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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
If the coil has been coated with a protective layer of oils to prevent corrosion during transport and storage. he adds additives to improve flame. due to the presence of oil residues and traces of cleaning chemicals. • 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. That is a process which the polymer supplier does not see. 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. the unfortunate manufacturer is in fact “blind” as far as the surface quality of his coils is concerned. the paint will exhibit poor adhesion or craters after application. such as surfactants. a moulded polymer part has to be coated. impact or heat resistance. . The same is true of the coating material itself. therefore. Modern high-performance paints have to fulfil many requirements simultaneously that are sometimes hard to match. for example. But he will do so without knowing if it is necessary and. there is no “magic” process for eliminating all the various kinds of contaminants. If. In most cases. One parameter the supplier is not concerned about is the paintability of the product made from the granules which he supplies.Surface 11 is there nonetheless. As these ultra thin layers are invisible. This not only creates a demand for characterisation of the raw materials and products. even worse. The chemical interaction of paint compounds and the reaction between each compound and the ingredients of the substrate (e. without knowing what to remove from the surface. a polymer) are also key parameters. it is not just the polymer which is of interest. light. As the paint and the painted substrate have to be a chemical match if good adhesion is to be obtained. the chemical composition of the outermost molecular layer plays a significant role. His efforts might well produce a surface quality worse than before. Even a monomolecular layer of some of these oils can have deleterious effects on coating procedures. Unfortunately. he will decide to install a cleaning process before applying the coating. In accordance with the requirements imposed on the polymer material. The manufacturer or supplier of the raw material matches the original polymer to customer demands. 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. When it comes to processing of the coil.g. a few questions need to be asked before the painting process is started. And sometimes even traces of contaminants can seriously impair the adhesion of a coating to a surface.
driven by temperature.1 Relevance of modern analytical techniques to paint analysis There are hundreds of techniques for analysing paints and coatings. This is an analytical gap that can be closed by the surface analytical techniques described in this book. The substance or inclusion particle causing this failure is too small to be characterised by standard techniques. The quantity of substance may be too low to be detected by standard techniques. gloss. . if a product is sub-quality and the question is asked as to why this happened. For example. especially in the offering good release from injection moulds. can prove disastrous for the painting process. This is a task that can easily be fulfilled by the techniques we are going to describe in this book. Most of the additives incorporated into a polymer migrate to the surface. there are many parameters which influence the decision as to which technique to employ for the analysis. Many manufacturers of paint for automotive interior parts have therefore discovered that it is essential not only to know their own paint manufacturing process. it takes an experienced user to find the best tool that can answer the questions raised about the sample.12 Surface However. 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. The standard techniques are perfect for finding out the quality of a product. hardness. a monomolecular layer of a release agent on the surface can easily cause severe adhesion failure if the material is to be painted. In fact. and wetting failure. etc. chemical reactions. the standard techniques are not very helpful. Or. On the other hand. They ensure that the desired level of quality is achieved. time or solvents. humidity. such as paint adhesion failure. 1. They yield information about viscosity. but also to learn something about the polymers which have to be painted. These considerations will be discussed later in this book. However. discoloration. In other words. haze. it has been shown in the past that additives present in polymers “designed” to enhance moulding processes. This sometimes leads to unpredictable results. poor cleaning procedures in a paint shop might cause paint defects of a few microns in size. it is necessary to know what has caused the paint defect. acid value. standard analytical tools often fall short when failures and production problems arise. Before this problem can be solved. 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. they describe the product and its properties.
No matter whether we are talking about infrared spectroscopy or TOF-SIMS or SEM. neutral particles and photons.2 General considerations Before we present the techniques that will be discussed in this book. energy and angle of incidence of the probing radiation and. of course. the main principle consists in probing a sample with radiation. which is called the primary radiation. ions. 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. The primary radiation triggers a reaction specific to the sample that may take the form of the emission of electrons. can consist of electrons.General considerations 13 1. The result can be displayed as a spectrum on a computer or be printed on paper. This radiation. 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 last step of the process is data evaluation by an experienced analyst. the sample material. This “reaction” by the sample is detected by an electronic system composed of an analyser and a detector. ions or X-rays. it would be helpful to find a common basic principle to describe them. Figure I-3: Interaction between the primary radiation and the sample . such as infrared waves and X-rays.
Each type of primary radiation can produce a different type of secondary radiation. The radiation emitted by the sample is called secondary radiation. Probing with an electron beam. Each type of sample reaction can be detected separately and analysed to reveal the chemical and physical composition of the sample and its surface. for example. 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 .14 Surface The primary radiation interacts with the sample in a specific way.
