Improved heat and solvent resistance of a pressure‐sensitive adhesive thermally processable by isocyanate dimer dissociation

Methods that do not involve use of an organic solvent are being considered for manufacturing environmental‐friendly pressure‐sensitive adhesive tapes. Among these methods, the hot‐melt method exhibits high productivity but is somewhat limited in terms of performance. Hot‐melt‐fabricated pressure‐sensitive adhesives require heating fluidization and cooling solidification, and it is extremely difficult to improve their heat resistance. We examine thermally processable pressure‐sensitive adhesives with a completely new structure, fabricated based on the thermal dissociation of the isocyanate dimer. This enables thermal processing of materials softened by thermal dissociation. Fabrication of crosslinkable pressure‐sensitive adhesive becomes possible through a reaction of isocyanate caused by dissociation of its dimer. It is found that improving thermal and solvent resistances, which are disadvantages associated with conventional hot‐melt pressure‐sensitive adhesives, is potentially possible with the pressure‐sensitive adhesive reported here. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41444.     

TRANSPORT PROPERTIES OF CELLULAR FOOD MATERIALS UNDERGOING FREEZE-DRYING

The samples of sliced and mashed apples were freeze-dried by controlling their surface temperatures over the usual pressure range of commercial operations. The surface of sliced samples could not be maintained at above 10°C in order to prevent the frozen layer from melting, while that of mashed samples was allowed to heat up to 70°C.

Thermal conductivities and permeabilities were determined by applying the uniformly-retreating-ice front model to the dried layer of the samples undergoing freeze-drying. The values of permeability for the mashed samples were found to depend on the ice-crystallization time during freezing. The results indicated that the drying rate of sliced samples was limited by the transfer rate of water vapor flowing through the dried layer. A cellular structural model is proposed for predicting the permeability of the dried layer, based on the resistance of the cell membrane to molecular transfer of water vapor.     

New polymer syntheses: 59. Homo-and copolyesters of 4-(4′-hydrophenoxy)benzoic acid

The homopolyester of 4-(4′-hydroxyphenoxy)benzoic acid (poly(4-HPBA)), was prepared under two different reaction conditions and compared with a sample provided by another research group. Depending on the synthetic route, different melting points, d.s.c. traces and crystal lattices were found. However, after repeated heating and cooling, one thermodynamically stable modification with a melting point of 370–375°C can be obtained. Copolyesters of 4-hydroxybenzoic acid and 4-(4′-hydroxyphenoxy)benzoic acid were prepared with various molar ratios either in the melt (condensation in bulk) or in solution. These copolyesters were characterized by elemental analyses, ¹H n.m.r. spectroscopy, d.s.c. measurements, wide-angle X-ray scattering measurements at various temperatures, and optical microscopy. Whereas copolyesters prepared in solution do not melt below 500°C, those prepared by polycondensation in bulk show melting points down to approximately 260°C and form a nematic melt.     

MELTING OF ICE AROUND A HORIZONTAL ISOTHERMAL CYLINDRICAL HEAT SOURCE

Processes during melting from a horizontal cylindrical heat source of uniform surface temperature embedded in ice have been studied experimentally. The volume of the melt and its shape were photographed at different times for various constant temperatures of the heat source. At early times and under all conditions, the melt occupied a cylindrical annulus. At later times free convective motion caused pear-shaped melt contours which pointed downward when the temperatures of the heat source were below 7°C and upward when the temperatures were above 8°C. Instabilities in cellular natural convection motion resulted in waviness of the interface. The location and magnitude of these ripples were found to depend on the temperature of the heat source and the melt layer thickness. Shadowgraph techniques were used to determine local heat transfer coefficients at the heat source surface.     

