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Part I Introduction 1 Surface

This book deals with the application of modern techniques to paint analysis, with a special focus on surface analysis. If we pause to consider the word “surface”, we soon realise what a relative and vague term it is. To a painter, “surface” does not mean the same as it does to a surface chemist. To a painter, the surface represents that part of an object which is usually presented to the outside world and can be touched and observed directly. However, it can also be defined as the boundary layer between a solid or liquid material and a surrounding liquid or gaseous phase. A surface physicist would probably refer to it as a phase interface. Alternatively, it could be defined as the area of a solid or liquid thing at which the bulk physical and chemical properties change instantly, a so-called property boundary. A surface chemist, however, is talking about the uppermost molecular layers of a material when he uses the word surface. This is an area that can’t be observed without the help of analytical techniques. In fact, the uppermost layers of an object often determine the quality and behaviour of the material as far as (paint) adhesion is concerned. Definition of surface So let’s first define how we shall use the word surface in this book. A surface is a boundary layer which separates a substrate from the surrounding environment (air, liquid). It is typically 1 nm to 1 µm thick. In contrast, a “thin layer” is defined as being 1 µm to 10 µm thick. The surface plays a significant role in the physical and chemical properties of a material. Let’s look, for example, at a toll manufacturer who paints and coats coils and metal profiles. The surface of the raw material might well look clean. However, the material has a long history before it has been delivered to this company to be painted or coated. Production, storage and transport of a coil, for example, afford much opportunity for numerous substances to be adsorbed onto the surface. This surface layer of, say, contaminants may not be visible, but it
Figure I-1: AFM (atomic force microscope) image of a paint surface (60 x 60 µm)
Roger Dietrich: Paint Analysis © Copyright 2009 by Vincentz Network, Hannover, Germany ISBN: 978-3-86630-912-8

a polymer) are also key parameters. The manufacturer or supplier of the raw material matches the original polymer to customer demands. The chemical interaction of paint compounds and the reaction between each compound and the ingredients of the substrate (e. even worse. a few questions need to be asked before the painting process is started. the chemical composition of the outermost molecular layer plays a significant role. His efforts might well produce a surface quality worse than before. In most cases. In accordance with the requirements imposed on the polymer material. without knowing what to remove from the surface. But he will do so without knowing if it is necessary and. The same is true of the coating material itself. it is not just the polymer which is of interest. therefore. And sometimes even traces of contaminants can seriously impair the adhesion of a coating to a surface. the paint will exhibit poor adhesion or craters after application. Even a monomolecular layer of some of these oils can have deleterious effects on coating procedures. As the paint and the painted substrate have to be a chemical match if good adhesion is to be obtained. . That is a process which the polymer supplier does not see. As these ultra thin layers are invisible. light.Surface 11 is there nonetheless. One parameter the supplier is not concerned about is the paintability of the product made from the granules which he supplies. Unfortunately. When it comes to processing of the coil. the unfortunate manufacturer is in fact “blind” as far as the surface quality of his coils is concerned. he will decide to install a cleaning process before applying the coating. a moulded polymer part has to be coated. If the coil has been coated with a protective layer of oils to prevent corrosion during transport and storage. • What is the chemical composition of the substrate surface? • Which pre-treatment can be used to improve paint adhesion and what effect will it have? • How do the paint ingredients influence the surface of the material that has to be painted? • What influence do the paint additives have on paint adhesion? Unfortunately.g. such as surfactants. for example. impact or heat resistance. these questions often can’t be answered by simple tests or classical chemical analysis because they require an ability to analyse tiny amounts of substances that have high surface sensitivity. due to the presence of oil residues and traces of cleaning chemicals. If. This not only creates a demand for characterisation of the raw materials and products. he adds additives to improve flame. Modern high-performance paints have to fulfil many requirements simultaneously that are sometimes hard to match. there is no “magic” process for eliminating all the various kinds of contaminants. Only the surface analysis techniques described in this book can answer these questions A growing field of application for modern surface analytical techniques is not only paint application but also paint production.

