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Effect of Molding and Machining on Neoflon CTFE M400H Polychlorotrifluoroethylene Rod Stock and Valve Seat Properties

Since 1997 numerous fires have been reported to the Food and Drug Administration involving cylinder valves installed on medical use oxygen cylinders sold and operated within the United States. All of the cylinder valves in question had polychlorotrifluoroethylene (PCTFE) valve seats. Subsequent failure analysis showed that the main seat was the primary source of ignition. A review of the incidents involving cylinder valve fires indicated three possible ignition mechanisms: contaminant promotion, flow friction, and resonance. However, gas purity analysis showed that uncombusted, residual oxygen was within specification. Infrared and energy dispersive spectroscopy further showed that no contaminants or organic compounds were present in the remaining, uncombusted valve seat material or on seat plug surfaces. Therefore, contaminant-promoted ignition did not appear to be responsible for the failures. Observations of extruded material along the outer edge of the coined or loaded seat area produced by cylinder overuse or poppet overload led to concerns that accelerated gas flow across a deformed seat surface could generate enough localized heating to ignite the polymeric seat. Low molecular weight or highly amorphous quick-quenched PCTFE grades might be expected to be especially prone to this type of deformation. Such a failure mechanism has been described as flow friction; however, the corresponding mechanistic parameters are poorly understood. Subsequent revelation of low-temperature dimensional instability by thermomechanical analysis (TMA) in a variety of PCTFE sheet and rod stock samples led to new concerns that PCTFE valve seats could undergo excessive expansion or contraction during service. During expansion, additional extrusion and accompanying flow friction could occur. During contraction, a gap between the seal and adjacent metal surfaces could form. Gas flowing past the gap could, in turn, lead to resonance heating and subsequent ignition as described in ASTM Guide for Evaluation Nonmetallic Materials for Oxygen Service (G 63). Attempts to uncover the origins of the observed dimensional instability were hindered by uncertainties about resin grade, process history, and post-process heat history introduced by machining, annealing, and sample preparation. An approach was therefore taken to monitor property changes before and after processing and machining using a single, well-characterized lot of Neoflon CTFE.1 M400H resin. A task group consisting of the current PCTFE resin supplier, two molders, and four valve seat manufacturers was formed, and phased testing on raw resin, intermediate rod stock, and finished valve seats initiated. The effect of processing and machining on the properties of PCTFE rod stock and oxygen gas cylinder valve seats was then determined. Testing focused on two types of extruded rod stock and one type of compression-molded rod stock. To accommodate valve seat manufacturer preferences for certain rod stock diameters, two representative diameters were used (4.8 mm (0.1875 in.) and 19.1 mm (0.75 in.)). To encompass a variety of possible sealing configurations, seven different valve seat types with unique geometries or machining histories were tested. The properties investigated were dimensional stability as determined by TMA, specific gravity, differential scanning calorimetry (DSC), compressive strength, zero strength time, and intrinsic viscosity. Findings are discussed in the context of polymer structure-process-property relationships whenever possible.

Waller, Jess M.↗

GRCop-84: A High-Temperature Copper Alloy for High-Heat-Flux Applications

GRCop-84 (Cu-8 at.% Cr-4 at.% Nb) is a new high-temperature copper-based alloy. It possesses excellent high-temperature strength, creep resistance and low-cycle fatigue up to 700 C (1292 F) along with low thermal expansion and good conductivity. GRCop-84 can be processed and joined by a variety of methods such as extrusion, rolling, bending, stamping, brazing, friction stir welding, and electron beam welding. Considerable mechanical property data has been generated for as-produced material and following simulated braze cycles. The data shows that the alloy is extremely stable during thermal exposures. This paper reviews the major GRCop-84 mechanical and thermophysical properties and compares them to literature values for a variety of other high-temperature copper-based alloys.

