We are driven by innovation and customer satisfaction.

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3 Claus Linseis Managing Director Since 1957 LINSEIS Corporation has been delivering outstanding service, know how and leading innovative products in the field of thermal analysis and thermalphysical properties. We are driven by innovation and customer satisfaction. Customer orientation, innovation, flexibility and high quality are what LINSEIS stands.thanks to these fundamentals our company enjoys an exceptional reputation among the leading scientific and industrial companies. LINSEIS has been offering benchmark products in highly innovative branches for many years. The LINSEIS business unit of thermal analysis is involved in the complete range of thermo analytical equipment for R&D and quality control in sectors such as polymers, chemical industry, inorganic building materials as well as environmental analytics. In addition, Thermophysical properties of solids, liquids and smelts can be analyzed. LINSEIS Corp.thrives for technological leadership. We develop and manufacture thermo analytic and Thermophysical testing equipment to the highest standard and precision. Do to our innovative drive and ultimate precision, we are a leading manufacturer of Thermal Analysis equipment. The development of thermo analytical testing machines requires significant research and a high degree of precision. LINSEIS Corp. invests in this research to the benefit of our customers.

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5 Steel Corrosion Lanthanum Galliumoxid Invar Molybdenum Titanium Titanium Alloys Aluminium Aluminium Hydroxide Iron Steel 16MnCr5 INCONEL INCONEL 718 Nickel-based-Superalloy (INCONEL 600) INCONEL 600 Dental Alloys Semiconductor Substrates Cold-forged Iron Copper Alloy Oxide Melts-Slags Steel (Low-alloyed Steel) Thin Samples Metal Films /

6 STEEL CORROSION Picture 1: Steel corrosion under a humid atmosphere Analysis using STA Corrosion is a reaction between a metallic material and his environment. This generate a measurable change in material und can cause to a damage of function of the metallic component or the whole system. The reaction can be electrochemical, chemical or metal-physical. In the most common use of the word Corrosion, this means a loss of electrons of metal reacting with water and oxygen. Weakening of iron due to oxidation of the iron atoms is a well-known example of electrochemical corrosion. This is commonly known as rusting. Most structural alloys corrode merely from exposure to moisture in the air, but the process can be strongly affected by exposure to certain substances (acids, bases, corrosion, halogens, etc.). The corrosion process can similar be simulated with the Thermogravimetry. Picture 1 shows a steel sample under a humid atmosphere heated and kept isothermal at 800 C. The corrosion reflected in increase in the sample mass. 6

7 LANTHANUM GALLIUMOXID LaGaO3 heating rate: 10K/min sample weight: mg Max/Min C Heat flow [ml/s] point of reaction C Enthalpy 1.02 J/g Offset C Onset C Temperature [ C] Picture 2: Metal Oxide (LaGaO 3 ) Lanthanum - Galliumoxid Analysis using DSC The Metal Oxide Lanthanum-Galliumoxid (LaGaO 3 ) is used as lambda sensors for catalytic converters, in batteries and as membrane in solid oxide fuel cells (SOFCs). The substance is very interesting when fast oxygen (ion conductors are required. The used HiRes Sensor enables the determination of smallest caloric effects such as crystalline structure change of Lanthanum Galiumoxid (Picture 2). 7

8 INVAR Delta-L [µm] Delta-L [Sam_2] Delta-L [Sam_3] Delta-L [Sam_4] Delta-L [Sam_5] Min: µm Max: µm Diff: 0.013µm=> +/- 6.5nm C µm C µm C µm C µm Temperatur [ C] Picture 3: Laser Dilatometer Invar Sample Analysis using Laser Dilatometer Invar (FeNi36) is a nickel steel alloy with a 36% nickel concentration. Invar shows in certain temperature ranges abnormal small or in part negative thermal expansion coefficients. It is used where high dimensional stability is required, such as precision instruments, clocks, seismic creep gauges, television shadow mask frames, valves in motors, and antimagnetic watches. An Invar sample was evaluated four times during heating in an air atmosphere. The temperature range was room temperature up to 200 C. This comparison clearly demonstrates the unbeaten accuracy of the Laser measuring technique. The difference of the four measurements is as low as 0.01% FS. With the patented LINSEIS Laser Dilatometer, resolutions can be obtained which are up to a factor 33 higher than the resolution possible up to date with a conventional Dilatometer (Picture 3). 8

