Thermodynamics of crystalline linear high polymers. V - Extended-chain copolymers of polyethylene
Melting point, melting range, and crystallinity of extended-chain copolymer crystals
COPOLYMER↗
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Effects of Melt Processing on Evolution of Structure in PEEK
We report on the effects of melt processing temperature on structure formation in Poly(ether-ether-ketone), PEEK. Real time Small Angle X-ray Scattering, SAXS, and thermal analysis are used to follow the melting behavior after various stages of processing. Assignment of peaks to structural entities within the material, the relative perfection of the crystals, and the possibility of their reorganization, are all influenced by the melt processing history. With the advent of high intensity synchrotron sources of X-radiation, polymer scientists gain a research tool which, when used along with thermal analysis, provides additional structural information about the crystals during growth and subsequent melting. PEEK is an engineering thermoplastic polymer with a very high glass transition temperature (145 C) and crystal melting point (337 C). PEEK has been the subject of recent studies by X-ray scattering in which melt and cold crystallization were followed in real-time. X-ray scattering and thermal studies have been used to address the formation of dual endothermic response which has been variously ascribed to lamellar insertion, dual crystal populations, or melting followed by re-crystallization. Another important issue is whether all of the amorphous phase is located in interlamellar regions, or alternatively whether some is located in "pockets" away from the crystalline lamellar stacks. The interpretation of scattering from lamellar stacks varies depending upon whether such amorphous pockets are formed. Some groups believe all of the amorphous phase is interlamellar. This leads to selection of a smaller thickness for the crystals. Other groups suggest that most amorphous phase is not interlamellar, and this leads to the suggestion that the crystal thickness is larger than the amorphous layer within the stacks. To investigate these ideas, we used SAXS and Differential Scanning Calorimetry to compare results of single and dual stage melt crystallization of PEEK using a treatment scheme involving annealing/crystallization at T(sub a1) followed by annealing at T(sub a2) where either T(sub a1) < T(sub a2) or T(sub a1) > T(sub a2). We proposed a model to explain multiple melting endotherms in PPS, treated according to one or two-stage melt or cold crystallization. Key features of this model are that multiple endotherms: (1) are due to reorganization/recrystallization after cold crystallization; and, (2) are dominated by crystal morphology after melt crystallization at high T. In other words, multiple distinct crystal populations are formed by the latter treatment, leading to observation of multiple melting. PEEK 45OG pellets (ICI Americas) were the starting material for this study. Films were compression molded at 400 C, then quenched to ice water. Samples were heated to 375 C in a Mettler FP80 hot stage and held for three min. to erase crystal seeds before cooling them to T(sub a1) = 280 C . Samples were held at T(sub a2) for a period of time, then immediately heated to 360 C. In the second treatment samples were held at T(sub a1) = 31 C for different crystallization times t(sub c) then cooled to 295 C and held 15 min. In situ (SAXS) experiments were performed at the Brookhaven National Synchrotron Light Source with the sample located inside the Mettler hot stage. The system was equipped with a two-dimensional position sensitive detector. The sample to detector distance was 172.7 cm and the X-ray wavelength was 1.54 Angstroms. SAXS data were taken continuously during the isothermal periods and during the heating to 360 C at 5 C/min. Each SAXS scan was collected for 30 sec. Since the samples were isotropic, circular integration was used to increase the signal to noise ratio. After dual stage melt crystallization with T(sub a1) < T(sub a2) the lower melting endotherm arises from holding at T(sub a1). During cooling a broad distribution of crystals forms, and the low-melting tail is perfected during T(sub al). Heating to T(sub a2) melts these imperfect crystals and allows others with greater average long spacing to form in their place. After dual stage crystallization with T(sub a1) > T(sub a2), the amount of space remaining for additional growth at T(sub a2) depends upon the holding time at T(sub a1). The long period of crystals formed at T(sub a2) is smaller than that formed at T(sub a1) due to growth in a now-restricted geometry. Perfection of crystals is seen as an increase of the intensity of the population scattering at higher s, while the intensity of the population scattering at lower s stays constant. During heating from below to above the minor endotherm, we see rapid decrease of the intensity of the X-ray scattering corresponding to the population of crystals scattering in the shoulder. Another important observation is that after the sample is annealed at 295 C, the shoulder intensity is restored once again. The population scattering at higher s remains longer before it disappears in the sample treated to the second stage of melt crystallization, compared to the sample crystallized with a single stage. This could be interpreted as an effect of continued perfection of the less perfect population, which is also reflected in the increased melting temperature of the smaller endotherm as the holding time at 295 C increases. In the corresponding DSC scans we see a shift in the area and the peak temperature of the lower melting endotherm with an increase of the annealing time.
