Crystallization Activation Energy Research Articles

Colloidal Ink Engineering for Slot-Die Processes to Realize Highly Efficient and Robust Perovskite Solar Modules.

Perovskite solar cells (PSCs) have emerged as a promising alternative to silicon solar cells, but challenges remain in developing perovskite inks and processes suitable for large-scale production. This study introduces a novel approach using colloidal inks incorporating toluene and chlorobenzene as co-antisolvents for PSC fabrication via slot-die process. It is found that colloidal inks that are strategically engineered can significantly improve the rheological properties of perovskite inks, leading to enhanced wettability and high-quality film formation. The formation of large colloids such as α cubic perovskite, δ hexagonal perovskite and transition intermediate phases promotes heterogeneous nucleation and lowers activation energy for crystallization, resulting in superior crystal growth and improved film morphology. Notably, the co-solvent enhances the FA-PbI3 binding energy and weakens the dimethyl sulfoxide coordination, which is more thermodynamically favorable for perovskite crystallization. This colloidal strategy yields devices with a maximum efficiency of 21.32% and remarkable long-term stability, retaining 77% of initial efficiency over 10115 h. The study demonstrates the scalability of this approach, achieving 20.26% efficiency in lab-scale minimodules and 19.15% in larger convergence minimodules. These findings provide an understanding of the complex relationship between ink composition, rheological properties, film quality, crystallization kinetics, and device performance.

Effect of TiO2 on melting and crystallisation properties of CaF2(50%)-CaO-Al2O3-MgO(3%)-ZrO2(4%) electroslag

This study investigates the effect of highly fluorinated electroslag with TiO2 content of 0%, 3%, 6% and 9% on the melting process, crystallisation kinetics and crystalline product structure by using STA, XRD and SEM-EDS techniques. The results demonstrated a gradual decrease in the melting temperature, heat of fusion and first crystallisation temperature of the slag as the TiO2 content increased. The main precipitation phases in the slag are Ca12Al14O32F2, CaF2, CaZrO3, CaTiO3, (Ca, Zr, Ti)O2 and MgO. The larger the ratio of TiO2:ZrO2, the higher the precipitation rate of multi-faceted CaTiO3. The precipitation of dendritic CaZrO3 was also gradually suppressed. Crystallisation kinetic analysis revealed that the slag exhibited the highest activation energy for crystallisation at a TiO2 content of 6%. These findings have a positive impact on determining the TiO2 content in the electroslag and enhancing the surface quality of the ingot.

Effect of NiO, CuO, Co3O4, and Fe2O3 on the crystallization kinetics of glasses based on slags from joint smelting of silicate nickel and copper pyrite ores

ABSTRACT The effect of modification by addition of 6% by mass of a mixture of NiO, CuO, and Co3O4 taken in equal mass portions with the replacement of half of FeO by Fe2O3 of glass (<0.1 mm) based on slag from joint smelting of nickel and copper ores on kinetics of its crystallization has been studied. Using X-ray powder diffraction, scanning electron microscopy, energy-dispersive spectrometry, and differential scanning calorimetry, it was shown that modification does not change the nature of the released phases and the sequence of their appearance during crystallization. A decrease in the activation energy of crystallization from 663 to 527 kJ·mol−1 for the first period (pigeonite and anorthite release) and from 756 to 542 kJ·mol−1 for the second one (SiO2 release) without changing the process mechanism has been established. The results supplement the information necessary to substantiate non-isothermal and isothermal technological modes of glass processing to obtain glass-ceramics.

Synthesis and non-isothermal crystallization kinetics of polyamide 66 copolymers containing alicyclic structures.

