Annealing Behavior Research Articles

Controlled Fabrication of Distinct Nanostructures from Discrete Oligourethanes via Thermal Annealing.

The self-assembly of sequence-defined polymers (SDPs) enables the formation of a diverse array of nanostructures; however, the construction of complex hierarchical structures via thermal annealing from SDPs remains relatively unexplored. In this study, two series of oligourethanes, 2Cit-pBn-OH and 2Cit-mBn-OH, were synthesized to investigate their thermal annealing behaviors. Nanorod clusters were generated from 2Cit-pB6-OH in a mixture of 1,4-dioxane and toluene, whereas 2Cit-pB8-OH formed nanosheets after thermal annealing. Upon modifying the structure of the repeating units, 2Cit-mB6-OH self-assembled into ultrathin nanosheets, transitioning from nanospheres after thermal annealing in a mixture of isopropanol and cyclohexane, while "flower" micelles were produced from 2Cit-mB8-OH. Interestingly, when isopropanol was replaced with a mixture of isopropanol and tetrahydrofuran (THF), uniform nanotubes were generated by 2Cit-mB6-OH under the same thermal annealing conditions. Additionally, a discrete amphiphile (2Cit-mB4-(S)DPEG) was synthesized, leading to the formation of uniform nanosheets in aqueous solution after thermal annealing. This work highlights the significant effects of sequence and repeating unit structure of SDPs on their self-assembly behaviors and presents a novel strategy for the controlled fabrication of unique nanostructures from SDPs.

Thermally activated damage recovery in ion‐irradiated Gd2Ti2‐yZryO7 pyrochlore

AbstractIonizing events having a wide variety of radiation‐induced effects can radically affect the kinetics of defect production or structural transformation in the pyrochlore structured oxides (A2B2O7). Therefore, a thorough understanding of the kinetics associated with cation ordering and disordering is required for various technological applications. The structural responses of Gd2Ti2‐yZryO7 (y = 0.4, 1.2, 1.6) pyrochlore series irradiated by 120 MeV Au9+ ions were investigated using in situ synchrotron x‐ray diffraction (SR‐XRD), micro‐Raman spectroscopy, and scanning electron microscopy (SEM). Each pyrochlore composition irradiated at the highest fluence, where structural modifications occur, was subsequently isochronally annealed from room temperature to 1000°C. The SR‐XRD results indicate that Ti‐rich composition (y = 0.4) retains its pre‐irradiated pyrochlore structure (Fdm) at 1000°C. In contrast, Zr‐rich compositions exhibit recrystallization to an intermediate defect‐fluorite phase (Fmm) above 500°C, and the pre‐irradiated pyrochlore superstructure does not recover even on annealing at 1000°C. These results reveal that recrystallization temperature strongly depends on the accumulated radiation damage, generally described with the cationic radius ratio (rA/rB). Thus, investigation of the thermal annealing behavior of irradiated pyrochlores helps better understanding the general mechanisms of radiation damage and recovery of pyrochlores, which is important for their use in nuclear applications.

Effect of microstructural heterogeneity and grain morphology on the annealing behavior of additively manufactured metastable β titanium alloy

Abstract Titanium alloys fabricated by additive manufacturing usually exhibit significant heterogeneity in grain size and morphology. Recrystallization treatment is an effective approach to alter the microstructure and achieve a more homogeneous structure. In this study, recrystallization and grain growth behaviours of a metastable β titanium alloy fabricated by laser powder bed fusion (LPBF) and direct energy deposition (DED) were investigated. The LPBF sample developed a chessboard-like microstructure, with considerable variations in grain size and morphology across molten pools. Recrystallization started from the boundary of these pools, where grains were finer and the stored energy was higher. The DED sample had a heterogeneous structure with alternating layers of equiaxed grains and columnar grains oriented with <100> along the building direction. Results obtained from in-situ EBSD demonstrated that grain growth occurred preferentially in regions with fine equiaxed grains, and regions with columnar grains showed limited grain growth due to the relatively lower driving force and mobility.

Deformation and Annealing Behavior of Cr Coating Prepared by Pack-Cementation on the Surface of Austenitic Stainless Steel.

