Calorimetric Control of Aluminium Casting Quality

Differential scanning calorimetry (DSC) combined with an entrained droplet technique [1] has been successfully used on a series of melt spun alloys with deliberate impurity additions to study the nucleation related aspects of secondary phase selection during solidification of dilute Al alloys. This paper illustrates how DSC is a sensitive tool for determining the effect impurities can have on the nucleation of secondary phases, and hence material properties of these alloys. Stepped cooling/isothermal holding profile DSC has also been used in preliminary investigations of the thermodynamic range of formation of the Al—Fe eutectic phases and their nucleation and growth solidification kinetics.This revised version was published online in November 2005 with corrections to the Cover Date.     

Mathematical analysis of the heat measured by a power-compensated differential scanning calorimeter during the solidification of a multiphase alloy

The determination of the solidification characteristics of alloys using differential scanning calorimetry (DSC) is difficult because of the unknowns associated with the kinetic of phase transformations and the thermal resistance between the sample and the temperature measuring device. This paper shows how appropriate assumptions coupled with a thermodynamic software package and an accurate mathematical analysis of a power-compensated DSC, can enable a direct comparison between the experimental and the theoretical heat evolutions obtained during the solidification of a multiphase alloy. This comparison is helpful in order to assess the thermodynamic database and to validate the different assumptions made in the solidification model.

     

A method to estimate the Gibbs free energy of non-equilibrium alloys by thermal analysis

A method has been developed to estimate the Gibbs free energy $ \left( {G_{\text{S}}^{\text{NE}} } \right) $ of the non-equilibrium solid alloys with multicomponents based on differential scanning calorimetry (DSC) analysis. In this method, the DSC curves of the non-equilibrium and equilibrium alloys during heating up to fully melting and those of the alloys during solidifying were measured. Then the thermal effects of the solid phase transformations from non-equilibrium to equilibrium states and the equilibrium solidification could be calculated. By evolving the traditional equal-G curve principle to equal-G point, the Gibbs free energy of the equilibrium solid alloy with multicomponents could be obtained on condition that the free energy of the liquid alloy was known. Considering the thermal effects of the solid phase transformations from non-equilibrium to equilibrium states, the Gibbs free energy value of the non-equilibrium alloys with a given composition could be achieved although the phase constitution of the equilibrium solid alloys and the Gibbs free energy of each phase were not known, and the calculation errors could be reduced by dividing the alloys into many infinitesimal virtual pure metals. The Gibbs free energy of the non-equilibrium Al?CSi?CMn alloys was calculated by using this method, confirming the validity of this method.     

Cooling curve thermal analysis,phase constitution,and solidification characteristics of cast Mg–5Gd–2Y–xNd–Zr alloys

Journal of Thermal Analysis and Calorimetry - Mg–RE alloys are high-strength magnesium alloys with great application potential. The solidification pathways and microstructure formation of...     

Applications of thermal analysis in quality control of solidification processes

Summary Thermal analysis is widely used to determine solidification characteristics of metals and alloys in various metallurgical processes. Computer-Aided Cooling Curve Analysis (CA-CCA) is the most popular thermal analysis technique because of its ease of use and low cost. This paper discusses the principles of CA-CCA and zero curve calculations. The methods for calculating key solidification characteristics of metals from cooling curves are presented, and their importance in the quality control of manufacturing processes are demonstrated. Examples are presented for cast iron, copper and aluminum alloys.     

微量元素Sr对Al—Si合金凝固过程的影响

用差热分析法系统地研究了Sr对Al-Si共晶、亚共晶及超共晶合金的动态凝固过程的影响。结果表明,Sr既可促进α-Al成核,使其初晶析出温度比二元合金中α-Al相析出温度明显提高,又能抑制初晶Si成核,使超共晶中初晶Si相析出温度较二元合金中Si的初晶的实际析出温度明显降低,还能促使共晶合金成核,使加Sr后的共晶析出温度明显提高。     

快速凝固Ni-Zr-Al非晶态催化合金的制备与活化处理

As new catalytic materials, amorphous alloys have attracted much attention since 1980s. Rapid solidification is one of the main techniques to prepare amorphous alloys.However, as-cast rapidly solidified alloys usually can not be directly used as the catalyst for their poor surface area, oxide film on their surface, etc. Therefore, activation pretreatment must be carried out. Recently, leaching aluminum has been attempted to activate rapidly solidified amorphous catalytic alloys containing aluminum. In order to carry out such an activation pretreatment, the Al-rich amorphous precursor alloys must be obtained first, in which the content of active component must be sufficiently high so that the catalytic activity of the activated catalyst can be attained. On the other hand, the chemical composition of the precursor must approach eutectic point or contribute to the range of low liquidus temperature so that the glass transition can be easily achieved according to the solidification theory[1]. So far Al-based alloys which meet the dual confinement have not been found yet. For Ni-Al and Cu-Al systems,only the microcrystalline alloys can be obtained through rapid solidification[2,3].In the present study, glass formation was achieved by introducing promotion elements in Ni-Al system precursor alloys.     