To further improve the performance of PA66 and expand its applications, a new strategy was proposed to introduce an alicyclic structure into PA66 chain by the copolymerization method. Initially, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane (MACM) was reacted with 1,6-adipic acid to form MACM6 salt, and then, it was copolymerized with PA66 salt to synthesize PA66/MACM6 copolymers with alicyclic structures. PA66/MACM6 copolymers exhibited good thermal stabilities, and the presence of alicyclic structure had no significant effect on their thermal stabilities. Notably, the crystallization temperature, crystallinity and melting point of the PA66/MACM6 copolymer decreased gradually with increasing MACM6 content, indicating that the addition of the MACM6 segment disrupted the regularity of the original PA66 chain. Moreover, as the melting point of the PA66/MACM6 copolymer was in between 223.9 °C and 254.8 °C, it could be processed in a wide temperature range to meet the requirements of different industrial applications. The non-isothermal crystallization kinetics of PA66/MACM6 copolymers were investigated using the Jeziorny and Mo methods, and the crystallization activation energy was calculated using the Kissinger method. The results indicated that the introduction of the MACM6 segment into the PA66 chain by copolymerization inhibited its crystallization and increased its crystallization activation energy, thereby reducing its crystallization rate. In addition, PA66/MACM6 copolymers exhibited improved toughness with a slight decrease in the strength. When the content of MACM6 reached 40 wt%, the elongation at break of PA66/MACM6-40 was about 760% higher than that of PA66, suggesting its high toughness.

Synthesis, characterization, crystallization kinetics of amorphous Fe74.5Zr8.5B17 magnetic nanoparticles, and magnetoelectric properties of Fe74.5Zr8.5B17/BaTiO3 composite

This work reports the facile synthesis of amorphous Fe74.5 Zr8.5 B17 magnetic nanoparticles (MNPs) through a simple NaBH4-assisted chemical reduction method. The obtained MNPs were characterized in terms of amorphous/crystal structure, morphology, magnetic properties, composition, and crystallization kinetics. The saturation magnetization value was determined as 57.83 emu/g. The crystallization peak temperatures (Tp) and activation energy were determined to be 467.18 °C and 294 kJ/mol, respectively. Additionally, the FeZrB MNPs were combined with the BaTiO3 NPs via ball milling at low speed, using a mass ratio of 30/70%, respectively and the magnetoelectric coefficient value for FeZrB/BaTiO3 composite measured at a 1 kHz AC magnetic field is approximately 8.9 mV/Oe/cm. The study outcomes may provide a platform of nanotechnology for the preparation of MNPs with adjustable properties, which will be promising for practical applications.

Wetting and interface behavior between borosilicate glass and YAG

In this work, four kinds of borosilicate glasses (La2O3/SrO/MgO/BaO-B2O3-SiO2) were designed to investigate the wetting and interface behavior between glass filler and YAG crystal. The thermal property, coefficient of thermal expansion (CTE), crystallization activation energy, optical property and wetting behavior of four kinds of glasses were first studied. The results showed that SBS (SrO-B2O3-SiO2) glass had the most matching CTE with YAG. In addition, all four kinds of glasses had good transparency and exhibited good wettability on the surface of YAG. Furthermore, microstructural analysis of wetting samples indicated that the interface behavior between borosilicate glasses and YAG could be divided into three types: There was only dissolution and diffusion of elements between glass and YAG; The elements of YAG dissolved into glass filler, changing the chemical composition of glass and promoting glass crystallization; Interface reaction occurred between glass and YAG to form the interface layer. Finally, the SBS glass was chosen to bond YAG. The YAG/SBS/YAG joint with high shear strength (78.77 ± 4.3MPa) and good in-line transmittance (76.5% at 1064nm) was obtained.

Enhancing the Non-Isothermal Crystallization Kinetics of Polylactic Acid by Incorporating a Novel Nucleating Agent.

Polylactic acid (PLA) is a widely recognized biodegradable polymer. However, the slow crystallization rate of PLA restricts its practical applications. In this study, camphor leaf biochar decorated with multi-walled carbon nanotubes (C@MWCNTs) was prepared using the strong adhesive properties of polydopamine, and PLA/C@MWCNTs composites were fabricated via the casting solution method. The influence of C@MWCNTs as a novel nucleating agent on the melt behavior and non-isothermal crystallization behavior of PLA was investigated using differential scanning calorimetry (DSC). The crystallization kinetic parameters were obtained through the Jeziorny, Ozawa, and Mo methods, and the crystallization activation energy of the PLA/C@MWCNTs composites was calculated by the Kissinger method. The results show that the PLA/C@MWCNTs composites exhibit higher crystallinity and crystallization temperatures than those of PLA. Non-isothermal crystallization kinetic analysis reveals that the Mo method better describes the non-isothermal crystallization kinetics of both PLA and PLA/C@MWCNTs composites. In addition, it was found that C@MWCNTs, despite increasing the crystallization activation energy, can act as an efficient nucleating agent to increase the crystallization rate of PLA. These experimental results provide valuable insights for enhancing the slow crystallization rates associated with PLA.

