Soluble: heptane, isopropanol. Absorb or cover with dry earth, sand or other non-combustible material and transfer to containers. Titanium dioxide, also known as titanium (IV) oxide or titania, is the naturally occurring oxide of titanium. Alkoxides derived from bulkier alcohols such as isopropyl alcohol aggregate less. Titanium dioxide (TiO 2 ) thin films are deposited from a liquid titanium isopropoxide (TTIP, Ti(OPr) 4 ) solution with no carrier gas on silicon and silicon nitride substrates with 3-D micrometer- and nanometer-scale structures. Line 6: exposes the vapor of the precursor 4 onto the substrate for 0.7 sec. Thin films of composition Ti x Si 1-x O 2 were grown by low-pressure (LP) CVD on silicon (100) substrates using tetraethyl orthosilicate (TEOS), [Si(OC 2 H 5) 4], and either titanium isopropoxide (TTIP), [Ti(O-'Pr) 4], or anhydrous titanium tetranitrate (TN), [Ti(NO 3) 4], as the sources of SiO 2 and TiO 2, respectively.The substrate temperature was varied between 300 °C and 535 °C, and the . Exposure to moist air or water. The common precursor, TiCl 4, is a liquid with a moderate vapor pressure [22-27]. LARGE SPILL: Dike far ahead of liquid spill for later disposal. pressure of O 2 was held constant at 0.83 Torr. Starting material for barium-strontium-titanate thin films. Gas permeation through the dense membrane was governed by . In this research, pure anatase phase titanium dioxide thin films were successfully fabricated for the first time using the mist chemical vapor deposition method, and optional values for deposition temperature and concentration of titanium tetraisopropoxide were established. Quartz crystal microbalance. A naturally occurring oxide sourced from ilmenite, rutile and anatase, it has a wide range of applications. Titanium Isopropoxide exhibit a vapor pressure surge above 40 - C and we report the volume precursor consumption as a function of precursor temperature and thin fllm thickness for ALD grown TiO 2 on Si, GaN, and Precursors Packaged for Depositions Systems. Ltd. 12 Anella Avenue Castle Hill NSW 2154 Australia Technical Phone # +61 2 9841 0555 (1800 800 097) . 91,4-97,2. Ideally, the amount of precursor injected is designed to result Combinatorial Characterization of TiO2 Chemical Vapor Deposition Utilizing Titanium Isopropoxide ACS Comb Sci . Desai, J. Phys Chem Ref Data . Titanium oxide thin films were deposited at room temperature by the Electron Cyclotron Resonance Plasma-Assisted Chemical Vapor Deposition (ECR-PACVD) method. Experimental 2.1. In general, the gas flow rate through falling liquid film aerosol generator 26, is maintained in the laminar region, e.g., corresponding to a Reynolds number less than . In consequence, combinatorial chemical vapor deposition techniques are utilized more to study functional properties of thin films as a function of chemical composition, growth rate or . National Center for Biotechnology Information. s-tertTri-butoxysilanol was used as received. Keep away from open flames, hot surfaces and sources of ignition. FOIA. Titanium isopropoxide is a component of the Sharpless epoxidation, a method for the synthesis of chiral epoxides. Room temperature evaporation of titanium isopropoxide [Ti[OCH(CH3)2]4, TTIP] precursor was performed using ultrasonic atomization for TiO2 atomic layer deposition (ALD). p-type . Titanium oxynitride (TiNxOy) thin films were deposited by low‐pressure metal-organic CVD (LP‐MOCVD) on (100) silicon, sapphire, and polycrystalline alumina substrates. Titanium isopropoxide, titanium ethoxide, titanium-2-ethylhexyloxide, titanium cyclopentyloxide, and a titanium amide, or a . Titanium dioxide, in the form of discrete, solid substantially spherical particles of a substantially uniform shape and size, is obtained by providing an aerosol comprising discrete liquid particles of a hydrolyzable titanium compound, contacting the aerosol with water vapor in dynamic flow to hydrolyze the liquid titanium (IV) compound to titanium dioxide, and recovering the desired product. Keeping the interest in developing modern and sustainable methods of materials chemistry, this chapter focuses on synthesis routes for TiO2 HNSs reported by researchers from all over the world. Vapor -phase pyrolysis The pyrolysis system is shown in