Melting high pressure

V. V. Brazhkin, S. V. Popova, and R. N. Voloshin, High-pressure transformations in simple melts, High Pressure Res. 15, 267-305 (1997). 

Interest in AIN, GaN, InN and their alloys for device applications as blue light-emitting diodes and blue lasers has recently opened up new areas of high-pressure synthesis. Near atmospheric pressure, GaN and InN are nnstable with respect to decomposition to the elements far below the temperatures where they might melt. Thus, large boules of these materials typically used to make semiconductor devices caimot be grown from the... 

One of the principal problems in early commercialization of acryUc fibers was the lack of a suitable spinning method. The polymer caimot be melt spun, except possibly at high pressure in the presence of water. Solution spinning was the only feasible commercial route. However, hydrogen bonding between... 

Tra.nsitions and Relaxations. Only one first-order transition is observed, the melting poiat. Increasing the pressure raises mp. At low pressure, the rate of iacrease ia the melting poiat is ca 1.74°C/MPa (0.012°C/psi) at high pressures this rate decreases to ca 0.725°C/MPa (0.005°C/psi). Melting iacreases the volume by 8%. la the preseace of the HFP comonomer, crystal distortioa occurs with an iacrease ia iatramolecular distance that, ia turn, reduces the melting poiat (54). 

In the high pressure process, a resia melt containing a chemical blowiag ageat is iajected iato an expandable mold under high pressure. Foaming begias as the mold cavity expands. This process produces stmctural foam products with very smooth surfaces siace the skin is formed before expansion takes place. 

Extmsion processes have been used to produce high and low density flexible cellular poly(vinyl chloride). A decomposable blowiag ageat is usually bleaded with the compouad prior to extmsioa. The compouaded resia is thea fed to an extmder where it is melted under pressure and forced out of an orifice iato the atmosphere. After extmsion iato the desired shape, the cellular material is cooled to stabili2e it and is removed by a belt. 

Even at the lowest temperatures, a substantial pressure is required to soHdify helium, and then the soHd formed is one of the softest, most compressible known. The fluid—soHd phase diagrams for both helium-3 and helium-4 are shown in Eigure 1 (53). Both isotopes have three allotropic soHd forms an fee stmeture at high pressures, an hep stmeture at medium and low pressures, and a bcc stmeture over a narrow, low pressure range for helium-4 and over a somewhat larger range for helium-3. The melting pressure of helium-4 has been measured up to 24°C, where it is 11.5 GPa (115 kbar) (54). 

Styrenic block copolymers (SBCs) are also widely used in HMA and PSA appHcations. Most hot melt appHed pressure sensitive adhesives are based on triblock copolymers consisting of SIS or SBS combinations (S = styrene, I = isoprene B = butadiene). Pressure sensitive adhesives typically employ low styrene, high molecular weight SIS polymers while hot melt adhesives usually use higher styrene, lower molecular weight SBCs. Resins compatible with the mid-block of an SBC improves tack properties those compatible with the end blocks control melt viscosity and temperature performance. 

Many polymers, including polyethylene, polypropylene, and nylons, do not dissolve in suitable casting solvents. In the laboratory, membranes can be made from such polymers by melt pressing, in which the polymer is sandwiched at high pressure between two heated plates. A pressure of 13.8—34.5 MPa (2000—5000 psi) is appHed for 0.5 to 5 minutes, at a plate temperature just above the melting point of the polymer. Melt forming is commonly used to make dense films for packaging appHcations, either by extmsion as a sheet from a die or as blown film. 

The second important component is the cooling agent or reactor coolant which extracts the heat of fission for some usefiil purpose and prevents melting of the reactor materials. The most common coolant is ordinary water at high temperature and high pressure to limit the extent of boiling. Other coolants that have been used are Hquid sodium, sodium—potassium alloy, helium, air, and carbon dioxide (qv). Surface cooling by air is limited to unreflected test reactors or experimental reactors operated at very low power. 

Cyclohexanedimethanol (47) starts from dimethyl terephthalate. The aromatic ring is hydrogenated in methanol to dimethyl cyclohexane-l,4-dicarboxylate (hexahydro-DMT) and the ester groups are further reduced under high pressure to the bis primary alcohol, usually as a 68/32 mixture of trans and cis forms. The mixed diol is a sticky low melting soHd, mp 45—50°C. It is of interest that waste PET polymer maybe direcdy hydrogenated in methanol to cyclohexanedimethanol (48). 

Static Pressure Synthesis. Diamond can form direcdy from graphite at pressures of about 13 GPa (130 kbar) and higher at temperatures of about 3300—4300 K (7). No catalyst is needed. The transformation is carried out in a static high pressure apparatus in which the sample is heated by the discharge current from a capacitor. Diamond forms in a few milliseconds and is recovered in the form of polycrystalline lumps. From this work, and studies of graphite vaporization/melting, the triple point of diamond, graphite, and molten carbon is estimated to He at 13 GPa and 5000 K (Fig. 1)... 

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