Non-Isothermal Crystallization Kinetics and Properties of CaO-Al2O3-SiO2 (CAS) Glass-Ceramics from Eggshell Waste, Zeolite, and Pumice.

In this study, the crystallization behavior, microstructure, and mechanical and physical properties of CaO-Al2O3-SiO2 (CAS)-based glass-ceramics prepared from eggshell waste, zeolite, and pumice were investigated using X-ray diffraction (XRD), differential thermal analysis (DTA), scanning electron microscopy (SEM), a nanoindentation tester, and the Archimedes method. XRD analysis revealed that anorthite and wollastonite crystalline phases precipitated in the glass-ceramic samples after sintering at temperatures of 1000 °C and 1100 °C. However, diffraction peaks belonging to the wollastonite phase disappeared after sintering at 1200 °C, while peaks representing the pseudowollastonite phase were detected together with anorthite in the samples. SEM images showed that the crystals become coarser as the sintering temperature increased, with the crystal morphology transitioning from needle-like to rod-like. The crystallization activation energy (Ea) and Avrami parameter (n), both kinetic parameters, were calculated from DTA curves plotted at different heating rates using the Kissinger, Ozawa, and Matusita approaches. The results indicated that the crystallization activation energy of the CASZ glass ranged from 406 to 428 kJ mol-1, while that of the CASP glass varied from 356 to 378 kJ mol-1, depending on the method used. Additionally, the Avrami constant (n) was calculated to be 3.33 for CASZ and 2.89 for CASP. The hardness and bulk density of the glass-ceramic samples were significantly affected by the porosity present in the structure, with the highest hardness and bulk density values achieved for the CASZ glass-ceramic sample at the initial sintering temperature of 1000 °C.

Crystallization behaviour, structure, and photocatalytic properties of SiO2-B2O3-Li2O-WO3-Bi2O3 glass-ceramics containing Bi2WO6 crystals

SiO2-B2O3-Li2O-WO3-Bi2O3 system parent glass was prepared by the melt-quenching method and glass-ceramics containing the Bi2WO6 crystals were obtained by a one-step heat treatment. The crystallization kinetics of the parent glass were investigated, and the effect of the different heat-treatment regimes on the microscopic morphology and optical bandgaps of the glass-ceramics was discussed. The results show that the crystallization activation energy of the parent glass is about 300 kJ/mol and the precipitated Bi2WO6 crystals exist in a columnar structure. As obtained from the UV–Vis spectra, the glass-ceramic with a heat treatment regime of 640 °C/2 h has the smallest optical bandgap (2.45 eV). During the photocatalytic degradation of methylene blue dye, the glass-ceramic with a heat treatment regime of 640 °C/2 h shows the best catalytic degradation performance, reaching a dye degradation rate of 76 % at 120 min. The experimental results indicate that glass-ceramics containing Bi2WO6 crystals have promising applications in the field of sewage treatment.

Crystallization Behavior and Structure of CaO–SiO2–Al2O3 Melts Representing the Oxide Inclusions in Si‐Mn Deoxidized Steel

For further optimization of the inclusion plasticization control process of Si‐Mn deoxidized steel, the crystallization behavior and structure of CaO–SiO2–Al2O3 system inclusions are investigated. The crystallization behavior of four typical low melting point CaO–SiO2–Al2O3 inclusions at 1000 to 1250 °C is studied by steel crucible isothermal heating experiment. The obtained results reveal that the glassy stability of the inclusions is high when the composition of low melting point inclusion is located in the eutectic region of tridymite, pseudowollastonite, and anorthite in the ternary phase diagram. However, when the composition of the inclusion is located in the eutectic region of melilite, pseudowollastonite, and anorthite, it is easy to undergo glass‐crystallization transformation and precipitate wollastonite and anorthite crystalline phases when isothermal heating at 1100 to 1200 °C. In addition, the crystallization mode of these inclusions is mainly surface crystallization, and the crystallization degree of inclusions increases with the increase of heat treatment temperature and time. The activation energy of crystallization and the content of nonbridging oxygen in the silicate structure NBO/T can be used to predict the crystallization ability of inclusions. The greater the activation energy of crystallization and the smaller the NBO/T value, the higher the glassy stability of the inclusions.