In this paper, a Cr coating was prepared by induction heating and pack-cementation chromizing on AISI 304 austenitic stainless steel. Then, the cold-rolling deformation and annealing treatment were introduced to refine the coarse matrix grains caused by pack-chromizing and improve the overall performance of 304 austenitic stainless steel. The phase composition, element distribution, and microstructure of the coating were carefully characterized. The microhardness, wear resistance, and corrosion resistance of the coating were tested. The results show that the Cr coating with a thickness of 100 μm is mainly composed of a (Cr,Fe)23C6, (Cr,Fe)7C3, and α-Fe-Cr solid solution. After the cold-rolling deformation and subsequent annealing treatment, the grains are significantly refined and the Cr coating is divided into two layers, consisting of carbon-chromium compounds such as Cr23C6, Cr7C3, Cr2C, and Cr3C2 in the surface layer and a Fe-Cr solid solution in the subsurface layer. The cold-rolling deformation and annealing treatment significantly improved the microhardness and wear resistance of the coated sample, and the corrosion resistance was also better than that of the uncoated sample.

Femtosecond laser ultrafast photothermal exsolution

Exsolution, as an effective approach to constructing particle-decorated interfaces, is still challenging to yield interfacial films rather than isolated particles. Inspired by in vivo near-infrared laser photothermal therapy, using 3 mol% Y2O3 stabilized tetragonal zirconia polycrystals (3Y-TZP) as host oxide matrix and iron-oxide (Fe3O4/γ-Fe2O3/α-Fe2O3) materials as photothermal modulator and exsolution resource, femtosecond laser ultrafast exsolution approach is presented enabling to conquer this challenge. The key is to trigger photothermal annealing behavior via femtosecond laser ablation to initialize phase transition from monoclinic zirconia (m-ZrO2) to tetragonal zirconia (t-ZrO2) and induce t-ZrO2 columnar crystal growth. Fe-ions rapidly segregate along grain boundaries and diffuse towards the outmost surface, and become ‘frozen’, highlighting the potential to use photothermal materials and ultrafast heating/quenching behaviors of femtosecond laser ablation for interfacial exsolution. Triggering interfacial iron-oxide coloring exsolution is composition and concentration dependent. Photothermal materials themselves and corresponding photothermal transition capacity play a crucial role, initializing at 2 wt%, 3 wt%, and 5 wt% for Fe3O4/γ-Fe2O3/α-Fe2O3 doped 3Y-TZP samples. Due to different photothermal effects, exsolution states of ablated 5 wt% Fe3O4/γ-Fe2O3/α-Fe2O3-doped 3Y-TZP samples are totally different, with whole coverage, exhaustion (ablated away) and partial exsolution (rich in the grain boundaries in subsurface), respectively. Femtosecond laser ultrafast photothermal exsolution is uniquely featured by up to now the deepest microscale (10 μm from 5 wt%-Fe3O4-3Y-TZP sample) Fe-elemental deficient layer for exsolution and the whole coverage of exsolved materials rather than the formation of isolated exsolved particles by other methods. It is believed that this novel exsolution method may pave a good way to modulate interfacial properties for extensive applications in the fields of biology, optics/photonics, energy, catalysis, environment, etc.

An In-Depth Study of Ring Oscillator Reliability under Accelerated Degradation and Annealing to Unveil Integrated Circuit Usage.

The reliability and durability of integrated circuits (ICs), present in almost every electronic system, from consumer electronics to the automotive or aerospace industries, have been and will continue to be critical concerns for IC chip makers, especially in scaled nanometer technologies. In this context, ICs are expected to deliver optimal performance and reliability throughout their projected lifetime. However, real-time reliability assessment and remaining lifetime projections during in-field IC operation remain unknown due to the absence of trustworthy on-chip reliability monitors. The integration of such on-chip monitors has recently gained significant importance because they can provide real-time IC reliability extraction by exploiting the fundamental physics of two of the major reliability degradation phenomena: bias temperature instability (BTI) and hot carrier degradation (HCD). In this work, we present an extensive study of ring oscillator (RO)-based degradation and annealing monitors designed on our latest 28 nm versatile array chip. This test vehicle, along with a dedicated test setup, enabled the reliable statistical characterization of BTI- and HCD-stressed as well as annealed RO monitor circuits. The versatility of the test vehicle presented in this work permits the execution of accelerated degradation tests together with annealing experiments conducted on RO-based reliability monitor circuits. From these experiments, we have constructed precise annealing maps that provide detailed insights into the annealing behavior of our monitors as a function of temperature and time, ultimately revealing the usage history of the IC.