On the other hand. and wetting failure. the standard techniques are not very helpful. it has been shown in the past that additives present in polymers “designed” to enhance moulding processes. especially in the offering good release from injection moulds. In fact. they describe the product and its properties. standard analytical tools often fall short when failures and production problems arise. Or. They ensure that the desired level of quality is achieved. can prove disastrous for the painting process. Most of the additives incorporated into a polymer migrate to the surface. a monomolecular layer of a release agent on the surface can easily cause severe adhesion failure if the material is to be painted. In other words. Before this problem can be solved. haze. This is an analytical gap that can be closed by the surface analytical techniques described in this book.1 Relevance of modern analytical techniques to paint analysis There are hundreds of techniques for analysing paints and coatings. acid value. These considerations will be discussed later in this book. etc. there are many parameters which influence the decision as to which technique to employ for the analysis. This is a task that can easily be fulfilled by the techniques we are going to describe in this book.12 Surface However. The standard techniques are perfect for finding out the quality of a product. They yield information about viscosity. This sometimes leads to unpredictable results. hardness. if a product is sub-quality and the question is asked as to why this happened. 1. it is necessary to know what has caused the paint defect. However. but also to learn something about the polymers which have to be painted. The quantity of substance may be too low to be detected by standard techniques. For example. The substance or inclusion particle causing this failure is too small to be characterised by standard techniques. chemical reactions. time or solvents. such as paint adhesion failure. They will help to answer the question: Why does a product have unexpected properties and why do failures happen? Typical topics in paint analysis are: • What do contaminants in paint layers or wet paint samples consist of? • What is the chemical composition of paint layers at a certain depth from the surface? • How are chemical bonds formed between paint components? • Why does a paint layer peel off a substrate and where does the delamination take place? • What is the reason for paint spots? It should be mentioned that there is no all-embracing technique that can answer these questions. humidity. gloss. discoloration. it takes an experienced user to find the best tool that can answer the questions raised about the sample. including: • additional information about the appearance of the defect • preliminary sample investigation by optical light microscopy • chemical and physical properties of the coating • Desired detection limit In other words. driven by temperature. poor cleaning procedures in a paint shop might cause paint defects of a few microns in size. . Many manufacturers of paint for automotive interior parts have therefore discovered that it is essential not only to know their own paint manufacturing process.

The evaluation must include • plausibility check • comparison with databases • interpretation with respect to the analytical problem The nature of the interaction which occurs between the probing beam and the sample depends on the type. the main principle consists in probing a sample with radiation. ions or X-rays. energy and angle of incidence of the probing radiation and.2 General considerations Before we present the techniques that will be discussed in this book.General considerations 13 1. The last step of the process is data evaluation by an experienced analyst. The result can be displayed as a spectrum on a computer or be printed on paper. such as infrared waves and X-rays. This “reaction” by the sample is detected by an electronic system composed of an analyser and a detector. Figure I-3: Interaction between the primary radiation and the sample . the sample material. Figure I-2: General concept of probing the surface of a sample with radiation The sample is essentially analysed by radiation that probes for specific properties and characteristics of the material. can consist of electrons. The primary radiation triggers a reaction specific to the sample that may take the form of the emission of electrons. neutral particles and photons. of course. This radiation. it would be helpful to find a common basic principle to describe them. No matter whether we are talking about infrared spectroscopy or TOF-SIMS or SEM. which is called the primary radiation. ions.

The radiation emitted by the sample is called secondary radiation. may lead to the formation of: • • • • secondary electrons X-rays back-scattered electrons fluorescence Figure I-4: Components of primary radiation Figure I-5: Result of sample excitation by primary radiation . Probing with an electron beam.14 Surface The primary radiation interacts with the sample in a specific way. for example. Each type of primary radiation can produce a different type of secondary radiation. Each type of sample reaction can be detected separately and analysed to reveal the chemical and physical composition of the sample and its surface.