Effect of the synergistic interaction of zinc adipate, hydrotalcite and ethylene propylene rubber on the performances of polypropylene

Polypropylene (PP) is widely used in a range of areas due to its excellent physical and chemical properties, but its low-temperature brittleness and low-impact resistance largely limits its application. Hence, this study investigated the changes in mechanical and thermal properties of isotactic polypropylene (iPP) modified by the addition of the β-nucleating agent zinc adipate (ZnAA), the inorganic rigid particle hydrotalcite (HT), and the rubber elastomer bipropylene rubber (EPR). The structure and properties of modified PP were investigated by Fourier transform infrared (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), electronic universal material testing machine, and simple-beam impact testing machine. At last, the non-isothermal crystallization kinetics of iPP was investigated by the Caze method. It was found that with the addition of EPR reached 30 wt%, the notched impact strength of iPP was 34.74 kJ/m2, which was 542.43 % higher than that of pure iPP, and more than twice as high as that of ZnAA and HT modification, and the relative crystallinity ( K β) value of the β-crystalline form reached 79.66 % when 10 wt% EPR was added to the iPP. The addition of ZnAA, HT and EPR could significantly increase the crystallisation peak temperature ( T c), shorten the half-crystallisation time ( t 1/2) and increase the crystallisation activation energy ( ΔE) of iPP.

Non-isothermal crystallization kinetics and activation energy modeling of carbon nanotubes dispersed high-density polyethylene and polypropylene blends

The study presents the effect of the reinforcement of carbon nanotubes (CNT) into high-density polyethylene (HDPE) and polypropylene (PP) blends. The Avrami exponent of CNT blends ranges within the 1.3–1.6 range. It demonstrates the 3D growth of crystals and nucleation activity during crystallization. The change in the Ozawa exponent indicates a two-stage crystallization process. The values of the Mo exponent show that the nucleation activity is affected by changing temperatures during the cooling process and the formation of high-quality crystal growth. The activation energy of the HDPE/PP matrix is 420.5 kJ/mol and adding 1.5% CNT resulted in 369.9 kJ/mol for Run-3. The polymer chains encounter difficulties in transitioning during the cooling process and release a significant amount of energy. The composition of the nanofiller in the blend affects the nucleation activity of the crystals. The permeability of the pure HDPE/PP sample obtained from sorption studies is 1.05 × 10−5 m2/s and adding 1.5% CNT in Run-3 provides a permeability of 5.2 × 10−5 m2/s. The CNT has a homogeneous dispersion in the matrix to form a net-like morphology. The crystallinity index calculated using the Seagal method for HDPE/PP, Run-3, Run-4 and Run-5 is 75%, 75.8%, 77.34% and 78%, respectively.

Estimating the activation energy of crystallization in blends of poly L‐lactic acid and poly(propylene 2,5‐furan dicarboxylate) during isothermal melt crystallization using temperature dependent infrared spectroscopy

Estimating the activation energy of crystallization in blends of poly L‐lactic acid and poly(propylene 2,5‐furan dicarboxylate) during isothermal melt crystallization using temperature dependent infrared spectroscopy

Thickness dependence and crystallization properties of amorphous GeTe thin films on silicon dioxide

Radio frequency magnetron sputtering was used to prepare the amorphous GeTe thin films on silicon dioxide and the thickness effects on the crystallization behavior were investigated. With the film thickness reducing, the crystallization temperature, crystallization activation energy, amorphous and crystalline resistance increase remarkably, indicating the great improvement in thermal stability and power consumption. Ozawa’s model was used to estimate the crystallization kinetics of GeTe thin films, it shows that nucleation and grain growth occur simultaneously, and grain growth dominates ultimately. XRD analysis demonstrated that the grain size can be reduced and the crystallization process of GeTe thin film can be inhibited with the film thickness decreasing. Furthermore, the thinner film has smaller resistance drift index and surface roughness, which are beneficial to improve the reliability of storage device. T-type phase change memory devices based on 25 nm GeTe thin film were fabricated by 0.13 μm CMOS technology, and the current–voltage and resistance-voltage characteristics demonstrate the excellent electrical performance, including the fast resistance switching between SET and RESET processes, low threshold current and voltage. All the results proved the strong dependency relationships between the crystallization properties and film thickness of GeTe thin film, which paves the way for developing high-density phase change memory in the fields of big data and artificial intelligence.