9 MOLYBDENUM Picture 4: Specific heat curve of Molybdenum Analysis using DSC Molybdenum is a white-glittering, very hard, and in pure condition elastic metal with high mechanical resistance. The melting point of Molybdenum is at 2620 C, the boiling point at 4825 C. The mainly application of Molybdenum is in alloyed steels. Pure Molybdenum is used as material for electrodes and catalysers. Other applications are in aircraft, nuclear industry and as conductive metal layers in thin-film transistors. Picture 4 shows the specific heat of a pure molybdenum sample between room temperature and 1400 C. Molybdenum is extremely sensitive to oxygen at elevated temperature. Therefore, an unclean atmosphere leads to a non-linear curve and overlapping effects. Consequently, a pure inert atmosphere is essential for this measuring. 9

10 TITANIUM Picture 5: Analysing a titanium sample with STA Analysis using STA Titanium is the ninth-most abundant element in the earth s crust and the seventh-most abundant metal. Titanium is always bonded to other elements in nature. It has a low density and is a strong, lustrous, corrosion-resistant (including to sea water, aqua regia and chlorine) transition metal with a silver colour. Titanium can be alloyed with iron, aluminium, vanadium, molybdenum, among other elements, to produce strong lightweight alloys for aerospace, industrial process, automotive, agri-food, medical prostheses, orthopaedic implants and something else. Picture 5 shows the TG, DTA and DTG signal of a titanium sample. The DTA curve exhibits an exothermic peak which is typical for oxidation. At 858 C the sample mass increased (66%). An additional mass spectrometer would show a consumption of O 2 in a peak during oxidation. 10

11 TITANIUM ALLOYS Picture 6: Ti60Cr40 analysed with DSC Analysis using DSC Titanium alloys are metallic materials which contain a mixture of titanium and other chemical element. Such alloyed materials get the special properties of titanium, for example high tensile strength, toughness, light weight, extraordinary corrosion resistance and ability to withstand extreme temperature. The high cost of the material limiting the usage (aircraft, spacecraft, medical devices, some premium sports equipment and consumer electronic). The addition of chromium optimizes the burn-resistance. Picture 6 shows the specific heat of titanium chromium alloy. The peak at 723 C is the cold-crystallization of amorphous contents. At 1210 C the transition for the α- to the β-phase can be seen in the peak. Melting of the titanium chromium alloy started at 1400 C with a heat of fusion 282 J/g. 11

12 ALUMINIUM Picture 7: Determination of the reaction temperature between aluminium and nitrogen Analysis using TG Aluminium is a silvery white and ductile member of the boron group of chejical elements. It is not soluble in water under normal circumstances. Aluminium is the most abundant metal in the earth s curst. Aluminium is too reactive chemically to occur in nature as a free metal. Aluminium is remarkable for its ability to resist corrosion and its low density. Aluminium is used in the aerospace industry, and other areas of transportation and building. Its reactive nature makes it useful as a catalyst or additive in chemical mixtures. Following example shows the determination of the reaction temperature between aluminium and nitrogen. By means of the DTA method you can determine the melting point of aluminium (658 C) as well as the reaction temperature of the very strong exothermal nitride reaction (1100 C). You can see a clear increase of the sample mass with the Thermogravimetric analysis (TG signal), which can be determined quantitatively. There is a correlation between the increase of weight and the content of aluminium of the sample (Picture 7). 12

13 ALUMINIUM HYDROXIDE Picture 8: Thermal behaviour of aluminium hydroxide (dehydration and phase change) Analysis using TG Aluminium hydroxide (Al(OH) 3 ) is found in nature as the mineral gibbsite (also known as hydrargillite) and - contaminated with AlO(OH), iron-hydroxide, clay mineral, titanium-dioxide as Bauxite. As amphoterous hydroxide Al(OH) 3 dissolving in acid and bases. In the first case occur aluminiumsalt Al 3+ and in the second case occur aluminate (Al(OH) - ). During the heating of aluminium hydroxide 4 Al(OH) 3 evolve aluminiumoxide (Al 2 O 3 ). At about 150 C you can see that 1.7% humidity is leaving the sample (Picture 8). Between 300 and 600 C you can watch the endothermal change from aluminum hydroxide to aluminium oxide (loss of weight: approx. 14%). Between 1250 C and 1350 C you can find another phase change, which is not connected to any Thermogravimetric signal. 2γ-Al(OH) C γ-al 2 O H 2 O A continues heating cause another phase change: 1200 C γ-al 2 O 3 α-al 2 O kj/mol 13

14 IRON Picture 9: Linear thermal expansion (ΔL) and the CTE of an Iron Sample Analysis using Dilatometer Iron and iron alloys (steels) are by far the most common metals and the most common ferromagnetic materials in everyday use. Chemical clean iron is a silvergrey, relative soft, dilative, reactive metal with a melting point at 1535 C. The linear thermal expansion (ΔL) and the CTE of the iron sample under argon atmosphere are evaluated. The heating rate was 5 K/min. After 769 C (peak temperature of CTE) shrinkage was detected, which is due to a change in the atomic structure, known as the curie-point. The difference of measured and literature result can be attributed to contamination of the sample (Picture 9). 14