Georgiev, Georgi↗
Evaluation of Graphite Fiber/Polyimide PMCs from Hot Melt vs Solution Prepreg
Carbon fiber reinforced high temperature polymer matrix composites (PMC) have been extensively investigated as potential weight reduction replacements of various metallic components in next generation high performance propulsion rocket engines. The initial phase involves development of comprehensive composite material-process-structure-design-property-in-service performance correlations and database, especially for a high stiffness facesheet of various sandwich structures. Overview of the program plan, technical approaches and current multi-team efforts will be presented. During composite fabrication, it was found that the two large volume commercial prepregging methods (hot-melt vs. solution) resulted in considerably different composite cure behavior. Details of the process-induced physical and chemical modifications in the prepregs, their effects on composite processing, and systematic cure cycle optimization studies will be discussed. The combined effects of prepregging method and cure cycle modification on composite properties and isothermal aging performance were also evaluated.
Shin, E. Eugene↗
Evaluation of Graphite Fiber/Polyimide PMCs from Hot Melt versus Solution Prepreg
Carbon fiber reinforced high temperature polymer matrix composites (PMC) have been extensively investigated as potential weight reduction replacements of various metallic components in next generation high performance propulsion rocket engines. The initial phase involves development of comprehensive composite material-process-structure-design-property in-service performance correlations and database, especially for a high stiffness facesheet of various sandwich structures. Overview of the program plan, technical approaches and current multi-team efforts will be presented. During composite fabrication, it was found that the two large volume commercial prepregging methods (hot-melt vs. solution) resulted in considerably different composite cure behavior. Details of the process-induced physical and chemical modifications in the prepregs, their effects on composite processing, and systematic cure cycle optimization studies will be discussed. The combined effects of prepregging method and cure cycle modification on composite properties and isothermal aging performance were also evaluated.
Shin, Eugene E.↗
Superheating of extended-chain polymer crystals
Extended chain polymer crystals temporary superheating before final melting, discussing hexagonal selenium crystals data
Jaffe, M.↗
Hot forming graphite/polyimide structures
Hot forming process has been developed in which structural shapes and panels are fabricated directly from stabilized graphite/polyimide preforms. Process can be used with thermosetting polymers that have high-temperature melt phase just before final cure. This phase allows fibers to move without destroying matrix-to-fiber adhesion. One of key advantages of this process is that prestages preforms are very stable and do not require refrigerated storage.
Baucom, R. M.↗
A new brominated polymeric additive for flame retardant glass-filled polybutylene terephthalate
Attention is called to the undesirable effects (poor ultraviolet light stability and blooming) sometimes introduced by brominated flame retarders. A brominated polymeric additive (BPA) with little or none of these undesirable side effects is compared with decabromobiphenyl oxide (DBBPO). The additive bears the product name F-2300. It is found to be more easily dispersed than DBBPO. The F-2300 is as effective as the DBBPO in the oxygen index test. The improved efficiency of the F-2300 may be explained by its better dispersion in polybutylene terephthalate (PBT). Glass-filled PBT containing F-2300 is found to be more resistant to UV degradation than DBBPO-containing formulas. Formulations with F-2300 therefore have a longer useful outdoor life. F-2300 is a diglycidyl-type polymer containing 50 percent aromatically bound bromine. Its melting point is 112 C, and it is stable up to 372 C. It is pointed out that since its melts at a relatively low temperature, it can be introduced into the formulation as a large agglomerate and still be dispersed evenly throughout the polymer.
Nir, Z.↗
Levitation of superconducting composites
The inverse levitation of a high temperature superconductor polymer composite consisting of powdered quench melt growth Ba2YCu3O(7-delta) and cyanoacrylate is reported. Magnetic hysteresis loop measurements for the composite are compared to those measured for the bulk material prior to powdering. Differences in the flux pining capability between the two material forms are small but significant.
