesized via the ring-opening polymerization of caprolactam.

Figure 1. Molecular structure of caprolactam.
Figure 2. Molecular structure of Polyamide 6.

Polyamide 66 (PA66), also known as Nylon 66, is one of the most popular thermoplastics for engineering purposes and is primarily used as a metal replacement for various applications. Nylon 66 is synthesized via the polycondensation of hexamethylenediamine and adipic acid (two monomers containing six carbon atoms each).

Figure 3. Molecular structure of Polyamide 66.

The differences between both PA6 and PA66 come down to a lot of little things. While both are cost effective, Nylon 6 is typically around 30% cheaper than Nylon 66. A comparison of different factors is made for the two polymers in Table 1.

Table 1. Comparison of PA6 and PA66
Parameter PA6 PA66
Machinability – low tool wear and surface finish Good Better
Mold shrinkage Lower Higher
Water absorption rate Higher Lower
Tensile strength 6.2 × 104 kPa (Good) 8.2 × 104 kPa (Better)
Crystalline melting point 225 °C 265 °C
Density 1.15 g/mL 1.2 g/mL
Typical molding shrinkage ratio 1.2 % 1.5 %
Key properties of PA66 and PA6

As stated earlier, Polyamide 66 (PA66) and Polyamide 6 (PA6) are used in so many different applications because of their excellent performance and relatively low cost. Some of the most important properties of these polyamides are listed below:

  • High strength and rigidity at high temperatures
  • Good impact strength, even at low temperatures
  • Good abrasion and wear resistance
  • Excellent resistance to fuels and oils
  • Good fatigue resistance
  • Very good flow for easy processing
  • PA6 has excellent surface appearance and better processability than PA66 due to its very low viscosity
  • Good electrical insulating properties
  • High affinity for water absorption can limit the applications and usage
  • Low dimensional stability (water absorption results in dimensional change)

Near-infrared spectroscopy as a tool to assess the quality of polyamides

Near-infrared spectroscopy (NIRS) has been an established method for both fast and reliable quality control within the polyamide 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, a short overview of polyamide applications is presented, followed by available turnkey solutions for polyamide analysis developed according the NIRS implementations guidelines of ASTM E1655-17.

Did you miss the first parts in this series? Find them here!

For more detailed information about NIRS as a secondary technique, read our previous blog posts on this subject.

Applications and parameters for polyamides with NIRS

Polyamide production requires that certain important quality parameters be checked on a regular basis. Typical parameters are relative viscosity as well as the amine and carboxylic end groups, and moisture content. Functional group and viscosity analysis of polyamides is normally a lengthy and challenging process due to the limited solubility of the sample and the need to use different analytical methods. Furthermore caprolactam, an important precursor for polyamide production, is very hygroscopic and water soluble—therefore it is crucial to have a reliable analysis technique for determination of water content. Otherwise the quality of the final product could be compromised.

The most relevant applications for NIRS analysis of PA quality parameters are indicated later in this article in Table 2.

Where can NIRS be used in the production process of polyamides?

Figure 4 shows the individual steps from plastic producer via plastic compounder and plastic converter to plastic parts and textile producer. The first step in which near-infrared lab instruments can be used is when the pure polymers like PA are produced, and their purity needs to be confirmed. NIRS is also a very useful technique during the next step where polymers are compounded into intermediate products to be used for further processing.

Figure 4. Illustration of the production chain for polyamides.

Easy implementation of NIR spectroscopy for plastic producers

Metrohm has extensive expertise with analysis of polyamides and offers a turnkey solution in the form of the DS2500 Polymer Analyzer. This instrument is a ready-to-use solution for the determination of multiple quality parameters in different polyamides.

Figure 5. Turnkey solution for PA analysis with the Metrohm DS2500 Polymer Analyzer.

Application example:

Pre-calibrations available for the polyamide industry on the DS2500 Polymer Analyzer

The determination of the parameters listed below in Table 2 is a lengthy and challenging process with conventional laboratory methods. To measure them all, several different techniques are required which takes a significant amount of time, not only to analyze the sample (which has limited solubility, further complicating the situation), but also for the instrument management and upkeep.

Table 2. Primary method vs. NIRS for the determination of various quality parameters in PA samples.
Parameter Primary method Time to result (primary method) Relevant NIRS Application Notes NIRS benefits
Relative viscosity

Viscosity

90 min. preparation + 1 min. Viscometer

AN-NIR-077

AN-NIR-060

AN-NIR-005

All four parameters are measured simultaneously within a minute, without sample preparation or the need of any chemical reagents
Carboxyl end groups

Titration

90 min. preparation + 20 min. Titration
Amine end groups

Titration

90 min. preparation + 20 min. Titration
Moisture content

Karl Fischer Titration (oven)

2 min. preparation + 15 min. KF Titration (oven)

 

The NIRS prediction models created for polyamides are based on a large collection of real product spectra and is developed in accordance with ASTM E1655-17 Standard practices for Infrared Multivariate Quantitative Analysis. For more detailed information on this topic, download the free white paper.