多熔点相变材料堆积蓄热床蓄热性能分析

对采用多种不同熔点相变材料（PCM）构成的堆积蓄热床进行了数值分析。热水作为换热流体（HTF）自上而下流经蓄热床,熔化相变材料、蓄积相变潜热。石蜡作为相变材料被注射入聚碳酸酯球壳内形成相变胶囊,根据熔点高低依次排放在蓄热床的不同位置,熔点越高距离热水进口越近。假定流场稳定,采用一维Schumann模型计算HTF温度,相变模拟采用显热容法。分别对两种排列方式下采用2种、3种以及4种相变材料的蓄热床的蓄热过程进行了基于热力学第一及第二定律的性能分析,并将结果与单相变材料蓄热床进行比较。基于热力学第一定律分析结果表明,采用多种相变材料构成的蓄热堆积床蓄热速度更快,能量效率更高。基于热力学第二定律分析表明,平均熔点更高的蓄热床能够储存更高的火用。结果表明采用多熔点相变材料构成的堆积蓄热床能够显著地缩短蓄热时间,改进蓄热性能。     

Determination of critical heat transfer for the prediction of materials damages during a flame engulfment test

The personal protective equipment of workers exposed to heat can consist of materials with a relatively low melting point of approximately 250°C (membranes, zippers, and underwear). In particular, users of heat protective clothing (such as volunteer firefighters or industrial workers) are often consider using functional sports underwear for an optimized sweat transport and lower heat stress. However, in an emergency situation (flame engulfment), this kind of clothing can be potentially dangerous because of its low melting temperature. In this study, we investigated the critical heat transfer needed to melt synthetic underwear worn under heat protective clothing and developed a model to predict possible damage to material layers exposed to a flame engulfment condition. The fire protection properties of four clothing systems with varying layer structures were assessed. These combinations were tested on an instrumented manikin according to ISO 13506 (flame engulfment test). The thickness and thermal resistance of the individual garments were measured in order to examine the influence of each parameter on the performance of the complete clothing combination. The measurements showed that synthetic polyester underwear worn underneath heat protective clothing can withstand a 4s flame engulfment exposure without damage when the outer layer has an adequate thermal resistance. By using a simple heat transfer model, we could define a ‘critical thermal resistance’ as the thermal resistance of the outer layer required to prevent the melting of the underwear material. Copyright © 2016 John Wiley & Sons, Ltd.     

Synthesis and characterization of gadolinium phosphate neutron absorber

Hydrated gadolinium phosphate (GdPO₄·1H₂O) was synthesized by reacting high purity dissolved salts (gadolinium nitrates or chlorides) with phosphoric acid. The hydrated powders were shown to be extremely insoluble in water with a K_sp measured to be between 2.07 E-14 and 4.76 E-13. Calcination to between 800 and 1000 °C resulted in the formation of GdPO₄ in a monazite (monoclinic) crystal structure. This was correlated with the first exothermic differential thermal analysis (DTA) peak (864.9–883.4 °C). The DTA also showed small peaks in the 1200–1250 °C range, that could be associated with a change from the monazite (monoclinic) crystal structure to the xenotime (tetragonal) crystal structure. However, calcination of a sample to 1400 °C, followed by relatively rapid cooling and XRD, showed the structure was still monazite (monoclinic). DTA results showed a melting point at 1899–1920 °C (endothermic peak). It was therefore concluded that the melting point probably was the melting of the monazite (monoclinic) phase, but may have been xenotime if a phase change at 1200–1250 °C was reversible and very rapid. The higher part of the melting range was achieved with material derived using the slightly higher purity nitrate salt. The results show that GdPO₄ is an excellent candidate for a chemically stable, water-insoluble neutron absorber for inclusion in spent nuclear fuel canisters.     

Das Scaling‐Down‐Problem bei der Zweistoff‐Gaszerstäubung von Metallschmelzen

The production capacities of plants for metal pulverisation are frequently rated according to the minimum throughput of melt flowing from the distributor crucible to pulverisation. Especially in the case of high‐melting point metals and their alloys deficiencies occur in the thermal balance of the crucible in the exit section as a result of gas expansion at the pulverisation gas jets, which act as heat sinks. Minimum throughputs and associated limiting values of the convective heat transfer of the melt are stipulated in order to prevent "freezing" (solidification of the melt) in the crucible. The pertinent situation is illustrated for copper and steel melts and technical possibilities for compensating for heat deficiencies by inductive heating of the distributor exit are presented. In addition, the demand for minimum throughputs can be abandoned, and there result possibilities of scaling‐down and energy conservation as well as improvement of powder discharge.     