Chiang, C. K.↗
High-Temperature Shape Memory Polymers
physical conformation changes when exposed to an external stimulus, such as a change in temperature. Such materials have a permanent shape, but can be reshaped above a critical temperature and fixed into a temporary shape when cooled under stress to below the critical temperature. When reheated above the critical temperature (Tc, also sometimes called the triggering or switching temperature), the materials revert to the permanent shape. The current innovation involves a chemically treated (sulfonated, carboxylated, phosphonated, or other polar function group), high-temperature, semicrystalline thermoplastic poly(ether ether ketone) (Tg .140 C, Tm = 340 C) mix containing organometallic complexes (Zn++, Li+, or other metal, ammonium, or phosphonium salts), or high-temperature ionic liquids (e.g. hexafluorosilicate salt with 1-propyl-3- methyl imidazolium, Tm = 210 C) to form a network where dipolar or ionic interactions between the polymer and the low-molecular-weight or inorganic compound forms a complex that provides a physical crosslink. Hereafter, these compounds will be referred to as "additives". The polymer is semicrystalline, and the high-melt-point crystals provide a temporary crosslink that acts as a permanent crosslink just so long as the melting temperature is not exceeded. In this example case, the melting point is .340 C, and the shape memory critical temperature is between 150 and 250 C. PEEK is an engineering thermoplastic with a high Young fs modulus, nominally 3.6 GPa. An important aspect of the invention is the control of the PEEK functionalization (in this example, the sulfonation degree), and the thermal properties (i.e. melting point) of the additive, which determines the switching temperature. Because the compound is thermoplastic, it can be formed into the "permanent" shape by conventional plastics processing operations. In addition, the compound may be covalently cross - linked after forming the permanent shape by S-PEEK by applying ionizing radiation ( radiation, neutrons), or by chemical crosslinking to form a covalent permanent network. With respect to other shape memory polymers, this invention is novel in that it describes the use of a thermoplastic composition that can be thermally molded or solution-cast into complex "permanent" shapes, and then reheated or redissolved and recast from solution to prepare another shape. It is also unique in that the shape memory behavior is provided by a non-polymer additive.
Yoonessi, Mitra↗
Development of an impact- and solvent-resistant thermoplastic composite matrix, phase 4
Polyimides from BTDA with m-phenylenediamine and three aliphatic diamines were prepared in cresol and characterized. Characterization tests included compression strength and modulus, stressed solvent resistance, and melt-flow tests. Efforts to reduce the molecular weights of these polymers by either stoichiometric imbalance or phthalic anhydride end capping produced opacity in the polymer moldings when the stoichiometry was less than 99 percent. Use of 2,4-diaminotoluene in place of the m-phenylenediamine allowed clear polymer moldings to be obtained at all stoichiometries by end capping or stoichiometric imbalance. After melt-flow/molecular-weight studies, carbon fabric composites were prepared from three polyimide compositions containing BTDA, 2,4-diaminotoluene and two aliphatic diamines. Flexural strengths of two of the resins were in excess of 689 MPa (100 ksi) at both room temperature and 93 C. The polyimide from BTDA was selected for scale-up and neat resin characterization tests. The Tg of this polymer was 233 C.
Delano, C. B.↗
Morphological control of inter-penetrating polymer networks
Synthetic organic polymer chemistry has been successful in producing composition of matter with thermal oxidation stability and progressively higher glass transition temperatures. In part, this was done by increasing the steric-hindrance of moieties in the chain of a macromolecule. The resulting polymers are usually quite insoluble and produce molten polymers of very high viscosities. These types of polymers are not easily processed into graphite fiber prepregs by melt or solution impregnation methods. Hence, a technological need exists to produce new knowledge of how to produce polymer-fiber composites from this class of polymers. The concept of freeze drying amic-acid prepolymers with reactive thermoplastic was proposed as a research topic for the ASEE/NASA Summer Faculty Program of 1989 as a means of producing polymer-fiber composites. This process scheme has the thermodynamic attribute that the magnitude of phase separation due to differences in solubility of two organic constituents in solution will be greatly reduced by removing a solvent not by evaporation but by sublimation. Progress to date on evaluating this polymer processing concept is briefly outlined.
Hansen, Marion↗
Self-Healing Polymer Materials for Wire Insulation, Polyimides, Flat Surfaces, and Inflatable Structures
Materials based on low melt polyimide, polyurea, or polyurethane chemistry have been developed which exhibit self-healing properties. These high performance polymers can be utilized either by themselves or in combination with microcapsule technology to deliver self-healing properties to electrical wire insulation or in other high performance, thin wall technologies such as inflatable structures.
