164 Modem Physical Metallurgy and Materials En neering depth, is based upon the well-known phenomenon of sputtering. The target surface is bombarded with a ocused beam of primary ions that has been accelerated with a potential of 1-30 kV within a high-vacuum chamber (10-—10-" torr). These ions. generate a series of collision cascades in shallow surface layer, (0.5-S nm deep, causing neutral atoms and, to a much smaller extent, secondary ions to be ejected (sputtered) from the specimen surface. Thus, a metalic oxide (MO) sample may act as a source of M, 0, M', 0", Mz, 0-, MO" and MO™ species. The secondary ions, Which afe thus ether monatomic or clustered, postive for negative, are directed into a mass spectrometer (analyser), Wherein they are sorted and identified faceording to their mass/charge ratio. Exceptionally high elemental sensitivities, expressed in parts. per million and even parts per billion, ae achievable. All clements in the Periodic Table ean be analysed and it is possible to distinguish between individual isotopes Studies of the selfiffusion of oxygen and nitrogen have been hindered because these ight elements have ro isotopes that can be used as radioactive traces SIMS based on the stable isotope "O provides a rapid rcthod for determining self-diffusion coeficients. The Physical process whereby ions are ejected is difficult {o express in rigorous theoretical terms, consequently SIMS is usually semiquantitative, with dependence ‘upon calibration with standard samples of known composition. SIMS is valuable complement to other mthods of surface analysis ‘The available range of beam diameter is 1 ym to several millimetres. Although various types of ion beam are available (eg. Ar, "0; , "0", Cs’, ete.) positively-charged beams are'a common choice. How= ever, if the sample is insulating, positive charge tends to accumulate in the bombarded region, changing the elfective value of the beam voltage and degrading the quality of signals. One partial remedy, applicable at Tow beam voltages, is to flood’ the ion-bombarded area with @ high-intensity electron beam. In some variants ff SIMS laser beams are sed instead of ion beams. OF the large and growing variety of methods covered by the tem SIMS, the dynamic, static and imaging modes are especially useful, Materials being investigated include metas, ceramics, polymers, catalysis, semiconductors and composites. Dynamic SIMS, which uses a relatively high beam eurrent, is an {important method for determining the distribution and very low concentration of dopants in semiconductors, The beam seans a raster, 100-500 jam in size, and slowly erodes the surface of the sample. Secondary fons from the central region of the erater are analysed to produce a precise depth profile of concentration Static SIMS uses a much smaller beam current and the final spectra tend to be more informative, providing chemical data on the top few atomic layers of the sample surface. Little surface damage occurs and the rethod has been applied to polymers. The imaging version of SIMS has @ resolution comparable to SEM and provide ‘maps’ that shovr the lateral distibution fof clements at grain boundaries and precipitated particles and hydrogen segregation in alloys. Imaging SIMS has been applied to transverse sections through the complex scale layers which form when alloys are exposed to hot oxidizing gases (eg. O2, COs) lis sensitivity is greater than that obtainable with ‘conventional EDX’ in SEM analysis and has provided fa better understanding of growth mechanisms and the special role of trace elements such as yttrium, 5.7 Thermal analysis 8 fies of thermal analysis Heating a material ata steady rate ean produce chemi- cal changes, such as oxidation and degradation, andor physical changes, such as the glass transition in poly- ‘mers, conversions/inversions in ceramics and phase changes in metals, Thermal analysis is used to comple= ‘ment X-ray difiction analysis, optical and electron ‘microscopy during the development of new materi- als and in production control. Sometimes itis used to define the temperature and energy change associated ‘with a structural change; at otber times iti used quali- tatively to provide a characteristic ‘fingerprint’ trace of ‘4 particular material. The various techniques of thermal analysis measure one or more physical properties of a ‘sample asa funetion of temperature. Figure 5.46 illus- trates three basie methods of thermal analysis, namely. thermogravimetrie analysis (TGA), differential thermal analysis (DTA) and differential scanning calorimetry (DSC). Respectively, they measure change in mass (TGA) and energy flow (DTA, DSC). They can apply programmed heating and cooling, but usually operate ‘with a slowly rising temperature. The sample chamber ‘may contain ait, oxygen, nitrogen, argon, ete. or be ‘evacuated. A sample of a few tens of milligrams will ‘often suffice. Recently-dleveloped methods have extended the range of thermal analysis and other aspects of Jbehaviour can now be studied, For instance, using dynamie mechanical thermal analysis (DMTA), ‘mechanical as well as structural information can be ‘obtained on the viscoelastic response of a polymeric ‘sample to tensile, bend or shear stresses during heating. General capabil 58.7.2 Thermogravimetric analysis In a thermobalance the mass of a sample is contin- uously determined and recorded while the sample is being slowly heated (Figure 5.463). Temperatures. up to at least 1000°C are available, It has been applied to the decomposition of rubbers (Figure 5.47), kinetic studies of metallic oxidation, glass transitions and soft- fening in polymers. Equilibrium is not atfained within the sample and the method is insensitive to the more subtle solid-state changes. When changes overlap, it cean be helpful to plot the fist derivative, Sms of“The characterization of mat Pye Mains | parameter Apparat aon vse @ + Toa | Mass m ™ Lal = © : Exomerme Oran ceaie are at > e Tea = = Hr ~ + t Enso psc | oH cone Ea a ae a q To Figure £46 Basic methods of thermal analysis (a) Thermogravinerie analysis (TGA). () differential thermal analysis (DEY) and () diffrent Scanning calorietrs (DSO) the graphical trace in a procedure known as derivative theemogravimetric analysis (DTGA), 5.7.3 Differential thermal analysis DTA! reveals changes during the heating of a sample whieh involve evolution or absorption of energy. AS shown diagrammatically in Figure $.46b, a sample S tnd a chemically and thermally inert reference material R (sintered alumina or precipitated silica) are mounted in a recessed heating block and slowly heated. The thermocouples in S and R are connected in opposi= tion; their temperature difference 7 is amplified and plotied against temperature. Peak arca on this trace is a function ofthe change in enthalpy (4/1 as well as the ‘mass and thermal characteristics ofthe sample S, Small, samples can be used to give sharper, narrower peaks, provided that they are fully representative ofthe source "sual acreited to H. Le Chateier (1887): improved version and forennner of modem DTA used by WC. Roberts-Austen (1899) in metallurgical studies of alloys. ‘material. Meally, the specific heat capacities of $ and R should he similar. DTA is generally regarded as a semiquantitative or qualitative method, It has been used in studies of devitrificaton in oxide glasses and the glass transition in polymers. Figure $47 shows ‘comparison ofthe thermal response of high-alumina ‘cement (HAC) and Portland cement. The amount of an undesirable weakening phase ean be derived from the relative lengths of the ordinates X and Y in the HAC 5.7.4 Differential scanning calorimetry In this method, unlike DTA, the sample and reference body have separate resistive heaters (Figure 5.460). When a difference in temperature develops between sample S and reference R, an automatic control loop hheats the cooler of the two until the difference is climinated. The electrical power needed to accomplish this equalizer is plotted against temperature. An endothermic change signifies that an enthalpy increase hhas occurred in S; accordingly, its peak is plotted upwards (unlike DTA traces). Differences in thermal ‘conductivity and specific heat capacity have no effect