URTHER DEVELOPMENT OF A COMPUTER PROGRAM SIMULATING HEAT PIPE FUNCTIONING IN CONDEBELT PAPER DRYING

A previously developed computer program for depicting the heat and mass transfer behavior of heat pipe conduits, slightly open to a large ambient at their far ends, inside moist paper webs is developed further. The addition consists of accounting for the thermal dynamics of a hot metal slab from which the latent heat of evaporation corresponding to vapor generation in the hot end of the heat pipe is drawn. Values are used for the input parameters representing as closely as possible an approximately 40 % dry (by total weight) printing paper sheet being suddenly pressed against a hot steel or iron slab at l50°C or 200°C. These are conditions that could occur in Condebelt drying. Temperature distributions in the metal and inside the web, as well as the pressure distribution inside the web, are determined as functions of the distance from the hot surface and time. Important parameters are the initial metal and web temperatures, the interface Biot number, the structural geometry of the web, and the metal Fourier number. It is shown that there is a S to 25°C metal surface temperature drop in the first 100 μs after contact with the web. This can be significant in reducing possible web surface damage.     

Thermal characterization of polylactides

Three important thermal characteristics of polylactides have been measured and discussed. These are glass transition temperature, melting temperature, and degradation behaviour. The glass transition temperatures at infinite molecular weight for - and -optical isomers were 58 and 57°C, respectively. Melting temperature for the crystalline -isomer was 184°C at infinite molecular weight. Number-average molecular weight, melt viscosity, differential scanning calorimetry, infra-red analysis and thermogravimetric analysis were used to study the degradation behaviour under different conditions. Polylactides were found to be highly sensitive to heat, especially at temperatures higher than 190°C. Most of the degradative reactions were thought to involve the highly concentrated ester bond on the main chain. These reactions included thermohydrolysis, depolymerization and cyclic oligomerization, intermolecular and intramolecular transesterifications. Low molecular weight compounds associated with the polymer seemed to play an important role in lowering the molecular weight at high temperatures, as well as the hydroxyl end group of the main chain. The compounds include water, monomers, oligomers, and polymerization catalysts. Removal of the non-polymeric contents and blocking the hydroxyl end-group enhanced the thermal stability of the polymers. The increased amount of the polymerization catalyst in the end product contributed to the degradative reactions.     

Hot corrosion and protection of Ti2AlC against Na2SO4 salt in air

The hot corrosion behavior of Na₂SO₄-coated Ti₂AlC was investigated by means of thermogravimetric analysis, X-ray diffraction, and scanning electron microscopy/energy dispersive spectroscopy. This carbide displays good hot corrosion resistance below the melting point of Na₂SO₄ while the corrosion attacks become virulent when the salt is molten. A protectively continuous Al₂O₃ layer forms and imparts good corrosion resistance, and consequently, the corrosion kinetics is generally parabolic at 850 °C. However, porous oxide scales fail to protect the Ti₂AlC substrate at 900 and 1000 °C. The segregation of sulfur at the corrosion scale/substrate interface accelerates the corrosion of Ti₂AlC. Furthermore, a convenient and efficient pre-oxidation method is proposed to improve the high-temperature hot corrosion resistance of Ti₂AlC. An Al₂O₃ scale formed during pre-oxidation treatment can remarkably restrain the infiltration of the molten salt into the substrate and prevent the substrate from severe corrosion attacks.     

Enhancement of Energy Efficiency of a Chemical Heat Pump-Assisted Convective Dryer

In earlier studies we have shown by simulation and experimental studies that the proposed chemical heat pump (CHP) unit can be used to recover waste heat from dryers and reuse it by storing and releasing heat with upgrading the temperature or by dehumidification. However, the final thermal energy production efficiency of the CHP for drying was found to be low. In this paper we present experimental results to demonstrate the potential for improved heat-recovery/storage and the heat-release/production of hot dry air for batch drying applications using the heat enhancement mode of the CHP. A new laboratory scale experimental CHP dryer system was built utilizing the calcium oxide/calcium hydroxide hydration/dehydration reversible reaction. The aim of this study is to improve the efficiencies of the heat recovery from heat source in the heat-storage step and the hot dry air production in the heat-release step of the CHP for heating up the air to around 100°C. The results of this experimental study utilizing a new reactor design showed that the shallow reactor/heat exchanger could accomplish 94% chemical heat storage and produce 100°C air at better than 75% efficiency for the reaction heat by controlling the preheating condition. The reaction conversion reached 90% in these experiments. The proposed CHP-assisted convective dryer system is found to be energy-efficient over a wide temperature range of industrial interest.     