Jolley, Scott T.↗
Modifying Silicates for Better Dispersion in Nanocomposites
An improved chemical modification has been developed to enhance the dispersion of layered silicate particles in the formulation of a polymer/silicate nanocomposite material. The modification involves, among other things, the co-exchange of an alkyl ammonium ion and a monoprotonated diamine with interlayer cations of the silicate. The net overall effects of the improved chemical modification are to improve processability of the nanocomposite and maximize the benefits of dispersing the silicate particles into the polymer. Some background discussion is necessary to give meaning to a description of this development. Polymer/silicate nanocomposites are also denoted polymer/clay composites because the silicate particles in them are typically derived from clay particles. Particles of clay comprise layers of silicate platelets separated by gaps called "galleries." The platelet thickness is 1 nm. The length varies from 30 nm to 1 m, depending on the silicate. In order to fully realize the benefits of polymer/silicate nanocomposites, it is necessary to ensure that the platelets become dispersed in the polymer matrices. Proper dispersion can impart physical and chemical properties that make nanocomposites attractive for a variety of applications. In order to achieve nanometer-level dispersion of a layered silicate into a polymer matrix, it is typically necessary to modify the interlayer silicate surfaces by attaching organic functional groups. This modification can be achieved easily by ion exchange between the interlayer metal cations found naturally in the silicate and protonated organic cations - typically protonated amines. Long-chain alkyl ammonium ions are commonly chosen as the ion-exchange materials because they effectively lower the surface energies of the silicates and ease the incorporation of organic monomers or polymers into the silicate galleries. This completes the background discussion. In the present improved modification of the interlayer silicate surfaces, the co-ion exchange strengthens the polymer/silicate interface and ensures irreversible separation of the silicate layers. One way in which it does this is to essentially tether one amine of each diamine molecule to a silicate surface, leaving the second amine free for reaction with monomers during the synthesis of a polymer. In addition, the incorporation of alkyl ammonium ions into the galleries at low concentration helps to keep low the melt viscosity of the oligomer formed during synthesis of the polymer and associated processing - a consideration that is particularly important in the case of a highly cross-linked, thermosetting polymer. Because of the chemical bonding between the surface-modifying amines and the monomers, even when the alkyl ammonium ions become degraded at high processing temperature, the silicate layers do not aggregate and, hence, nanometer-level dispersion is maintained.
Campbell, Sandi↗
LARC-TPI 1500 series controlled molecular weight polyimide
LARC-TPI, a linear high temperature thermoplastic polyimide, was developed several years ago at NASA Langley Research Center. This material has been commercialized by Mitsui Toatsu Chemicals, Inc., Tokyo, Japan, as a varnish and powder. More recently, a melt-extruded film of a controlled molecular weight of this same polymer has been supplied to NASA Langley Research Center for evaluation. This new form, called LARC-TPI 1500 series, has been prepared in three molecular weights - high, medium and low flow polymers. The subject of this investigation deals with the rheological properties of the high and medium flow powders and the adhesive properties of the medium flow melt-extruded film. Rheological studies indicate that the high and medium flow forms of the polymer fall in the flow range of injection moldable materials. Adhesive data generated on the medium flow extruded film shows this form to be well suited for structural adhesive bonding. The data are as good or better than that for LARC-TPI data of previous studies.
Progar, Donald↗
Superheating of linear high-polymer polyethylene crystals.
Superheating of linear high polymer polyethylene crystals, evaluating time dependence of melting, differential thermal analysis and calorimeter techniques
SUPERHEATING↗
Biaxial extrusion of polyimide LARC-TPI and LARC-TPI blends
Biaxial films of polyimide LARC-TPI and LARC-TPI/liquid crystal polymer Xydar were extruded directly from the melt for the first time via an innovative extrusion technique. Three types of films, neat LARC-TPI, LARC-TPI/10 wt pct and 30 wt pct blends were processed as a part of this NASA-funded program. Processability was greatly enhanced by incorporating Xydar. The coefficient of thermal expansion was reduced from 34 ppm/C for the neat LARC-TPI to 15 ppm/C for the 10 wt pct Xydar blend and ultimately down to 1 to 3 ppm/C for the 30 wt pct blend films in the direction of extrusion. The maximum improvement in stiffness was realized by incorporating 10 wt pct Xydar (2.8 GPa up to 4.9 GPa). Tensile strength, however, experienced a drop as a result of Xydar addition, probably caused by inefficient mixing of the two phases.