Effects of particle size on the crystallization kinetics characterization in CaO–SiO2‐based glass, Part 2: In complex crystallization processes with two or more crystal phases

AbstractBased on the Matusita–Sakka equation and the exothermic peaks in the differential thermal analysis (DTA) curves, in silicate glasses with complex crystallization processes containing the precipitation of two or more crystal phases, the effects of particle sizes on the calculations of crystal growth dimensionality and activation energy of crystal growth have been studied in depth. In crystallization processes with two or more crystal phases but one exothermic peak, 0.3 mm is considered as the boundary between the fine and the coarse particles in this type of glass. For glass samples with a particle size less than 0.3 mm, the crystal growth dimensionality is a three‐dimensional mechanism, and EG increases slightly with decreasing particle size. For glass samples with a particle size greater than 0.3 mm, the crystal growth dimensionality is a two‐dimensional mechanism, and EG increases with decreasing particle size. The EG for the fine‐particle starting material is much lower than that of the coarse‐particle starting material. In crystallization processes with two or more crystal phases and two exothermic peaks, 0.104 mm is considered as the boundary between the fine and the coarse particles in this type of glass raw material. For the first peak, in glass samples with a particle size less than 0.104 mm, the crystal growth mechanism is mainly one‐dimensional growth, and EG increases slightly with decreasing particle size. And for glass samples with particle size greater than 0.104 mm, the crystal growth mechanism is mainly two‐dimensional growth, and EG decreases with decreasing particle size. For the second peak, the crystal growth mechanism is mainly a three‐dimensional growth, and EG increases with decreasing particle size.

Crystallization Kinetics and Melting Behavior of Novel Biobased Poly(butylene 2,5‐thiophenedicarboxylate)

AbstractPoly(butylene 2,5‐thiophenedicarboxylate) (PBTh) is a novel biobased semicrystalline polyester with superior thermal, mechanical, and gas barrier properties; however, the crystallization kinetics and melting behavior of PBTh have not been studied in detail so far. The crystallization kinetics of PBTh was first studied in this research. The Ozawa equation failed to describe the nonisothermal melt crystallization kinetics of PBTh due to the secondary crystallization. The crystallization activation energy value was calculated by the Friedman method, which was negative and exhibited the conversion dependence. The isothermal melt crystallization kinetics of PBTh was well described by the Avrami equation in a wide range of crystallization temperature from 84 to 120 °C. PBTh showed the fastest crystallization rate at 104 °C; moreover, the Avrami exponent value slightly varied between 2.2 and 2.7, suggesting the same crystallization mechanism within the investigated temperature range. PBTh displayed one or two melting endotherms depending on crystallization temperature, which was well explained by the melting, recrystallization, and remelting mechanism. In addition, the equilibrium melting point of PBTh was estimated to be 163.1 °C with the Hoffmann−Weeks equation.

Revealing the effect of annealing at Tg on the crystal growth in Au49Ag5.5Pd2.3Cu26.9Si16.3 metallic glass via nanocalorimetry

In this study, Au49Ag5.5Pd2.3Cu26.9Si16.3 metallic glass is annealed at Tg and its impact on crystal growth is demonstrated with nanocalorimetry. With annealing following the rapid quenching, an amorphous phase free of nuclei, a relaxed amorphous phase, an amorphous phase with nuclei, and an amorphous phase with crystals are sequentially produced. With the reheating at rates ranging from 100 to 50,000 K/s, these four stages are quantitatively distinguished. Additionally, crystal growth behaviors of these four stages are demonstrated by the Kissinger and Mauro-Yue-Ellison-Gupta-Allan model. For the quenched and relaxed amorphous phases, the apparent crystallization activation energy (Ea) decreases with increasing heating rate, with a noticeable upward deviation at ultrahigh heating rates. When nuclei and crystals form in the amorphous phase, Ea keeps decreasing with the heating rate. As the annealing time increases, the maximum growth rate (umax) exhibits a monotonic increase while the temperature corresponding to umax displays a maximum.