Experimental Study of Electrical-Assisted Nanomachining of Monocrystalline Copper Using Customized Tungsten Tip

As a promising micro/nanofabrication method, electrical-assisted nanomachining has obtained substantial attention due to its high material removal rate and attainable superior surface quality. In this study, a rectangular wave electrical signal was applied for nanomachining by a customized tungsten tip. Owing to the coupling effect between the electric field and mechanical force, the cutting depth of the machined grooves can be expanded. In electrical-assisted groove processing, a depth of 270 nm and an aspect ratio of 0.6 on the copper sample can be achieved. The influence of operation parameters including applied voltage, frequency, duty ratio, normal force and cutting speed on the machining performance was investigated in terms of the groove depth, width, aspect ratio, and surface roughness. The potential machining mechanisms should be a combination of electric field force, nanoscale electric discharge, electric contact thermal effects, possible annealing behavior, and scraping and plowing actions induced by mechanical forces.

The near surface damage and recovery of low nitrogen diamond implanted with MeV phosphorus ions

The purpose of this work is to provide a novel perspective for investigating the damage of diamond surfaces implanted by MeV phosphorus (P) ions and recovery of the surfaces after high-temperature annealing. SRIM simulation and low-temperature luminescence spectroscopy were performed to analyze the properties of the samples comprehensively. The results revealed that a certain degree of diamond lattice damage was caused without graphitization by the irradiation of 1 MeV P ions with a fluence value of 1015 ions/cm2. The SRIM simulation revealed that the ions that were implanted into the lattice collided with carbon atoms. These ions stopped at a depth of approximately 0.55 μm and generated intrinsic diamond defects on the diamond near the surface. The simulated defects were confirmed by the appearance of neutral single vacancy (GR1) centers in the photoluminescence (PL) spectrum after annealing at 400 °C. In addition, the annealing behavior of optical centers at 900 °C indicated significant damage recovery, including the disappearance of GR1 centers, combined with the increased intensity, slightly blue-shifted peak position, and narrowed FWHM of the nitrogen-vacancy (NV) center.

Thermal stability of artificial radiation-induced defects in kaolinite: Enhancing EPR dating protocol

Kaolinite naturally contains radiation-induced electron defects in its structure induced by ionizing radiations and can be analyzed with electron paramagnetic resonance spectroscopy (EPR). They include the so-called A-center, which is crucial for geochronological applications due to its stability at the scale of geological periods. Indeed, previous studies have substantiated the thermal stability of naturally occurring A-centers in kaolinite through annealing experiments. However, the stability of artificially created A-centers, which are used to determine paleodose through calibration via irradiation experiments and subsequent dating of kaolinite formation, still needs to be more adequately specified to confirm their relevance. Therefore, this research probed the thermal stability of A-centers produced by ionizing 1.5 MeV He+ beams in two samples, i.e., the reference KGa-2 and a very disordered lateritic soil kaolinite. Heating experiments showed that the annealing of irradiated samples at 250 °C was relevant to determining A-center concentration. Second, the annealing of artificial A-centers at higher temperatures was found to be a second-order process, as for natural A-centers. Annealing parameters such as activation energy (2–2.6 eV) were determined with estimates of half-life at 300 K, which was found to be >1012 years for natural and artificial A-centers. Thus, the parameters for artificial A-centers are consistent with the thermal annealing behavior of their natural counterparts. These new findings affirm that artificially generated A-centers mimic natural ones in terms of EPR spectra and thermal stability, enhancing the reliability and precision of the EPR dating methodology used in kaolinite dating.