Haghighat, R. Ross↗
Thermal characteristics of Lithium-ion batteries
Lithium-ion batteries have a very promising future for space applications. Currently they are being used on a few GEO satellites, and were used on the two recent Mars rovers Spirit and Opportunity. There are still problem that exist that need to be addressed before these batteries can fully take flight. One of the problems is that the cycle life of these batteries needs to be increased. battery. Research is being focused on the chemistry of the materials inside the battery. This includes the anode, cathode, and the cell electrolyte solution. These components can undergo unwanted chemical reactions inside the cell that deteriorate the materials of the battery. During discharge/ charge cycles there is heat dissipated in the cell, and the battery heats up and its temperature increases. An increase in temperature can speed up any unwanted reactions in the cell. Exothermic reactions cause the temperature to increase; therefore increasing the reaction rate will cause the increase of the temperature inside the cell to occur at a faster rate. If the temperature gets too high thermal runaway will occur, and the cell can explode. The material that separates the electrode from the electrolyte is a non-conducting polymer. At high temperatures the separator will melt and the battery will be destroyed. The separator also contains small pores that allow lithium ions to diffuse through during charge and discharge. High temperatures can cause these pores to close up, permanently damaging the cell. My job at NASA Glenn research center this summer will be to perform thermal characterization tests on an 18650 type lithium-ion battery. High temperatures cause the chemicals inside lithium ion batteries to spontaneously react with each other. My task is to conduct experiments to determine the temperature that the reaction takes place at, what components in the cell are reacting and the mechanism of the reaction. The experiments will be conducted using an accelerating rate calorimeter (ARC), which uses a heat-wait-search mode until an exothermic reaction is detected. After an exotherm is found the calorimeter maintains an adiabatic environment around a bomb which holds the test sample. The ARC will help identify important reactions and what temperature these exothermic reactions take place at. In order fully understand the battery, we are first going to take apart the battery and test the individual components of the battery using the ARC. I will first conduct a test on the electrolyte solution by itself. We will then test the electrolyte solution with the anode. We would like to see how the electrolyte solution reacts with the anode and its binder material. The next would be the same test using the cathode instead of the anode. By comparing the results of the electrolyte, electrolyte with anode, and the electrolyte with the cathode we can determine the reactions that are taking place due to each component. Using the heat capacity of the each individual sample and the temperature by which the sample increases, kinetic and thermo-dynamical information can then be found. A Gas chromatograph could be used to help with the task of identifying the by-products at the end of each test. One way of increasing the cycle life is to increase the stability of the materials inside the
Hauser, Dan↗
Characterization of SiC/SiC Composites Subjected to Sequential Tensile Creep and Dwell Fatigue in Air under Thermal Gradient Conditions
Uncoated SiC/SiC composites, with 2D and 3D fiber architectures, were investigated under steady state thermal gradient conditions with sequential tensile creep and dwell fatigue. Melt infiltration (MI), chemical vapor infiltration (CVI), polymer impregnation and pyrolysis (PIP), and hybrid (CVI and PIP) techniques were used to fabricate ceramic matrix composites (CMCs) with a 2D balanced fiber architecture. CMCs with 3D fiber weaves were also fabricated using MI and hybrid methods. Steady state through the thickness thermal gradients were generated for the tensile specimens using laser heating on the front (hot side) and forced air cooling on the back (cold side). Hot side and cold side temperatures of 2400 and 2200 °F, respectively, were used for testing CMCs fabricated with the MI process, whereas hot side and cold side temperatures of 2700 and 2400 °F, respectively, were used for CMCs fabricated with CVI, PIP, and hybrid processes. Each CMC specimen was initially tested under tensile creep at 69 MPa (10 ksi) for 80 hours, which was then followed by tensile dwell fatigue testing at a maximum stress of 69 MPa (10 ksi) for another 80 hours for a total of 160 hours. This type of sequential tensile creep followed by tensile dwell fatigue testing was performed to ascertain the integrity of uncoated CMCs under steady state thermal gradient conditions. Tensile creep and dwell fatigue test results, generated under steady state thermal gradient conditions on different types of SiC/SiC composites, are compared with corresponding creep behaviors observed under isothermal conditions to determine the influence of both monotonic creep (static fatigue) and dwell fatigue on accumulated strains and deformation behaviors of the CMCs.
Kalluri, Sreeramesh↗