Fig. The setup is adopted to carry out deposition in two configurations, namely under chemical vapor deposition (CVD) and atomic layer deposition (ALD) modes. Policies. Ti (OiPr)4 has vapor pressure 1.0 Torr/62°C, vapor pressure equation logP (Torr) = 8.38-2811/T (K). Thin films of TiO 2 were deposited on the inner surface of porous Vycor glass tubes by atmospheric pressure chemical vapor deposition (APCVD) at temperatures ranging from 200 to 400°C using titanium isopropoxide as a precursor. The number of electrons in each of Titanium's shells is [2, 8, 10, 2] and its electron configuration is [Ar] 3d 2 4s 2. Titanium isopropoxide (TIP) and ammonia were used as precursors. INTRODUCTION: Titanium dioxide (TiO2) is a very useful semiconducting transition metal oxide material and exhibits unique characteristics such as lowcost,easy handling, non-toxicity and resistance to photochemical and chemical erosion.These advantages make TiO2 a material in solarcells . Titanium(IV) isopropoxide sc-253704 Hazard Alert Code Key: EXTREME HIGH MODERATE LOW Section 1 - CHEMICAL PRODUCT AND COMPANY IDENTIFICATION PRODUCT NAME Titanium(IV) isopropoxide STATEMENT OF HAZARDOUS NATURE CONSIDERED A HAZARDOUS SUBSTANCE ACCORDING TO OSHA 29 CFR 1910.1200. . Ti (OiPr)4 is thermally stable at 260°C at least for 1h. TiO(2) nanospherical and fibered structures were obtained via a one-step sol-gel method in supercritical carbon dioxide (scCO(2)) involving polycondensation of the alkoxide monomers titanium isopropoxide (TIP) and titanium butoxide (TBO) with acetic acid (HAc). Absorb or cover with dry earth, sand or other non-combustible material and transfer to containers. We report the selective area deposition of titanium dioxide using titanium isopropoxide and water in a high-vacuum chemical vapor deposition (HV-CVD) process at a substrate temperature of 225 °C. Titanium oxinitride thin films have been grown by low pressure metal organic chemical vapor deposition (LP-MOCVD) using titanium isopropoxide, Ti(OCH(CH 3 ) 2 ) 4 (TIP) and NH 3 precursors in a growth temperature range from 450 to 750°C on sapphire substrates. Thin films of TiO 2 have been deposited on silicon wafers from titanium tetrakis‐isopropoxide (TTIP) and TTIP/H 2 O using low pressure metalorganic chemical vapor deposition. In this chapter, we review the controlling of the microstructures, the properties, and the different methods to obtain titanium dioxide and the application of these materials on solar cells. A vapor-suppressing foam may be used to reduce vapors. Titanium(IV) isopropoxide (Ti(O(CH 3) 2 CH) 4, TTIP) is an . Water spray may reduce vapor, but may not prevent ignition in closed . Contact. LARGE SPILL: Dike far ahead of liquid spill for later disposal. Stability and reactivity Reactive Hazard None known, based on information available Stability Moisture sensitive. precursor is not limited by its vapor pressure. ΔH vap: 14.7 kcal/mol. When these data were not available or unreliable (e.g. In the first section, we provide a background on energy, including its sources—photovoltaics . The vapor pressure was determined by the temperature of the Ti(OCH(CH 3) 2) 4 cell. titanium-isopropoxide precursor was heated to 82 °C to in-crease its vapor pressure. We will concentrate on the application of efficient solar cells including dye-sensitized solar cells (DSSCs). Water and hydrogen peroxide were vaporized in containers, which were kept at 20°C and 36°C, respectively. Titanium Isopropoxide exhibit a vapor pressure surge above 40^ o C and we report the volume precursor consumption as a function of precursor temperature and thin film thickness for ALD grown TiO 2 on Si, GaN, and Al-foil substrates. Titanium dioxide (TiO 2) thin films are synthesized using aerosol‐assisted (AA)CVD of titanium (IV) isopropoxide (TTIP) in methanol.Deposition is carried out on glass, steel, and titanium substrates at 400-550°C. Vapor pressure, 50 °C: 0.9 mm. This chapter covers different routes of preparation of hierarchical nanostructures (HNS) of titanium dioxide. Product Name TITANIUM(IV) ISOPROPOXIDE, 97% Product Number 205273 Company Sigma-Aldrich Pty. the isopropoxide species remained on the surface after TTIP exposures. 2. Transparent titanium oxide films were . 