Transition mechanism and thermokinetic analysis of Sr0.5Zr2(PO4)3–Ce0.5Sm0.5PO4 composite ceramics for nuclear waste forms based on in-situ synthesis

In this study, the novelly designed Sr0.5Zr2(PO4)3–Ce0.5Sm0.5PO4 composite ceramics were utilized as nuclear waste form to simultaneously immobilize simulated fission products Sr and actinide nuclides. The phase transition mechanism, thermokinetics and densification behavior of Sr0.5Zr2(PO4)3–Ce0.5Sm0.5PO4 composite ceramics based on in-situ synthesis were systemically analyzed by XRD, in-situ XPS, TG-DSC, SEM and density measurements. The results demonstrate that the formation of Ce0.5Sm0.5PO4 solid solution phase preceded that of Sr0.5Zr2(PO4)3 phase, of which there is a valence change of Ce from Ce4+ to Ce3+ before 1023 K. Additionally, as for the exothermic crystallization enthalpy, change of exothermic crystallization enthalpy and activation energy, the values of Sr0.5Zr2(PO4)3 and Ce0.5Sm0.5PO4 phases in composite ceramics are 286.17 – 515.61 mJ, 19.11 – 35.38 J/g, 702.45 kJ/mol and 145.21 – 232.44 mJ, 9.26 – 15.44 J/g, 450.04 kJ/mol, respectively. It is then indicated that the formation of Ce0.5Sm0.5PO4 phase is definitely more favorable than that of Sr0.5Zr2(PO4)3 phase. Simultaneously, the relative densities of Sr0.5Zr2(PO4)3–Ce0.5Sm0.5PO4 composite ceramics are more than 95 % when the sintering temperature exceeds 1273 K.

Influence of high field strength ions on the crystallization characteristics and properties of slag glass-ceramics

Blast furnace slag glass–ceramics were prepared by melting using rare-earth-containing blast furnace slag (REBFS) as the main raw material and Fe2O3 and Cr2O3 as composite nucleating agents. By adding different TiO2 contents, the study comprehensively revealed the effects of high field strength ions on the glass network structure, crystalline properties, elemental distribution and physicochemical properties. Raman spectroscopy and differential scanning calorimetry revealed that TiO2 acted primarily as a network modifier in the glass network. The appropriate TiO2 content disrupted the glass network, decreasing the crystallization activation energy (EC) of the glass–ceramic. However, excess TiO2 repaired the network structure, thereby increasing the EC. The combined effect of the Cr and Ti substantially improved the crystallization characteristics of the glass-ceramics. Cr2O3 induced the formation of spinel, which promoted the crystallization of the main crystalline augite phase. The self-aggregation of the high field strength Ti4+ ion induced the formation of a titanium- and cerium-containing titanite phase, which also contributed to grain refinement. This titanite phase effectively increased the Vickers hardness and acid and alkali resistances of the glass-ceramics to 9.16 GPa and over 98.5 %, respectively. The excellent physicochemical properties render REBFS glass–ceramics as being promising materials for various construction applications. This research provides theoretical support for comprehensively utilizing blast furnace slag and provides theoretical guidance for preparing slag glass–ceramics possessing desirable physicochemical properties.

Kinetics of crystallization and soft magnetic properties of Co72Fe8B10Si10 amorphous alloys

Co72Fe8B10Si10 amorphous alloy was prepared in an Ar atmosphere using a single roller rapid quenching technique at a wheel speed of 25 m/s. The prepared ribbons were annealed for 1 h at temperatures ranging from 473 to 773 K. X-ray diffractometer was used to observe the microstructure transformation. Field emission scanning electron micrographs exhibit mosaic type structures that become more prominent with increasing annealing temperature. Energy dispersive X-ray spectroscopy was also utilized to observe the concentrations of elements. The Kissinger and Ozawa equations were utilized to determine the amorphous alloy's crystallization activation energy. The two methods revealed consistent findings in their calculations. At 473 K, the obtained maximum real initial permeability (μ′max) is 376 which remains unchanged up to 10 kHz, whereas for 573 K, μ′max is noted to be 361 to 100 kHz. Other magnetic parameters such as loss factor, quality factor, and relative quality factor were also investigated for the Co72Fe8B10Si10 amorphous alloy to elucidate its suitability in such materials based devices.