Vacancy‐Type Defects and Their Trapping/Detrapping of Charge Carriers in Ion‐Implanted GaN Studied by Positron Annihilation

Annealing behaviors of vacancy‐type defects in ion‐implanted GaN are studied by positron annihilation. Mg+ and N+ ions are implanted to obtain 700 nm deep box profiles with Mg and N concentrations of 1 × 1018 cm−3, and the samples are annealed using an ultrahigh‐pressure annealing system. For as‐implanted samples, the major defect species is identified as Ga‐vacancy (VGa)‐type defects. For N‐implanted GaN, the size of the vacancies increases as the annealing temperature increases up to 1100 °C and then shrank above 1200 °C. This behavior is attributed to recombinations between N‐vacancy (VN)‐type defects and excess N. For Mg‐implanted GaN, the major defect species after annealing above 1000 °C is vacancy clusters such as (VGaVN)3. Some of them act as nonradiative recombination centers for blue and ultraviolet luminescence. Their energy levels corresponding to the transition from positive to neutral are located between 2.6 eV above the valence band maximum and the conduction band minimum. The thermal activation process of electron detrapping from the vacancy clusters is also studied. For Mg‐implanted GaN, one of the major secondary defects is collapsed vacancy disks forming dislocation loops. They are eliminated by additional N implantation, which is associated with vacancy agglomerations under the annealing in VGa‐rich condition.

Simulation of defect evolution in tungsten during annealing by developing a vacancy and interstitial-type defect evolution model

In this work, a Vacancy and Interstitial-Type Defect Evolution (VITDE) model is developed to study the annealing and clustering behaviors of the irradiation-induced defect in tungsten (W). The post annealing of W-ion damaging at 300 K (called post-damaging annealing) and simultaneous annealing of W-ion damaging (called dynamic annealing) are simulated. In the post-damaging annealing case, the W is damaged by 20 MeV W-ion irradiation for 1h at 300 K, then the damaged W is annealed for 1h via increasing the temperature to 1000 K. In the dynamic annealing case, the defect evolution under simultaneous damaging and annealing is simulated using the same parameters as Case 1. The simulation results indicate the dynamic annealing case has lower induced defects concentration than the post-irradiation annealing case, which is in qualitative agreement with the experiment. The diffusion of interstitial, vacancy, di-interstitial and di-vacancy, and the cluster properties in the defect annealing are investigated and larger size Vn clusters are observed in dynamic annealing case than in post-damaging annealing case. The dependences of the defect evolution on material temperature (T) and grain size are revealed. By increasing the T, the defect concentration is decreased, which reproduces and explains the experimental result. The Vn trap amount with the reduction of grain size for two cases show a larger difference at T = 400 K, observing the Vn trap amount is unchanged for post-damaging annealing, whereas it is significantly increased by dynamic annealing.

Role of δ-phase on recrystallisation behaviour of Inconel 718

The present work investigates the annealing behaviour of prior-coldworked Inconel 718 (IN718) sheets over wide reduction and temperature ranges by performing cold-rolling and isothermal annealing, followed by mechanical testing and structural characterisation. The study reveals that, with increasing annealing temperature, the prior-coldworked alloy shows non-monotonic M-Type variation with double peak-hardening at 0.3 Tm and 0.6 Tm. The study discovers that the first peak is due to the ‘static–strain–aging phenomenon’ that precedes recovery-softening. The second peak-hardening is due to precipitation-hardening, following which, the alloy softens due to recrystallisation. Supported by SEM, electron back-scattered diffraction and X-Ray diffraction results, the investigation suggests that the precipitation of fine rod-shaped δ-phase creates numerous nucleation sites at the shear bands that cause recrystallisation-burst at 0.75 Tm. However, above 0.75 Tm absence of the δ-phase activates grain-boundary migration resulting in rapid grain-coarsening.