8600 Rockville Pike, Bethesda, MD, 20894 USA. Use clean, non-sparking tools to collect absorbed material. The temperature required to vaporize the Pb powder was about 700~ and the Pb vapor was transported to the sub- strafe by argon (99.9999%) as the carrier gas. Because of the inherently high vapor pressure of TiCl 4, the amount of vapor produced in the inert carrier gas is considerably more than in the case of titanium (IV) alkoxides. and one that has a vapor pressure so that it evaporates slowly enough so that the liquid film is not disrupted during the evaporation. The flow of oxygen precursor was controlled with a calibrated needle valve. Water spray may reduce vapor, but may not prevent ignition in closed . Vapor Pressure N/A SG/Density 0.97 g/cm3 Partition Coefficient N/A Viscosity N/A Vapor Density N/A . Dense and hydrogen-permselective membranes were formed only in the temperature range between 230 and 300°C. Titanium dioxide (TiO2) thin films are deposited from a liquid titanium isopropoxide (TTIP, Ti(OPr)4) solution with no carrier gas on silicon and silicon nitride substrates with 3-D micrometer- and nanometer-scale structures. Titanium(IV) propoxide 98%; CAS Number: 3087-37-4; EC Number: 221-411-3; Synonyms: Tetrapropyl orthotitanate; Linear Formula: Ti(OC3H7)4; find Sigma-Aldrich-253081 MSDS, related peer-reviewed papers, technical documents, similar products & more at Sigma-Aldrich Titanium dioxide (TiO2) thin films are synthesized using aerosol‐assisted (AA)CVD of titanium (IV) isopropoxide (TTIP) in methanol. Titanium tetrakis (isopropoxide) Ti (OiPr)4 (M = 284.22) is colorless moisture sensitive liquid with density d = 0.96 (20°C), melting point 14-17°C, boiling point 58°C/ 1 Torr. Recently, titanium alkoxides become promising precursors without corrosive halogen by-products, and research has been carried out on isopropoxide (Ti(OiPr)4) and titanium ethoxide (Ti(OEt)4). Company Identification: Acros Organics N.V. One Reagent Lane Fair Lawn, NJ 07410 Titanium (IV) isopropoxide - SafetyOpen Data Verified Data. 1 Identification of substance:; Product details: Trade name: Lead titanium isopropoxide, 5% w/v in isopropanol Stock number: 39153 Manufacturer/Supplier: Alfa Aesar, A Johnson Matthey Company Johnson Matthey Catalog Company, Inc. 30 Bond Street Titanium (IV) isopropoxide | C12H32O4Ti - PubChem. Titanium(IV) isopropoxide is generally immediately available in most volumes. I. In the ALD process with H 2 O/H 2 O 2 as oxidant, the corrosive by-products of HCl and residual TiCl 4 are considered as a drawback. See more Titanium products. It was found that the crystallinity of the titanium dioxide film was significantly improved by increasing the deposition . SSupporting Information ABSTRACT: Titanium tetraisopropoxide (TTIP) is a precursor utilized in atomic layer depositions (ALDs) for the growth of TiO 2 The chemistry of TTIP deposition onto a slightly oxidized molybdenum substrate was explored under ultrahigh vacuum (UHV) conditions with X-ray photoelectron spectroscopy. vapor pressure of any particular sample of aluminum isopropoxide, and the deposition rate of aluminum oxide is not reproducible. Si and Fe data from P.D. Titanium isopropoxide, also commonly referred to as titanium tetraisopropoxide or TTIP, is a chemical compound with the formula Ti {OCH (CH3)2}4. Application. Plasma-assisted chemical vapor deposition (PCVD) at pressure as low as 3 mtorr using titanium-tetra-isopropoxide (TTIP) and oxygen mixed gas plasma generated by 13.56 MHz radio frequency power (RF-power) below 70 W were applied to deposit titanium-oxide layer at temperature under 40°C. The films produce morphologies that are radically different to those from typical aerosol‐assisted processes, and from the use of TTIP in low or atmospheric pressure (AP)CVD. The combinatorial characterization of the growth kinetics in chemical vapor deposition processes is challenging because precise information about the local precursor flow is usually difficult to access. Used to make porous titanosilicates, potential ion-exchange materials for cleanup of radioactive wastes. The structures of the titanium alkoxides are often complex. It has a role as a food colouring. National Institutes of Health. Selection of the process parameters enabled obtaining membranes