INFLUENCE OF DESIGN AND OPERATING CONDITIONS ON THE SYSTEM PERFORMANCE OF A TWO-STAGE ADSORPTION CHILLER

This article aims at clarifying the possible design and operating conditions for silica gel-water adsorption refrigeration cycles driven by near-ambient temperature waste heat sources (between 45 and 75°C) with relatively small regenerating temperature lifts (15 to 45 K). A two-stage silica gel-water advanced adsorption chiller is introduced and a simulation model of the chiller was developed to analyze the influence of operating and design conditions on the system performance (coefficient of performance, COP, and cooling capacity). It was hypothesized that the proposed chiller can be driven by low temperature waste heat at 55°C to produce effective cooling. Simulation results show that the operating conditions such as cycle time and hot and cooling water inlet temperature have an influential effect on cooling capacity and COP. COP is proportional to cycle time and heat transfer coefficient as well as inversely proportional to the cooling water inlet temperature, while there are optimum values of hot water temperature and silica gel weight for maximum COP. Cooling capacity mainly improves with the addition of silica gel weight and decreases as cooling water temperature increases. Simulation results also revealed that the system performance can be improved significantly by setting the design and operating conditions optimally.     

Shrinkage in extruded moisture crosslinked silane‐grafted polyethylene wire insulation

Shrinkage studies were conducted on silane‐grafted moisture crosslinkable linear low‐density polyethylene (LLDPE) insulation stripped from extrusion‐coated copper conductors. The insulation, which possesses orientation imparted during melt processing, showed remarkable levels of shrinkage when heated above the melting point of the polymer, though the shrinkage can be greatly reduced by moisture crosslinking the insulation below the melting point of the LLDPE. Shrinkage along the direction of orientation was accompanied by swelling in the other dimensions. Differential scanning calorimetry (DSC) revealed several trends, including a decrease in both melting point and degree of crystallinity with increasing crosslinking. In the first heat after annealing, crosslinked samples exhibited a shoulder in the DSC endotherm several degrees below the normal melting point of the LLDPE. In agreement with prior studies in silane‐grafted HDPE, relaxation of orientation by annealing appeared to result in an increase in the enthalpy of melting. The degree of shrinkage was also found to be dependent on the insulation thickness, which is attributed to faster cooling in thinner insulation immediately following extrusion coating. The results highlight the extensive built in stresses that can be frozen into polymer layers in fabricated articles due to melt orientation. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Lower purity dimer acid based polyamides used as hot melt adhesives: synthesis and properties

Hot melt polyamides exhibit high adhesive strength. The polyamides synthesized from dimer fatty acids and diamines can present low crystallinity and a broad range of melting temperatures. In this work, polyamides with different compositions of dimer fatty acids, piperazine, ethylenediamine, sebacic acid and stearic acid and different content of secondary diamine (piperazine) and primary diamine (ethylenediamine) were synthesized. Polyamides with higher purity of dimer acids showed greater molecular weight, adhesion performance and a better mechanical resistance evaluated in stress/strain test. Softening point increased with increase in monomers content. By differential scanning calorimetry analysis, it was observed that polyamides with low percentage of monomer content show only one narrow melting peak in 100 °C. The increase in the acids monomer content leads to a larger temperature range of melting peak. The use of dimer fatty acid with a low content of monomers (up to 6%) in the polyamides synthesis promotes the formation of hot melt adhesives with good adhesion performances. The lowest monomer content leads to an increase in molecular weight, viscosity and mechanical properties of polyamide. Increase in the content of primary amines in polyamides increases crystallinity, viscosity and mechanical properties due to the higher number of hydrogen bonds formed by amide groups.     

Heat transfer to walls in a high temperature fluidized bed of group II particles

High temperature heat transfer data in the particle diameter range 0.73 – 1.41 mm and temperature range 490 – 918 °C are presented. The original measurement method is based on an overall thermal balance over a 0.40 m² heat exchange surface. Experimental data are analyzed using results from the literature and a ‘particle-based’ heat transfer model. It is found that gas convective heat transfer is significant for the largest particles (1.41 mm) but it may be neglected for 1.18 mm particles at temperatures above 700 °C. An analysis of this result on the basis of Saxena and Ganzha's powder classification scheme is proposed. A general correlation based on Archimedes and Planck numbers is presented. It takes into account the interaction between radiation and conduction at high temperatures, utilizing the experimental results for beds of corundum particles (0.28, 0.425, 0.6, 0.73, 1, and 1.18 mm) in the temperature range 500 – 900 °C.     