15 STEEL 16MnCr5 Picture 10: Alpha to Beta transition of steel with Quenching Dilatometer Analysis using Quenching Dilatometer 16MnCr5 is special steel. This steel will be here an example for the Quenching Dilatometer. This is a highspeed Dilatometer with induction furnace (temperature range: -150 C to 1600 C). The method is perfectly suited for creation of CHT, CCT and TTT diagrams. In the diagram (Picture 10) the actual temperature (red trace), the calculated set-value of the temperature (blue trace), the measured change in length (green trace) and the heating power applied (purple trace) are displayed. At T=15s the alpha to beta transition of the steel takes place. The expansion changes to a temporary shrinkage, additional power is consumed by the sample for the phase change. Between T=50 70 s the opposite transition occurs. The shrinkage changes to an expansion and the temperature decreases slower, since the energy `stored is set free. 15

16 STEEL 16MnCr5 Time [s] Time [min] Time [h] Temperature [ C] Picture 11: CCT-Diagram Quenching-Dilatometer L78 RITA 16

17 INCONEL Picture 12: Inconel 718 measured with LFA Analysis using LFA Inconel refers to a family of austenitic nickel-chromium-based superalloys. Inconel alloys are typically used in high temperature applications. In addition they are oxidation and corrosion resistant materials and have a high strength. When heated, Inconel forms a thick, stable passivating oxide layer protecting the surface from further attack. Inconel is often encountered in extreme environments. It is used in gas turbine blades, seals, and combustors, as well as turbocharger rotors and seals, high temperature fasteners, chemical processing and pressure vessels, heat exchanger tubing, steam generators in nuclear pressurized water reactors and something else. Picture 12 shows a measurement with LFA on an Inconel 718 sample. The measurement was a heat-cool experiment. Between heating and cooling there are no significant differences. A solid-solid-phase transition can be seen between 600 C and 900 C as a slight slope. The increase of thermal diffusivity at 1200 C is caused by melting in material. From 1300 C the thermal diffusivity increases linear. 17

18 INCONEL 718 Picture 13: Inconel 718 measured with DSC Analysis using DSC Naturally it s also possible to analyze Inconel 718 with DSC. In Picture 13 can be seen the specific heat curve. The little peak between 600 C and 900 C is caused by solid-solid-phase changes. A small endothermal effect is also between 1000 C and 1200 C. Melting of Inconel 718 started at 1250 C. 18

19 NICKEL-BASED SUPERALLOY (INCONEL 600) Picture 14: Nickel-based Superalloy (Inconel 600) measured with LFA Analysis using LFA Some declarations are found in chapter 13. Inconel 600 consists of 72% nickel, 16% chromium and 8% nickel. Through the high chromium and nickel contents Inconel offers a high oxidation and corrosion resistance, even at very high temperatures. It also retains a high mechanical strength. It is therefore often used under extreme conditions (aircraft engine parts, chemical processing, turbocharger turbine wheels, pressure vessels, pressure tubes of nuclear reactors). In Picture 14 can be seen the thermal diffusivity of six different runs with two different furnace systems. The minimum (below 0 C) observe a change in magnetic properties. The formation of NiCr 3 cluster is reflected in the step between 500 C and 700 C. 19

20 INCONEL 600 Picture 15: Nickel-based Superalloy (Inconel 600) measured with DSC Analysis using DSC Picture 15 shows six different runs on the nickel-based superalloy. After the linear increase in the specific heat, an endothermal step can be seen (formation of Ni 3 Cr) between 550 C and 700 C. 20

21 DENTAL ALLOYS Picture 16: Dental Alloy Pt0.89Au0.1Ir0.01 measured with STA Analysis using STA There are a large number of metal alloys used in dentistry. The alloys are used for inlays, crowns and bridges. The assumption of a dental alloy for dental applications is its bio-compatibility, malleability and resistance to corrosion. The aim is an alloy that is easy for the dentist to manipulate but is strong, stiff, durable and resistant to tarnish and corrosion. Three samples of Pt0.89Au0.1Ir0.01 were measured in the heat-flow rate (Picture 16). The melting onset temperature was observed at approx C. The melting peak is at approx C. 21

22 SEMICONDUCTOR SUBSTRATES Picture 17: Semiconductor Substrates measured with STA and MS Analysis using STA Integrated circuits (ICs), for example electronic control units (ECUs) like sensors and actuators, play an increasingly important role for electronic devices and in the automotive industry. Highly clean substrates are required to produce such integrated circuits. Thermogravimetry together with simultaneous mass spectroscopy allows division between clean substrate (dashed lines) and contaminated metal substrate (full lines) (Picture 17). The contaminated sample shows a mass loss by 0.004%. The mass loss is most probably caused by wax impurities. The simultaneously detection of several organic alcyl and carbonyl molecules and fragments approved this. 22