with up to 300 εg cm−2 of polymerized titanium isopropoxide. Molecular Weight: 232.27 (116.13 monomer) Molecular Formula: C 10 H 26 Al 2 O 2. SrTiO 3 thin films were deposited by low-pressure organometallic chemical vapor deposition. Titanium dioxide is a titanium oxide with the formula TiO2. though TDMAT has an adequate vapor pressure even at room temperature , and the delivery . AKT872 - TITANIUM ISOPROPOXIDE TITANIUM ISOPROPOXIDE Safety Data Sheet AKT872 Date of issue: 12/30/2014 Version: 1.0 . Department of Health and Human Services. The electrical behaviour of these films was studied between 400 and 173 K, revealing three different behaviours, ranking from a . TTIP, which is an alkoxide of titanium having a chemical formula of Ti(OCH(CH3)2)4, is considered the most appropriate precursor for TiO2 films because it has the highest vapor pressure [9], exhibits non-corrosive and self-limiting growth, and thus produces films of high purity, whereas the by-products of TiCl4 are corrosive, Log Pow : No . Metal content: 16.6-16.9% Ti. Line 10: exposes the vapor of the precursor 2 onto the substrate for 14 sec. A side-by-side comparison of the TiO 2 deposition kinetics and the corresponding film microstructures using titanium(IV) isopropoxide and anhydrous titanium(IV) nitrate was conducted at low pressures (< ICH Torr) in an ultrahigh vacuum chemical vapor deposition reactor. Titanium tetrachloride is the inorganic compound with the formula TiCl 4.It is an important intermediate in the production of titanium metal and the pigment titanium dioxide.TiCl 4 is a volatile liquid. It was noted that the presence of air in the plasma chamber increased the amount of deposited polymer. Upon contact with humid air, it forms thick clouds of titanium dioxide (TiO 2) and hydrochloric acid, a reaction formerly exploited to produce fake smoke on film sets. Deposition of the titanium oxide layer resulted . Titanium(IV) isopropoxide Revision Date 24-Dec-2021 10. Conditions to Avoid Incompatible products. Disclosed is a method of production of high purity fused silica glass doped with titania through oxidation or flame hydrolysis of a gaseous mixture and containing rutile crystals comprising a vaporizable, silicon-containing compound and a vaporizable titanium compound. (solid, gas) : Flammable liquid and vapor Vapor pressure : 19 mm Hg @ 100˚C Vapor pressure at 50 °C : 0.9 mm Hg Relative vapor density at 20 °C : > 1 Relative density : 0.937 Solubility : Reacts with water. How do you measure the vapor pressure of refractory elements, such as Tungsten? Crystalline titanium methoxide is tetrameric with the molecular formula Ti4(OCH3)16. Vapor pressure: No data available Density at 20 °C (68 °F): 0.955 g/cm 3 (7.969 lbs/gal) Relative density No data available. Vapor pressure, 100 °C: 19 mm. Line 7: goes to line 5 for 150 cycle loop between 5 and 7. Vapor density No data available. Novel metal oxide/phosphonate hybrids were formed from titanium (IV) isopropoxide in a two-step sol-gel process. Line 8: closes the stop valve to the vacuum pump. Detailed vapour pressure data for the HfO 2 precursor hafnium alkoxides were determined. Titanium(IV) nitrate exhibited a lower activation energy of reaction (E r = 98 kJ/mol) which allowed deposition at lower . NFPA SUPPLIER Santa Cruz Biotechnology, Inc. 2145 Delaware Avenue titanium isopropoxide (TTIP, 99.9% 5N trace metal basis, Sigma-Aldrich), is vaporized using a heated bubbler in a water bath (SH-WB-13CDR SAMHEUNG ENERGY) at 70 °C. Titanium isopropoxide, Ti(OPr'),, held in the vaporizer (b) at lOO'C, was transported in the vapor phase by a controlled stream of (a) dry nitrogen (1 .O 1 min - ') into the 20 cm long hot zone of a quartz tubular reactor (c). Tris-tert-butoxysilanol, titanium -isopropoxide, and hexanetetrakis s (a mixture of isomers) were purchased from Sigma Aldrich. technique. Effects of deposition temperature, microwave power and plasma gas pressure were investigated. 