Diffusion and conduction in melts

The difference between the conduction and diffusive transport modes in melts is discussed in terms of the movement of the basic entities of which the melt is composed. Data for conduction and diffusion in TlCl are used to illustrate a suggested method of separating our the contributions of ions, ionic agglomerates and molecules to the conductive and diffusive transport modes. Indications are that a Grotthus mechanism is the predominant conductive vehicle just above the melting point of the salt, while ionic agglomerates are the predominant diffusive entity in the same region. At about 770°C the molecular character of the melt commences to become significant; thereafter it increases in importance up to the critical point, where it is predominant.     

AN EXPERIMENTAL STUDY OF MELTING VERTICAL ICE CYLINDERS IN COLD WATER

Short vertical ice cylinders were melted in quiescent ambient cold fresh water to visualize the melting and the resulting convective motions. Melting rates and heat transfer parameters were also determined. The cylinder penetrated the water surface, to model the melting of floating surface ice. Melting experiments over the ambient medium temperature range, t ∞, from 2 to 7°C covered the whole gamut of differing and complicated effects found to be associated with the occurance of a density extremum. At t ∞ = 2°C, simple general upflow is found, at t ∞ = 7°C simple downflow. Between these two limits, three different and much more complicated regimes arose. Buoyancy force reversal arises first, with increasing t ∞, at about 4°C. Then local flow reversal follows, in the range to about 5.3°C. Finally a convective inversion, that is, an average flow reversal, occurs. A tremendous variation of flow pattern occurs over a range of only a few degrees. Melting rates become very low in the region of inversion. This was also found in previous measurements with the simpler flows which occur adjacent to thin and completely submerged vertical ice slabs. However, many flow and transport effects were quite different, with a flat bottom surface and with the ice-water-air interface. Three flows of different configurations interact. It appears that the realistic modelling of the melting of multidimensional pieces of surface ice will require a composite of the different characteristics of these multiple regions.     

SIS技术参数对其热熔压敏胶性能的影响

研究了SIS的技术参数对SIS热熔压敏胶性能的影响。试验表明,星型结构的SIS热熔压敏胶熔融黏度较低,持粘性、剥离强度较大,软化点较高;嵌段比增大,SIS热熔压敏胶的初粘性降低、持粘性增大、熔融黏度减小、软化点升高;分子质量增大,SIS热熔压敏胶的初粘性降低、持粘性增大、熔融黏度增大、软化点升高;2嵌段SI含量增加,SIS热熔压敏胶初粘性增大、持粘性降低,180°剥离强度先增大后减小,且压敏胶的熔融黏度减小、软化点降低、分切性能变好。     

Vitreous fillers in intumescent coatings

The introduction of vitreous fillers in some intumescent coatings compositions proved to be useful both in improvement of thermal insulation and durability of char under fire and in smoke emission characteristics. In this paper a comprehensive experimental study is presented showing results for solvent-borne, 2K epoxy and water-borne intumescent paints.

Blends of vitreous fillers with different melting temperatures, between 350°C and 850°C, have been tested together with refractory fillers (with melting temperatures between 1100°C and 1350°C). Lead free vitreous fillers with very low melting temperatures (from 350°C to 550°C) and with low water solubility were developed. Different types of paints have been prepared by adding different amounts of vitreous fillers. These compositions were then fire tested after application on steel plates. The effect of vitreous fillers on fire performance and stabilization of char (by means of encapsulation, with or without self-extinguishing additives) has been studied. The fillers’ effect on smoke emission under fire was also examined both in terms of optical density and toxicity index.

A special attention was focused on water-borne intumescent paints modified with vitreous fillers of different solubility and melting temperature. Residual solubility of the vitreous fillers, which appeared as a very important parameter for paint stability, has been assessed. Vitreous fillers releasing alkaline ions in such an amount to give a conductivity higher than 500 μS cm, make the intumescent paint composition unstable.