Effect of rapid solidification on heat capacities of Al-Sr alloys

Heat capacities of both the ingot-like and melt-spun Al-Sr alloys have been measured through the temperature range 373 to 1060 K using differential scanning calorimetry. The experimental results show that rapid solidification has a slight effect on the temperature dependence of the heat capacities of the Al-Sr alloys. The heat capacities of the melt-spun Al-Sr alloys increase more slowly than those of the ingot-like alloys with increasing temperature from 373 to 900 K. Furthermore, the effect of rapid solidification on the heat capacities becomes more obvious with increasing Sr concentration in the Al-Sr alloys. The data of the heat capacities between 373 and 900 K have been fitted with the least square method and a linear dependence on temperature was assumed for that temperature range. This revised version was published online in July 2006 with corrections to the Cover Date.     

The effect of cooling rate on the solidification and microstructure evolution in duplex stainless steel

The effects of the cooling rate on the solidification and microstructure evolution in the duplex stainless steel SAF 2205 was studied using DSC and light microscopy. A ferritoscope was used to measure the ferrite content. It was revealed that the cooling rate has an influence on the ??-ferrite nucleation temperature and the width of the solidification interval. Moreover, with an increase in cooling rate, the content of ??-ferrite increases, while the quantity of austenite in the ferrite matrix decreases and its morphology changes to acicular. A two-cycle DSC experiment made possible a more accurate interpretation of the collected data.     

Differential scanning calorimetric assessment of high purity

The value and limitations of differential scanning calorimetry in the assessment of high-purity substances has been examined. In favorable cases, good agreement has been secured for polycyclic hydrocarbons between DSC purity values and GC assay values. For some halogenated benzoic acids, used as microanalytical reference standards, good agreement has been obtained between DSC purity values and acid—base titration results. DSC studies on cholesterol and urea, which have limited thermal stability, are presented. With the available instrument and technique, the practical upper limit of absolute DSC purity values may be 99.95 mole%, although higher numerical values can be obtained. Because the DSC technique is “blind” to equilibrium solid solution formation, DSC values should not be used as a sole criterion of purity; this recommendation is of special importance for compounds purified by fractional solidification processes.     

Differential scanning calorimetry study of the solidification sequence of austenitic stainless steel

The solidification sequence of austenitic stainless steels can be predicted with thermodynamic calculations. Another way is to use models where the value of the Cr_eq./Ni_eq. ratio determines the relationship between the solidification mode and the composition factor. In this study the solidification of AISI 304LN stainless steel at different cooling rates was studied using differential scanning calorimetry (DSC). The samples were linearly heated above the liquidus temperature to 1550 °C at heating rates of 5, 10, and 25 K/min. The solidification (cooling) scans from 1550 °C involved the same selected ramps. After the DSC measurements the samples were metallographically analyzed to reveal the variations in the solidification microstructures. The microhardness of the solidified samples was also measured. It was found that the cooling rate critically influenced the solidification. The solidification behavior, which depends on the cooling rate, determines the evolution of the microstructure. At the slowest cooling rates a relief-cell morphology was observed, and at the fastest cooling rate the formation of dendrites was evident. With an increasing cooling rate the liquidus temperature decreased and the reaction enthalpy increased.     

Effect of cooling rate and Al content on solidification characteristics of AZ magnesium alloys using cooling curve thermal analysis

The solidification behavior of AZ Magnesium alloys in various cooling conditions was investigated using a computer-aided cooling curve thermal analysis method. In each case, the cooling curve and its first and second derivative curves have been plotted using accurate thermal analysis equipment and solidification characteristics were recognized from these curves. The cooling rates used in the present study range from 0.22 to 8.13 °C s^?1. The results of thermal analysis show that the solidification parameters of AZ alloys such as nucleation temperature (T _N,α), nucleation undercooling (?T _N,α), recalescence undercooling (?T _R,α), range of solidification temperature (?T _S) and total solidification time (t _f) are influenced by variation of cooling rate. Also, the effect of Al content on these parameters was studied. Microstructural evaluation was carried out to determine the correlation between the cooling rate and secondary dendrite arm spacing.     

Amorphous alloys and differential scanning calorimetry (DSC)

Journal of Thermal Analysis and Calorimetry - A remarkable number of scientific papers are available in the literature about the bulk amorphous alloys and metallic glasses. Today, DSC is an...     