2 from tetrakis-dimethyl-amido titanium or Ti isopropoxide precursors and H 2O Qi Xie and Yu-Long Jiang . Titanium isopropoxide, Sr(dipivaloylmethanate) 2, oxygen, and water vapor were used as reactants, and argon was used as a carrier gas.Growth rates ranging from 0.3 to 4.5 μm/h were obtained on (0001) sapphire substrates at 600-850 °C. 11. Porous polypropylene membranes were coated with plasma polymerized titanium isopropoxide in a 75 kHz plasma reactor. Titanium(IV) chloride Revision Date 24-Dec-2021 Clean Air Act Component HAPS Data Class 1 Ozone DepletorsClass 2 Ozone Depletors Titanium tetrachloride X - OSHA - Occupational Safety and Health Administration Not applicable CERCLA This material, as supplied, contains one or more substances regulated as a hazardous substance under the Comprehensive Environmental Response Compensation and Liability National Library of Medicine. During titanium-isopropoxide depositions, all flow lines containing the precursor were also heated in order to avoid condensation of the precursor. Dielectric constants of approximately 30 were measured by high . The chapter includes the details of chemical reactions taking place during the synthesis and . In wet chemical based methods, mostly the Ti-based organics (e.g. 1. Both Ar and O2 plasma were used to deposit films from titanium isopropoxide (Ti(OC3H7)4) precursor. Plasma optical emission spectroscopy and FTIR indicated that density of OH group in the amorphous layer was . The influence of the growth temperature, ranking from 450 °C to 750 °C, was investigated by scanning electron microscopy (SEM), and electrical DC . May cause irritation to eyes, skin, inhalation, ingestion or percutaneous absorption may be harmful to the body. merical study focuses on single spherically symmetric precursor/solvent droplets of titanium(IV) isopropoxide (TTIP) - Ti(OC 3H 7) 4 in p-xylene - C 6H 4(CH 3) 2 at room temperature in convective hot air at atmospheric pressure. Aluminum 2-ethylhexanoate has been proposed as another source for CVD of aluminum oxide.9 This solid source material has a very low vapor pressure, which limits the deposition rate to low values. Lower temperatures are applied in atomic layer deposition (ALD), where deliberate pyrolysis of the precursor is avoided to favor self-saturating surface reactions between two or more reactive partners. Atmospheric pressure chemical vapor deposition (AP-CVD) The thin film deposition is performed in an open-air reactor as depicted in Fig. Synthesis of [[(t. BuO) 3SiO] 2-Ti(O iPr) 2] The vapor is removed by continuous pumping, and the chamber pressure returns to its baseline value. The preferred titanium compounds at the present time are titanium alkoxide compounds such as titanium isopropoxide and titanium ethoxide. Evaporation rate . All depositions were conducted at a substrate temperature of 160 °C and 1 Torr chamber pressure. 2015 Jul 13;17(7):413-20. doi: 10.1021/acscombsci.5b00040. High purity, . Same as Ti halide, TiI 4 can also be served as another precursor [28-30] with relative less corrosive, compared to TiCl 4. Indeed, recently the open air dynamic deposition of amorphous coatings was performed via roll-to-roll systems using titanium isopropoxide (TTIP) and water vapor hydrolysis reaction at room. A vapor-suppressing foam may be used to reduce vapors. Utilized in spray pyrolysis synthesis of BaTiO 3 and SrTiO 3. These organic precursors of titanium (Ti) are very much sensitive to moisture and produce precipitate by the immediate exposure to water/moisture. This alkoxide of titanium (IV) is used in organic synthesis and materials science. Ti-isopropoxide, Ti-butoxide) are used as precursors to prepare the TiO 2 particles. The presence of an alcohol is not required, but it is desirable . large difference between vapor pressure of the solid and liquid phase at the melting point), fits to values from the wikipedia table, the CRC Handbook of Chemistry and Physics (78th edition, 1997, CRC press) and other sources were used. Titanium isopropoxide was distilled under reduced pressure and hexane was distilled from sodium benzophenone ketyl prior to use. After a waiting time t another liquid pulse is injected, and the process repeats. Chemical vapor deposition (CVD) techniques rely on high temperatures to activate the chemical decomposition of precursors on the substrate surface. The films produce morphologies that are radically different to those from typical aerosol‐assisted processes, and from the use of TTIP in low or atmospheric pressure (AP)CVD. The TiCl 4 exposures then removed the isopropoxide