To elucidate the thermal and magnetic dimensional stability of Cr-based Invar, the effects of various alloying elements on thermal expansion and magnetic properties were investigated. The Cr-Fe-Mn alloys exhibit low thermal expansion characteristics near room temperature, with the addition of Mn significantly elevating the Néel temperature. Specifically, the addition of approximately 0.89% Mn adjusted the low thermal expansion region to be close to room temperature, while 1.4% Sn raised it to temperatures below 0°C. The average thermal expansion coefficient (CTE) of Cr-based Invar at a temperature range between 20 and 30°C was found to be 1.7ppm/°C, comparable to the 0.90ppm/°C of conventional Invar, and approached nearly zero around 50 to 60°C. Magnetic measurements indicated that Cr-based Invar exhibits negligible magnetization compared to conventional Invars, with magnetization less than one-thousandth of Invar 36. This low magnetization results in minimal magnetostriction, making Cr-based Invar suitable for applications requiring both thermal and magnetic stability. Under a magnetic field strength of 796kA/m, Cr-based Invar showed a slight contraction behavior, unlike other Invars which expanded. This contraction is attributed to the antiferromagnetic nature of Cr, where magnetic moments align in opposite directions, leading to a net magnetization of zero.
The effects of Fe and Mn on the thermal expansion characteristics of non-ferromagnetic Cr-Fe-Mn alloys, which exhibit the Invar effect, were investigated. It was found that the temperature range in which the alloy exhibits low thermal expansion characteristics is below 273 K when the Mn content is less than 0.3%. Conversely, this range shifts to between 273 and 350 K when the Mn content increases to 0.9% or higher. By incorporating small amounts of rare earth elements, the Cr94.6Fe4.7Mn0.7 alloy achieved an average coefficient of thermal expansion of 0.94 × 10−6/K between 273 and 350 K, which is lower than the 1.2 × 10−6/K observed in conventional Invar alloys. Additionally, measurements of magnetic hysteresis loops were conducted to assess the residual magnetization, which is critical for structural components near magnetic measurement equipment. The results indicated that the residual magnetization of the Cr-based Invar-type alloy is approximately 0.0033 mT, significantly lower than the 35 mT typically found in conventional Invar. These substantial differences underscore the potential of Cr-based Invar-type alloys as a superior alternative for applications requiring low thermal expansion and low residual magnetization.
A novel alloy, exhibiting extremely low thermal expansion, high temporal stability and superior Young’s modulus, has been developed based on the super invar (Fe64Ni31Co5). The average coefficient of thermal expansion (CTE) of the alloy, α18-28, is found to change with Fe content, CFe, and can be approximated by the linear equation of α18-28 = −0.4789CFe + 29.927 around room temperature. This linear approximation suggests that the CTE of the alloy can be regulated to zero near CFe of 62.5%, in contrast to the conventional super invar alloy, which is frequently used as the structural support components for stable optical systems and has a CTE of approximately 0.5 × 10−6 K−1 around room temperature. Based on these findings, we have successfully achieved an extraordinarily low thermal expansion of −0.046 × 10−6 K−1 average CTE in the temperature range between 18°C and 28°C through precise control of the chemical composition. the carbon content was reduced to below 0.02% to suppress the carbon-dependent expansion over time, which is known to occur in high carbon invar-based alloys. As a result, the dimensional change over the years of our developed cast alloy is less than 0.05 ppm/year. The low Young’s modulus due to the coarse and columnar grains microstructure in the cast alloys can be improved by 30% with a grain refinement technique using cryogenic and recrystallization thermal treatments.
Fe39Co49Cr10Ni2 has exhibited ultra-low thermal expansion with its average coefficient of approximately 0.13 × 10−6/K between 100 K and 300 K from cryogenic to room temperatures. This value is extremely close to that of the fused silica used for cameras and spectrographs mounted on astronomical telescopes. The nature of the low thermal expansion of Fe39−xCo49+xCr10Ni2 has been clarified by the measurements of the magnetic properties and the numerical simulations based on the path-integral effective-classical-potential theory. The saturation magnetization is found to decrease with increasing temperature in the range from 100 K to 350 K. The rate of decrease becomes larger at temperatures over 150 K. The numerical calculation has shown that this magnetic behavior is attributed to the electronic state changes from high spin state to low spin state in the Co atoms, which occurs at temperatures over 150 K. The electronic state changes in Co atoms are found to strongly contribute to the low thermal expansion for the first time in Fe39−xCo49+xCr10Ni2.
Thermal expansion characteristics of Fe39Co51Cr10 based stainless invar alloys were investigated with the aim of developing a novel structural material used at cryogenic temperature for infrared instruments mounted on astronomical telescopes. Ni-added stainless invar type alloys Fe39Co49Cr10Ni2 were found to exhibit anomalous thermal expansion behavior in the low temperature range between 100 K and room temperature. According to the measured thermal expansion curves, these alloys expanded with increasing temperature from approximately 100 K to 200 K and contracted from 200 K to 300 K. The coefficients of thermal expansion in each temperature range were estimated to be approximately 0.93 x 10-6 /K and −0.71 x 10-6 /K, respectively. As the results of thermal expansion measurements of Cr based alloys, similar negative thermal expansion behavior was observed in the same temperature range between 200 K and 300 K. These findings suggest that the Cr element plays a key role in the negative thermal expansion in the Fe39Co49Cr10Ni2 alloys. We concluded that the dimensional change between 100 K and room temperature could be precisely controlled in the extremely low thermal expansion range by controlling the negative thermal expansion. The coefficient of thermal expansion between 100 K and 300 K was achieved to be approximately 0.13 x 10-6 /K in the Fe38.4Co49.7Cr10.1Ni1.8 alloys developed in this study. As this value was close to that of the fused silica used for infrared instruments, the developed alloys can be a powerful tool for high precision observation in astronomical telescopes.
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