23 COLD-FORGED IRON Picture 18: Cold-forged iron measured with DSC Analysis using DSC Forging is the term for shaping metal by using localized compressive forces. Cold forging is done at room temperature or near room temperature. Hot forging is done at a high temperature, which makes metal easier to shape and less likely to fracture. Warm forging is done at intermediate temperature between room temperature and hot forging temperatures. Forged parts usually require further processing to achieve a finished part, for example heat treatment. This can result in various degrees of hardening or softening depending on the details of the treatment. During heat treatment defects in the crystal structure anneal or new faces are formed, resulting in a small energy release. The extremely weak exothermal effects caused by heat treatments (see 16.1) can bee detected with the DSC measurement. Picture 18 shows the specific heat flow on a cold-forged iron sample in a heat-coldheat-experiment. So the first heating curve is the measurement on a cold-forging sample. The second measurement is the curve on an annealed material. The exothermal peak in the first heating curves starts at 335 C and ends at approx. 500 C. The peak temperature was 401 C. This peak can not be seen at the second heating curve. 23

24 COPPER ALLOY Picture 19: Copper alloy measured with LFA Analysis using LFA Copper is a ductile metal with very high thermal and electrical conductivity. Copper is used as a thermal conductor, an electrical conductor, a building material, and a constituent of various metal alloys. The knowledge of the thermophysical properties is necessary to optimize the manufacturing process and for the later application of the copper alloy. Picture 19 shows the thermal diffusivity, thermal conductivity and specific heat measured with LFA and also the specific heat curve from a DSC measurement can be seen. The step in the thermal diffusivity is the phase transition occurred also in the cp-curve from DSC and LFA. This shows that the thermophysical properties can be determined with LFA without any problems. 24

25 OXIDE MELTS SLAGS Picture 20: Slag measured with LFA Analysis using LFA Slag is a partially vitreous by-product of smelting ore to purify metals. They can be considered to be a mixture of metal oxides, which contains basic and acid oxides and they can also contain metal sulfides and metal atoms in the elemental form. While slags are generally used as a waste removal mechanism in metal smelting, they can also serve other purposes, such as assisting in smelt temperature control and minimizing re-oxidation of the final liquid metal product before casting. In nature, the ores of metals such as iron, copper, lead, aluminum, and other metals are found in impure states, often oxidized and mixed in with silicates of other metals. During smelting, when the ore is exposed to high temperatures, these impurities are separated from the molten metal and can be removed. The collection of compounds that is removed is the slag. The thermal diffusivity of the slag increases nearly linearly versus temperature. It can be seen no significant difference between heating and cooling curve (Picture 20). 25

26 STEEL (LOW-ALLOYED STEEL) Picture 21: Low alloyed steel analyzed with DSC Analysis using DSC Steel is a metal alloy. The most constituent parts are Iron with carbon being the primary alloying material. Carbon is the most cost-effective alloying material for iron. It exist further alloying elements such as manganese, chromium, vanadium and tungsten. Varying the amount of alloying elements remarkable change of the properties (hardness, ductility, tensile strength, phase change behavior) received. Differential Scanning Calorimetry (DSC) is a helpful instrument in order that steel get the favored properties. In Picture 21 can be seen the measured specific heat flow rate of a low-alloyed steel. At 734 C happens the change in the crystal structure (from body center to face center) and change in the magnetic properties (ferromagnetic to paramagnetic) occurred. The melting point was measured at 1411 C. The liquidus temperature was measured at 1473 C. 26

27 THIN SAMPLES METAL FILMS Picture 22: Metal films measured with LFA Metal films are used for example in the packaging industry and in the electronic industry as electrical contacts and something else. Therefore, high thermal conductivity and low thermal expansion are necessary. Analysis using LFA LFA Inplane Sample Adapter (Thin metal films) Top cover Picture 22 shows Al foil and MoCu foil in a LFA measurement. The thermal diffusivity decrease with increasing temperature. The example demonstrates that foils with a high thermal conductivity and a small thickness can be analyzed without any problems. Sample Bottom cover

28 LINSEIS GmbH Vielitzerstr Selb Germany Tel.: (+49) Fax: (+49) LINSEIS Inc. 109 North Gold Drive Robbinsville, NJ USA Tel.: +01 (609) Fax: +01 (609) Products: DIL, TG, STA, DSC, HDSC, DTA, TMA, MS/FTIR, In-Situ EGA, Laser Flash, Seebeck Effect Services: Service Lab, Calibration Service