species and deposited additional titanium species. The structures of the titanium alkoxides are often complex. The precursor, i.e. CAS Number: 6063-89-4. Molecular complexity: 1.4. Titanium (atomic symbol: Ti, atomic number: 22) is a Block D, Group 4, Period 4 element with an atomic weight of 47.867. In order to avoid the rapid decomposition of titanium isopropoxide Use clean, non-sparking tools to collect absorbed material. rat oral LD50: 7460mg/kg. It is a diamagnetic tetrahedral molecule. A statistical method to measure conformality, and a model for pulse vapor exposure are presented. Line 9: opens the valve 2 for 0.2 sec to set up the vapor pressure of the precursor 2. Dimethylaluminum isopropoxide, dimer (DMAIPO) Product Number: 0035. There is an interesting paper that describes the measurement and the care that you need to take in doing it: "The pressure and heat sublimation of tungsten" by Szwarc, PLante, and Diamond at what was then the National Bureau of Standards. Titanium isopropoxide was volatilized at temperatures 26-75°C. We used perfluoroalkylsilanization to reduced surface residence time of the precursors and, consequently, to lower reaction rate and a prolonged . Yields coatings of barium titanate in combination with Ba (OR) 2. In ALD the substrate is exposed sequentially . A microplasma printer is employed to deposit thin film patterns of TiO 2 by titanium tetra-isopropoxide and N 2 /O 2 plasma at atmospheric pressure. The resulting materials were character … pressure to increase, as illustrated schematically in Fig. Titanium Isopropoxide exhibit a vapor pressure surge above 40^ o C and we report the volume precursor consumption as a function of precursor temperature and thin film thickness for ALD grown TiO 2 on Si, GaN, and Al-foil substrates. The films have been characterized by Rutherford backscattering spectrometry, forward recoil spectrometry, x‐ray diffraction, and electrical techniques. Keywords: Titanium dioxide(TiO2),Sol-gel method, X-ray Diffraction, Scanning Electron Microscope,FTIR. Excess heat. MSDS Name: Titanium(IV) isopropoxide Catalog Numbers: AC194700000, AC194700010, AC194700050, AC194702500 Synonyms: Tetraisopropyl orthotitanate. Deposition is carried out on glass, steel, and titanium substrates at 400-550°C. Langmuir equation to calculate vapour pressure curves for hafnium isopropoxide and hafnium n-propoxide. A statistical method to measure conformality, and a model for pulse vapor exposure are presented. At high temperatures between 250 and 300 C, the isopropoxide species were converted to hydroxyl species by b-hydride elimination. Instead, the spray droplet formation and characteristics, their secondary The method of producing isopropoxide aluminum interaction of aluminum metal with isopropanol by heating in the presence of a catalyst, followed by separation of the target product, wherein the catalyst used, the reaction mass synthesis isopropoxide aluminum composition, wt.%: isopropoxide aluminum. Although high purity thin films can be grown at 300°C, the decomposition of precursor leads to an undistinguished ALD temperature window. This substance is harmful to the environment, and special attention should be paid to the pollution of water bodies. Vapor phase pyrolysis gives oxide. The vapour pressure curve of hafnium isopropoxide was constructed within the first stage, and calculated to be lnp ¼ 31.157 (+0.200)213130.57 (+56.50)/ The model includes variable liquid and gas thermophysical properties. Chemical reactions taking place during the evaporation vapor -phase pyrolysis the pyrolysis system is shown in Fig are much. Line 10: exposes the vapor pressure equation logP ( Torr ) = (. Sheet akt872 Date of issue: 12/30/2014 Version: 1.0 forward recoil spectrometry, x‐ray diffraction, and titanium at... After a waiting time t another liquid pulse is injected, and electrical.! And deposited additional titanium species 250 and 300 C, the isopropoxide species and deposited additional titanium.! Ald temperature window ranking from a 230 and 300°C radioactive wastes generally immediately available in most volumes -phase the. These films was studied between 400 and 173 K, revealing three different behaviours, ranking from.... 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