Polymer alloys: science and practice

The diversity of applications, versatality of property modifications, motivations for development and commercial significance of polymer alloys are reviewed with reference to commercially available materials. The key steps and scientific considerations central to the development of thermoplastic blend systems are discussed. The scientific considerations in developing the technology, such as thermodynamics of polymer-polymer miscibility, thermal and mechanical compatibility, phase diagram/morphology, interphase adhesion, and kinetics of solidification are highlighted with the help of specific examples from practice. Specific areas for research and development in polymer alloys in India are indicated emphasizing the need for an applied research bias. Presented at the Symposium on ‘Polymer Science and Engineering’ during Annual Meeting of the Academy, Nainital October 1982.     

Thermal Treatment of Iron-Copper Metastable Alloys

Mechanical alloying is a versatile technique for the solid state synthesis of many materials, including alloys such as iron-copper where the elements are immiscible under equilibrium conditions. The structural and magnetic state of these alloys, and their thermal stability, have been investigated by means of thermomagnetometry, DSC, X-ray diffraction and Mössbauer spectroscopy. Comparison of the thermomagnetometry curves for the various alloys together with analysis of intermediate reaction products enabled the individual thermal processes to be identified. The Curie temperature of the alloys was measured, and it was found that on heating the metastable alloys underwent phase segregation between 300-400°C.     

Comparison of simulated and actual DSC measurements for first-order transitions

A system of differential equations modeling a heat flux DSC is solved and the results are compared with those obtained using a TA Instruments Q1000™ DSC.¹ It incorporates a new heat flow rate measurement technique that determines the heat flow rate between the sample and its pan. Two types of first-order transitions are investigated: melting of a pure substance and solidification of a pure substance including super-cooling. In both transitions, the peak shape obtained using the new heat flow rate measurement and predicted by the model is quite different from that measured using conventional DSC. It is shown that the differences are the result of simplifications implicit in the conventional heat flow rate measurement that is based solely on the difference between sample and reference calorimeter temperatures. Heat flow rates measured using the improved measurement agree very well with the model predictions for heat exchange between the sample and its pan.     

Rearrangement of hexadecane molecules confined in the nanopores of a controlled pore glass using positron annihilation and differential scanning calorimetry

The solidification/melting of cetane confined in nine silica glasses with specific controlled pores (CPG) with different pore sizes (r _p ranging from 3.7–72 nm) has been studied. Samples with variable coefficient of filling of cetane were prepared and analyzed. Combining the indication of the evolving solidification heats (via differential scanning calorimetry, DSC) with the lifetime spectra of positron annihilation, the mechanism of filling of cetane molecules in the pores of the hosting silica glass matrices has been searched. Three independent solidification effects—three independent DSC peaks—were observed in each measuring cycle, namely one crystallization exotherm Rb of the bulk-cetane (if present) and two crystallization sub-peaks Rc1 and Rc2 of the confined cetane in the case of continuous cooling. The temperatures of both Rc1 and Rc2 effects decrease on decreasing the r _p of the CPG matrix. The mutual relation between Rc1 and Rc2 has been analyzed. The kinetics of all three steps of the solidification in the continuous-cooling as well as isothermal regimes have been specified.     

掺杂元素对铝-硅共晶合金凝固过程的影响

国内外学者对掺杂元素对Al-Si共晶合金的影响进行了大量的研究,这些研究大都侧重于研究变质后的结果,如变质后的晶体结构形态以及掺杂元素对结构形态的影响,再根据变质结果反过来推测可能的变质机理,但对掺杂元素对Al-Si合金凝固过程本身的影响的研究却很少.本文拟采用差热分析法(DTA)和步冷曲线热分析法研究Na、Sr元素对Al-Si共晶合金凝固过程的影响,以探讨Al-Si共晶合金的成核机理。     

Study on the microstructure and liquid–solid correlation of Al–Mg alloys

Based on the available structural models and theories of electrical resistivity (ER) of liquid alloys, the structure and the liquid–solid correlation of Al _(100-x) Mg_x (x = 0, 10, 20, 30, 40, 50) alloys have been qualitatively studied by measuring the ER during the heating/cooling process using the direct-current (DC) four-probe method, as well as by characterizing the solidification morphology and testing the hardness. The result shows that the ER of Al–Mg alloys increases with the increasing temperature and the Mg content; thermal state and history have an effect on the solidification structure and properties: the ER of Al–Mg alloys exhibits a lag phenomenon of structure change during the heating/cooling process. A higher heating/cooling rate contributes to the more obvious relaxation effect of ER and the more uniform structure. Furthermore, higher pouring temperature (PT) leads the melts and solidification structure to be more homogeneous, which increases the hardness.     

Porosity of porous Al alloys

Two porosity models of porous Al alloys with different pore types (ball and polygon shape) were established. The experimental results coincide well with theoretical computations. The porosity of Al alloys (Prc) consists of three parts, porosity caused by preform particles (Prp), additional porosity (Pra), and porosity caused by solidification shrinkage (Prs). Prp is the main part of Prc while Pra is the key for fabricating porous Al alloys successfully in spite of its little contribution to Prc.