Improving the photocatalytic activity of graphitic carbon nitride through ionic liquid-mediated thermal annealing

Graphitic carbon nitride (g-C3N4) has shown a great promise in photocatalytic hydrogen evolution. However, the catalytic activity of g-C3N4 derived from nitrogen-rich compounds is still limited by fast charge carrier recombination and slow surface reaction dynamics. Herein, a series of primary g-C3N4 materials were prepared by thermal polymerization of melamine and/or urea, and then thermally treated with the involvement of different ionic liquids under altering heat conditions. Imidazole-containing ionic liquids, such as 1-propyl-3-methylimidazolium chloride ([PMIm]Cl), acted as an effective additive to mediate the thermal annealing behavior of primary g-C3N4, leading to the dissociation of aggregates into porous nanosheets with varying element compositions and with increased surface area. Regardless of little change in optical absorption and electronic structure, the resulting porous g-C3N4 nanosheets promoted the separation and transfer of photogenerated charges and modified surface hydrogen desorption. Hydrogen evolution tests confirmed that the catalytic activity of g-C3N4 from the co-polymerization of melamine and urea was enhanced by ∼3.4 and ∼7.4 times upon [PMIm]Cl-free and -mediated thermal annealing, respectively. This work suggests the potential effect of the additive involvement in the thermal annealing on the photocatalytic activity of g-C3N4.

Thermally induced reaction and transient hardening of miscible spinodoid alloys

Spinodoid alloys prepared by dealloying and deposition exhibit a bicontinuous dual-phase nanostructure with (semi-)coherent interfaces, resembling some features of the structure formed in spinodal decompostion. Composition fluctuation in such material and its spinodal-like hardening may then be tuned via thermally induced interdiffusion, even in undecomposable alloys. This paper studied the annealing behavior of miscible Cu/Au and Ag/Au spinodoid alloys with semi-coherent and coherent interfaces respectively. While the interdiffusion-dominated interfacial mixing occurs in both alloys, this process is interrupted in the Cu/Au alloys by a recrystallization-like reaction due to the large lattice mismatch between Cu and Au. We also found that interdiffusion does not monotonically soften these materials; instead, hardening can be observed in both alloys at the early stage of annealing, though further annealing eventually leads to softening. Thermally induced transient hardening is attributed to the formation of a diffuse Cu/Au or Ag/Au interface whose barrier strength to dislocation transmission is enhanced comparing to the sharp interface before annealing. Localized solid solution hardening and the dissociation of misfit dislocations within the diffuse interface might have led to the increase of interfacial barrier strength.

Effect of Heating Rate on the Annealing Behavior of Aluminium Alloys

This contribution presents a study on the effect of heating rate maintained during annealing treatment on the final microstructure and mechanical properties of cold rolled Al1050 sheet. This study is focused on microstructure and texture evolution of Al1050 annealed at various heating rates, annealing temperatures, and holding times. It was observed that the longer exposure time for deformed microstructure affects the Vickers hardness values, grain size, and texture intensity. It seems that the crystallographic texture evolution is not affected by heating rate on quantitative level since the same set of orientations tended to evolve in all studied cases. The sample annealed at slow heating rate in a box-type furnace produced recrystallized microstructure with fine grain size, and comparatively lower texture intensity & hardness.

Phase transition behaviors of Al nanoparticles with low oxidation degree: A molecular dynamics study

In this study, the ReaxFF reactive force field is applied to simulate the melting and annealing behaviors of aluminum (Al) nanoparticles (ANP) by molecular dynamics (MD) simulations. Potential energy, specific heat and FCC lattice number are used to study the thermal behavior of the entire phase transition process. First, the melting and solidification process of 3[Formula: see text]nm cubic Al and Al2O3 models under constant-pressure/temperature ensemble (NPT) system was simulated without boundary, and the steady-state simulation was discussed at specific temperature points. The non-boundary simulation proved the effectiveness of the Reaxff reactive force field for ANP phase transition simulations. It is confirmed that the physical properties of Al and Al2O3 could be effectively reflected in the MD simulations. ANP with low oxidation degree cannot be completely ignored in engineering applications. The existence of oxide layer hinders the annealing behavior. Therefore, this study also carried out an additional simulation process of 6 nm ANP and its oxide particles in canonical ensemble (NVT). Those obtained results show that a small amount of oxide layer can greatly change the thermal properties of ANP. If the surface of ANP is isolated, then its melting point could be increased by at least 30[Formula: see text]K.