It is commonly said that one technique on its own is no use and so a combination is the best way of achieving the right results. which contains information about the sample and its surface. too. which sometimes renders the technique useless for “real world samples”. The limiting features are: . angle and intensity of the primary radiation in accordance with the topography. can consist of electrons. The latter is a consequence of diffraction and dispersion that change the energy. structure and chemical composition of the sample. we will cover those techniques which have proven to be very useful for routine work and can deliver data in a reasonable time and at reasonable cost. Many of them. Others require vacuum conditions. analysed and displayed in the form of an angle-. In this book. The secondary radiation emanating from the sample is detected.or mass-resolved spectrum. allow only very limited sample sizes. but the secondary radiation emitted by the sample. Some of them are useful for solving practical problems and have made their way into routine work. never passed the experimental stage and have very limited application to technical samples outside of academia. The various types of probing primary radiation and detected secondary radiation have spawned more than 50 different analytical techniques over the decades. The parameters to know about a technique are its • • • • information depth detection limits information content suitability for technical problems Some techniques. Not only the primary radiation. It is very important to appreciate this when trying to find the right combination for the given analytical problem. ions. The in Table I-1 (page 16) mentioned techniques yield different data about the sample. energy. for example. Only a handful of techniques have proven useful for routine work. and that excludes liquid or volatile samples. neutral particles and photons that result from sample excitation or reflection of the primary radiation. however. Each has its particular strengths and weaknesses.General considerations 15 Figure I-6: Surface analysis techniques Each type of radiation conveys different information about the sample that all adds up to a comprehensive understanding of the sample’s properties.

If. it is the general surface quality of the sample which is of interest. a larger area measurement must be performed in order that a representative image of the surface composition may be obtained. the technique to use must allow for spot analysis.16 Surface Table I-1: List of analytical techniques Primary radiation electrons Secondary radiation electrons Technique Abbreviation Analysed area auger electron spectroscopy scanning electron microscopy AES SEM uppermost molecular layer sample surface down to a depth of a few microns sample surface down to a depth of a few microns sample surface down to a depth of a few microns X-rays electron microanalysis surface infrared spectroscopy Infrared microscopy ESMA EDX WDX FT-IR ATR IRRAS IRM XPS ESCA infrared infrared X-rays electrons X-ray photoelectron sample surface down to a depth of a few nanometres uppermost molecular layer ions ions secondary ion mass spectroscopy SIMS TOF-SIMS • • • • measuring time per sample suitability for technical samples comprehensive databases of reference materials sample preparation Another important question is the sample area to be analysed. for example. This means the investigation of a very small spot with a lateral resolution of a few microns. a paint crater a few microns in diameter has to be analysed for possible surface contaminants capable of causing cratering. If. Analysis of the distribution of a specific substance over a certain Figure I-7: Measuring modes in surface analysis . on the other hand.

Figure I-8: Schematic diagram of instrumentation 1. After interaction of the primary beam with the sample (surface). On the assumption that not only the chemical composition of a surface area has to be analysed but also the depth distribution. The instrumentation setup for all techniques consists of an excitation system (the primary system) that generates photons. Although they differ greatly in detail and in their chemical background. a depth-profiling mode needs to be chosen. That entails sputtering the sample layer by layer and analysing the surfaces as they become exposed. The detector records the separated or resolved signals and measures their intensity. . or energy.g. The signals generated by it are displayed as a spectrum. electrons or ions. Some techniques have an additional sputtering system (e. the instrumentation used follows a general concept. mass.Instrumentation 17 area calls for a scanning technique that generates a chemical map of the analysed area. The analyser separates the secondary radiation spectroscopically by energy. direction or mass. the excited secondary radiation is collected by a ray optics system which directs the secondary beam towards the analyser. which is a chart of intensity versus wavelength.3 Instrumentation Many of the analytical techniques we will describe here require vacuum conditions. The primary beam is directed by a focusing system onto the sample surface and into the desired area. an ion gun) that allows for subsequent sputtering of layers and thus for depth profiling.