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. Many of them. however. The various types of probing primary radiation and detected secondary radiation have spawned more than 50 different analytical techniques over the decades. In this book. Some of them are useful for solving practical problems and have made their way into routine work.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. analysed and displayed in the form of an angle-. It is very important to appreciate this when trying to find the right combination for the given analytical problem. Not only the primary radiation. angle and intensity of the primary radiation in accordance with the topography. Each has its particular strengths and weaknesses. which sometimes renders the technique useless for “real world samples”. Others require vacuum conditions. structure and chemical composition of the sample. never passed the experimental stage and have very limited application to technical samples outside of academia. ions. energy. too. The secondary radiation emanating from the sample is detected. 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. The in Table I-1 (page 16) mentioned techniques yield different data about the sample. Only a handful of techniques have proven useful for routine work. neutral particles and photons that result from sample excitation or reflection of the primary radiation. and that excludes liquid or volatile samples. can consist of electrons. The parameters to know about a technique are its • • • • information depth detection limits information content suitability for technical problems Some techniques. for example. allow only very limited sample sizes.or mass-resolved spectrum. which contains information about the sample and its surface. but the secondary radiation emitted by the sample. The latter is a consequence of diffraction and dispersion that change the energy. The limiting features are: .
Analysis of the distribution of a specific substance over a certain Figure I-7: Measuring modes in surface analysis . a larger area measurement must be performed in order that a representative image of the surface composition may be obtained. for example. This means the investigation of a very small spot with a lateral resolution of a few microns.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. it is the general surface quality of the sample which is of interest. the technique to use must allow for spot analysis. If. a paint crater a few microns in diameter has to be analysed for possible surface contaminants capable of causing cratering. If. on the other hand.
That entails sputtering the sample layer by layer and analysing the surfaces as they become exposed. mass. The signals generated by it are displayed as a spectrum. which is a chart of intensity versus wavelength. electrons or ions. After interaction of the primary beam with the sample (surface). or energy. direction or mass. Some techniques have an additional sputtering system (e. The primary beam is directed by a focusing system onto the sample surface and into the desired area. The instrumentation setup for all techniques consists of an excitation system (the primary system) that generates photons. The analyser separates the secondary radiation spectroscopically by energy.3 Instrumentation Many of the analytical techniques we will describe here require vacuum conditions. The detector records the separated or resolved signals and measures their intensity. the excited secondary radiation is collected by a ray optics system which directs the secondary beam towards the analyser. the instrumentation used follows a general concept.g. On the assumption that not only the chemical composition of a surface area has to be analysed but also the depth distribution. Although they differ greatly in detail and in their chemical background. Figure I-8: Schematic diagram of instrumentation 1. an ion gun) that allows for subsequent sputtering of layers and thus for depth profiling. .Instrumentation 17 area calls for a scanning technique that generates a chemical map of the analysed area. a depth-profiling mode needs to be chosen.
The first step in failure analysis is to find out what kind of problem we are dealing. This basic technique can be used to carry out a preliminary sample inspection to gain an overview of the problem. and in most cases the tool to use is (optical) light microscopy. However. Hannover. Light microscopy reveals initial. fibres. Germany ISBN: 978-3-86630-912-8 . Figure II-1: Painted key panel showing paint adhesion failure after laser treatment. 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. 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. A= light microscopy image of the border between lasered symbol and paint. 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. particles. 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.
a scanning electron microscope had to be used to scan the surface topography of rough and structured samples. extracts only the sharp details of each focal plane and adds them together to produce an image of unlimited depth of focus. Figure II-2: Light microscopy image of a paint crater (top) and calculated EFI-3D image of the same paint failure . It automatically takes pictures of several focal planes in rough objects. cannot be inspected both very sharply and at high resolution at the same time. rough material surfaces. even for low-resolution purposes. the depth of focus of light microscopy can be extended virtually by a so-called EFI option (Extended Focal Imaging). This is one module of the image-processing software “AnalySIS” developed by the company SIS/Olympus. such as those of structured polymers or metals. Therefore.Optical light microscopy 19 A main disadvantage of conventional light microscopy is the lack of depth of focus. At high resolution. Thanks to the latest developments in digital cameras and software solutions. in the past.
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 x1000.001 and 1. 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. amines and the like. 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. such as esters. acids. Hannover. it takes characteristic energies to excite them. As the bonds between different atoms have distinct bond energies.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. 2. 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. This corresponds to energies between 0. These energies correspond to certain wavelengths of the infrared beam. hydrocarbons. this is known as the “chemical shift”.6 eV. The basic principle of IR spectroscopy is the structural characterization of materials through the absorption of infrared radiation by inter-atomic bonds. 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. The energy needed to excite the vibrations is absorbed from the incident infrared radiation. This additionally permits the layer thickness and topography to be measured. Germany ISBN: 978-3-86630-912-8 . These photons excite characteristic vibrations of the interatomic bonds in a molecule.