Aqueous buffer solution-induced crystallization competes with enzymatic depolymerization of pre-treated post-consumer poly (ethylene terephthalate) waste

The complex relationship between kinetics and substrate morphology during enzymatic depolymerization of melt processed poly(ethylene terephthalate) (PET) is explored and the effects of competing transformations are analyzed. Extruded PET substrates from post-consumer recycled PET (RPET) bottles flakes subjected to enzymatic depolymerization are examined to reveal increases in crystallinity from ∼10% post-extrusion to > 30% after 3 days of depolymerization as well as increases in glass transition temperature (Tg) from ∼66 °C to > 80 °C. Further investigation into this behavior shows that post-extrusion RPET substrates do not exhibit changes in crystallinity when subjected to dry annealing at 65 °C in an oven over 7 days, but they do experience annealing in depolymerization buffer solution with no enzymes at 65 °C within 3 days. This difference may be attributed to plasticization of PET in the presence of water, also known as solvent induced crystallization. The impact of this plasticized annealing behavior is demonstrated by subjecting RPET substrates to increasing enzyme-to-substrate loads. As enzyme load increases, overall conversion of substrates increases despite crystallinity also increasing to similar levels regardless of the initial enzyme loading. The competition between depolymerization and crystallization suggests that the rate at which PET substrates are depolymerized at the operational temperature is integral to achieving high conversion to monomeric product. This, in turn, also suggests that savings from lowered enzyme loadings may be more detrimental than helpful in pursuing the most cost-effective recycling systems.

Isothermal annealing of radiation defects in silicon bulk material of diodes from 8” silicon wafers

The high luminosity upgrade of the LHC will provide unique physics opportunities, such as the observation of rare processes and precision measurements. However, the accompanying harsh radiation environment will also pose unprecedented challenged to the detector performance and hardware. In this paper, we study the radiation induced damage and its macroscopic isothermal annealing behaviour of the bulk material from new 8” silicon wafers using diode test structures. The sensor properties are determined through measurements of the diode capacitance and leakage current for three thicknesses, two material types, and neutron fluences from 6.5· 1014 to 1 · 1016 neq/cm2.

Effects of carbon doping on annealing behavior of a CoCrFeNiMn high-entropy alloy

A 1 at% carbon non-equiatomic doped Co19Cr5Fe38Ni19Mn19 high-entropy alloy was synthesized by vacuum arc-melting in a high-purity argon atmosphere, followed by homogenization, cold rolling, and annealing under various conditions. The evolutions of microstructure and mechanical properties during annealing were systematically studied and compared with the carbon free alloy. Results showed that nano-sized fibrous deformation grains were formed in the 90% cold rolled alloys, resulting in high strength but low plasticity. Recovery sub-structures and recrystallized grains gradually formed with increasing annealing temperature, leading to a significant decrease in defect density, thereby softening the materials and increasing their plasticity. The early stage of recovery was mainly related to the migration of vacancy and interstitial carbon atoms, while dislocation climb became the main recovery mechanism in the late recovery stage. The carbon-doped alloy exhibited a higher recovery activation energy compared with the carbon free alloy. Therefore, 1 at% interstitial carbon effectively increased the recovery and recrystallization resistance of the Co19Cr5Fe38Ni19Mn19 alloy.

Ionizing Radiation Effects on Hole Collection Backside-Illuminated p-Type Deep-Trench-Pinned Photo-MOS Pixels Under Image Acquisition

Dark current degradation, origins, and annealing behavior after x-ray irradiation are studied in a P-type, hole collecting, backside-illuminated image sensor currently being developed at STMicroelectronics and based on deep-trenched photo-MOS pixels. Different biasing conditions during irradiation, i.e. grounded or biased and sequenced, are compared. The dark current increase with total ionizing dose (TID) and the dark current annealing behavior seem to be driven by the backside interface between the P-epitaxy of the pixels and the ONO stack. Despite still being under development, this pixel architecture already exhibits both very good electro-optical performance and a better radiation hardness than pinned photodiode-based CMOS Image sensors that benefit from the same advanced CIS processing technologies. At high total dose range, the photogate challenges custom Radiation-Hardened-by-Design photodiodes by exhibiting a comparable radiation tolerance while bringing new features such as high-resolution or Correlated Double Sampling.