To learn more about pre-calibrations for polyamides, download our brochure and visit our website.

Figure 6 shows the results of the Metrohm turnkey solution for non-destructive determination of several quality parameters in PA listed in Table 2.

Figure 6. Turnkey solution for relative viscosity (RV), amine end groups, carboxyl end groups, and moisture in nylon (PA6) using the Metrohm DS2500 Polymer Analyzer. A: Sampling and analysis of PA6. B: Results of the four analyses from NIRS compared to a primary laboratory method along with the Figures of Merit (FOM) for each analysis.

This solution demonstrates that NIR spectroscopy is very suitable for the analysis of multiple parameters in polyamide in less than one minute without sample preparation or using any chemical reagents. Learn more about the procedure in our free Application Note!

The examples shown above refer to PA6 and PA66, but NIRS is undoubtedly a great tool for the rapid screening and QC of polyamides with different chain lengths.

Other installments in this series

This blog is a detailed overview of the use of NIR spectroscopy as the ideal QC tool for Polyamide 6 (PA6) and Polyamide 66 (PA66). The last installment of this blog series is dedicated to:

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.

NIR spectroscopy in the polymer industry: The ideal tool for QC and product screening – Part 3

NIR spectroscopy in the polymer industry: The ideal tool for QC and product screening – Part 3

Polyethylene terephthalate (PET): A brief introduction

PET is a very common plastic, mostly encountered in our lives as PET bottles and as a food packaging material. In this article you will learn how NIR spectroscopy can improve the efficiency of your PET analysis at different steps along the production cycle. Before getting into this, let’s introduce some background information about PET.

Polyethylene terephthalate (PET)

Polyethylene terephthalate (PET) is a general-purpose thermoplastic polymer which belongs to the polyester family. Polyester resins are known for their excellent combination of properties such as mechanical, thermal, and chemical resistance as well as dimensional stability.

PET is one of the most recycled thermoplastics and has the number 1 as its recycling symbol. Recycled PET can be converted into fibers, fabrics, sheets for packaging and for manufacturing automotive parts. PET is a highly flexible, colorless, and semi-crystalline resin in its natural state. Depending upon how it is processed, it can be semi-rigid to rigid. It exhibits good resistance to impact, moisture, alcohols, and solvents.

The chemical formula of PET is (C10H8O4)n and its molecular structure is shown in Figure 1.

Figure 1. Molecular structure of linear PET.

In addition to linear PET, there is also a branched version of the polymer. Branched PET is typically mixed with a small percent of isophthalic acid (C8H₆O4), because purified isophthalic acid (PIA, Figure 2) reduces the crystallinity of PET, serving to improve its clarity and increase the productivity of bottle manufacturing processes.

Diethylene glycol (DEG) as an additive also reduces the rate of crystallization of PET when crystallizing from the melt, isothermally and dynamically.

Figure 2. Molecular structure of isophthalic acid.
The key properties and advantages of PET resin are numerous:
  • very strong and lightweight, and therefore easy and efficient to transport
  • has good gas (oxygen, carbon dioxide) and moisture barrier properties, meaning low gas permeability (particularly against CO2)
  • exhibits excellent electrical insulating properties
  • broad range of use temperature (-60 to 130 °C)
  • high heat distortion temperature (HDT)
  • suitable for transparent application purposes
  • practically shatter-resistant – PET does not break or fracture and is used to replace glass in some applications
  • recyclable material
  • transparent to microwave radiation
  • very resistant to alcohols, aliphatic hydrocarbons, oils, greases, and diluted acids
  • moderately resistant to diluted alkalis, aromatic and halogenated hydrocarbons
  • PET is approved as safe for contact with foods and beverages by the FDA, Health Canada, EFSA, and other health agencies

What is polyethylene terephthalate (PET) used to make?

Polyethylene terephthalate is used in several types of packaging applications as shown in Figure 3. Due to its strength, light weight, and many other attractive properties, PET excels as a food packaging material.

Figure 3. PET is an ideal choice for many food packaging applications due to its strength to weight ratio.

Polyester makes up nearly two-thirds of synthetic fibers produced. There are many different types of polyester, but the type most often produced for use in textiles is PET. When used in a fabric, it is most often referred to as «polyester» or «poly» (Figure 4). This material costs very little to produce, which is the primary driver for its use in the textile industry.

Approximately 60% of the global PET production is used to make fibers for textiles while about 30% is used to make bottles for various purposes. Its ability to be recycled is especially attractive for manufacturers looking to save costs and operate in a greener manner.