basic answers to such questions as • What might be causing craters and spots in paint layers? • Where does paint delamination originate in a multi-layer system? • What does a residue in a raw material look like? The basic theory of light microscopy (LM) has been described elsewhere and will not be repeated in this book. However. A= light microscopy image of the border between lasered symbol and paint. and in most cases the tool to use is (optical) light microscopy. Germany ISBN: 978-3-86630-912-8 . Figure II-1: Painted key panel showing paint adhesion failure after laser treatment. cracks or material defects. Years of experience of failure analysis show that a great deal of the serious damage is due to very small defects. Hannover. B= EFI-3D image of the same area Roger Dietrich: Paint Analysis © Copyright 2009 by Vincentz Network.18 Theory of analysis Part II Theory of analysis 1 Optical light microscopy One of the main topics of this book is failure analysis. Light microscopy reveals initial. This basic technique can be used to carry out a preliminary sample inspection to gain an overview of the problem. it is worth focusing on a special method of LM that was developed a few years ago and offers highly interesting possibilities with respect to material surfaces. The first step in failure analysis is to find out what kind of problem we are dealing. fibres. particles.

At high resolution. Therefore. even for low-resolution purposes. It automatically takes pictures of several focal planes in rough objects. a scanning electron microscope had to be used to scan the surface topography of rough and structured samples. This is one module of the image-processing software “AnalySIS” developed by the company SIS/Olympus. in the past. such as those of structured polymers or metals. rough material surfaces. Thanks to the latest developments in digital cameras and software solutions.Optical light microscopy 19 A main disadvantage of conventional light microscopy is the lack of depth of focus. cannot be inspected both very sharply and at high resolution at the same time. Figure II-2: Light microscopy image of a paint crater (top) and calculated EFI-3D image of the same paint failure . the depth of focus of light microscopy can be extended virtually by a so-called EFI option (Extended Focal Imaging). extracts only the sharp details of each focal plane and adds them together to produce an image of unlimited depth of focus.

Figure II-4: Simplified model of an inter-atomic bond consisting of two masses m1 and m2 joined by a spring Roger Dietrich: Paint Analysis © Copyright 2009 by Vincentz Network. this is known as the “chemical shift”. Hannover. 2 Infrared spectroscopy Infrared spectroscopy (IR) is an analytical tool that has been well known for decades but only lent itself to routine work with the application of Fourier transform to data processing.001 and 1. This additionally permits the layer thickness and topography to be measured. hydrocarbons.6 eV. acids. such as esters. This corresponds to energies between 0. The spectrum is evaluated by comparison with reference spectra and by examining the individual peaks to identify the various functional groups in the molecule or material.20 Infrared spectroscopy It is thus an easy matter to obtain topographical images of extremely rough surfaces or paint failure without the help of scanning electron microscopy for magnifications of less than x1000. A defined wavelength range is scanned with infrared light to yield a collection of absorption information which can be displayed as bands in an infrared spectrum. 2. As the bonds between different atoms have distinct bond energies. Germany ISBN: 978-3-86630-912-8 . amines and the like. it takes characteristic energies to excite them. These photons excite characteristic vibrations of the interatomic bonds in a molecule. These energies correspond to certain wavelengths of the infrared beam. The basic principle of IR spectroscopy is the structural characterization of materials through the absorption of infrared radiation by inter-atomic bonds. The energy needed to excite the vibrations is absorbed from the incident infrared radiation.1 Physical background Figure II-3: Basic principle of infrared spectroscopy The probe used in IR spectroscopy is radiation from the infrared region of the electromagnetic spectrum.