Figure 4. PET makes up a significant portion of produced polyester fabric.

In the electronics industry, PET is chosen to replace less ideal materials due to its excellent electrical insulating properties and resistance to distortion even at high temperatures. PET is also used to manufacture many parts in the automotive industry (Figure 5).

Figure 5. PET is often used in the manufacturing of various automotive parts.

NIRS as a tool to assess the quality of PET

For over 30 years, near-infrared spectroscopy (NIRS) has been an established method for fast and reliable quality control within the PET industry. Despite this, many producers still do not consistently consider the implementation of NIRS in their QA/QC labs. Limited experience regarding application possibilities or a general hesitation about implementing new methods are some of the reasons behind this.

The advantages of using NIR spectroscopy for QA/QC are numerous. One major advantage of NIRS is the determination of multiple parameters in just 30 seconds with no sample preparation! The non-invasive light-matter interaction used by NIRS, influenced by physical as well as chemical sample properties, makes NIRS a suitable method for the determination of several critical quality parameters in these polymers and many more.

In the remainder of this article, a short overview of PET applications is presented, followed by available turnkey solutions for PET, developed according the NIRS implementation guidelines of ASTM E1655-17.

Did you miss the first parts in this series? Find them here!

For more detailed information about NIRS as a secondary technique, read our previous blog posts on this subject.

Applications and parameters for PET with NIRS

During production of PET it is important to check certain parameters to guarantee the quality. These parameters include the diethylene glycol content, isophthalic acid content, intrinsic viscosity (ASTM D4603), and the acid number (AN). Determination of these parameters is a lengthy and challenging process due to the limited solubility of the sample and the need to use different analytical methods.

The most relevant applications for NIRS analysis of PET are listed in Table 1.

Table 1Available application notes for use of NIR for PET
Polymer Parameter Related NIRS Application Notes
Polyethylene terephthalate (PET)

Diethylene glycol, Intrinsic Viscosity, Acid number, Isophthalic acid

AN-NIR-023

Where can NIRS be used in the production process of PET?

Figure 6 shows the individual production steps from the plastic producer via plastic compounder and plastic converter to the plastic parts producer. The first step in which near-infrared lab instruments can be used is when the pure polymers like PET are produced, and their purity needs to be confirmed. NIRS is also a very useful technique during the next step where polymers are compounded into intermediate products to be used for further processing.

Figure 6. Illustration of the polyethylene terephthalate production chain.

Easy implementation of NIR spectroscopy for plastic producers

Metrohm has extensive expertise with analysis of PET and offers a turnkey solution in the form of the DS2500 Polymer Analyzer. This instrument is a ready-to-use solution to determine multiple quality parameters in PET.

Figure 7. Turnkey solution for PET analysis with the Metrohm DS2500 Polymer Analyzer.

Application example:

Pre-calibrations available for the PET industry on the DS2500 Polymer Analyzer

Due to the limited solubility of polyethylene terephthalate and the need to use several different analytical methods, the determination of the parameters listed in Table 2 is a lengthy and challenging process with conventional laboratory techniques.

Table 2. Primary method vs. NIRS for the determination of various quality parameters in PET samples.
Parameter Primary method Time to result (primary method) NIRS benefits
Diethylene Glycol content

Extraction + HPLC-MS

45 min. preparation + 40 min. HPLC-MS All four parameters are measured simultaneously within a minute, without sample preparation or the need of any chemical reagents
Isophthalic acid content Dissolve + HPLC 45 min. preparation + 40 min. HPLC
Intrinsic viscosity Dissolve + Viscometer 90 min. preparation + 1 min. Viscometer
Acid number Dissolve + Titration 90 min. preparation + 10 min. Titrator

The NIRS prediction models created for PET are based on a large collection of real product spectra and is developed in accordance with ASTM E1655-17 Standard practices for Infrared Multivariate Quantitative Analysis. For more detailed information on this topic, download the free white paper.

To learn more about pre-calibrations for PET, download our brochure and visit our website.

The result of this turnkey solution for rapid non-destructive determination of the key quality parameters for PET listed in Table 2  is shown in Figure 8.

Figure 8. Turnkey solution for diethylene glycol, isophthalic acid, intrinsic viscosity and acid number in PET using the Metrohm DS2500 Polymer Analyzer. A: Sampling and analysis of PET granulate. B: Results of the four analyses from NIRS compared to a primary laboratory method along with the Figures of Merit (FOM) for each analysis.

This solution demonstrates the feasibility of NIR spectroscopy for the analysis of multiple parameters in PET in less than one minute without sample preparation or using any chemical reagents.  Learn more about the procedure in our free Application Note!

Other installments in this series

This article is a detailed overview of the use of NIR spectroscopy as the ideal QC tool for the analysis of polyethylene terephthalate (PET). Other installments in this series are dedicated to:

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.