Ellis, David L.↗

Properties of Extruded PS-212 Type Self-Lubricating Materials

Research has been underway at the NASA Lewis Research Center since the 1960's to develop high temperature, self-lubricating materials. The bulk of the research has been done in-house by a team of researchers from the Materials Division. A series of self-lubricating solid material systems has been developed over the years. One of the most promising is the composite material system referred to as PS-212 or PM-212. This material is a powder metallurgy product composed of metal bonded chromium carbide and two solid lubricating materials known to be self-lubricating over a wide temperature range. NASA feels this material has a wide potential in industrial applications. Simplified processing of this material would enhance its commercial potential. Processing changes have the potential to reduce processing costs, but tribological and physical properties must not be adversely affected. Extrusion processing has been employed in this investigation as a consolidation process for PM-212/PS-212. It has been successful in that high density bars of EX-212 (extruded PM-212) can readily be fabricated. Friction and strength data indicate these properties have been maintained or improved over the P.M. version. A range of extrusion temperatures have been investigated and tensile, friction, wear, and microstructural data have been obtained. Results indicate extrusion temperatures are not critical from a densification standpoint, but other properties are temperature dependent.

Waters, W. J.↗

Friction Modifier Using Adherent Metallic Multilayered or Mixed Element Layer Conversion Coatings

A process for creating conversion coatings and spin, drawing, and extrusion finishes for surfaces, wherein the conversion coatings and spin, drawing, and extrusion finishes contain potassium, phosphorus, nitrogen, and one or more non-alkaline metals and/or one or more metalloids. The process comprises forming an aqueous solution of water, phosphoric acid or sulfuric acid, ammonium hydroxide, an alkali metal hydroxide, and one or more non-alkaline metals and/or one or more metalloids. The aqueous solution forms an anti-friction multilayer conversion and/or mixed element coating or a spin, drawing, and extrusion finish on a surface when applied to the surface, either directly without the use of applied external electromotive force, or as an additive in lubricating fluids.

Schramm, Harry F.↗

Friction modifier using adherent metallic multilayered or mixed element layer conversion coatings

A process for creating conversion coatings and spin, drawing, and extrusion finishes for surfaces, wherein the conversion coatings and spin, drawing, and extrusion finishes contain potassium, phosphorus, nitrogen, silicon, and one or more non-alkaline metals. The process comprises forming a first aqueous solution of silicate, potassium hydroxide, and ammonium hydroxide; forming a second aqueous solution of water, phosphoric acid, ammonium hydroxide, an alkali metal hydroxide, and one or more non-alkaline metals, and then combining the first solution with the second solution to form a final solution. This final solution forms an anti-friction multi-layer conversion coating or a spin, drawing, and extrusion finish on a surface when applied to the surface, either directly or as an additive in lubricating fluids.

Schramm, Harry F.↗

Preliminary investigation of inertia friction welding B2 aluminides

An attempt is made to achieve inertia friction-welding in FeAl and NiAl samples, taking into account their intermetallics' compositions, extrusion parameters, and microstructural data. The energy required for the weld is stored in a rotating flywheel mass attached to one of the two pieces to be joined; when enough energy is introduced, the flywheel is disconnected and an axial load is applied which forces the spinning piece against the stationary one, converting the energy into heat by means of friction. Due to the inherent brittleness of the aluminides, a step-load program was used in which an initial, low-pressure heat buildup increased the work pieces' ductility.

Whittenberger, J. Daniel↗

Tribological Properties Of Ceramics

Report reviews adhesion, friction, and micromechanical properties of ceramics - properties increasingly important as more ceramic materials used in bearings, seals, and gears in advanced engines and in cutting tools and extrusion dies. Report considers effects of contaminating surface films, temperature, and chemical interactions. Examines ceramics, in both monolithic and coating form, in contact with themselves, with other harder materials, and with metals.

Miyoshi, Kazuhisa↗

Dissimilar metals joint evaluation

Dissimilar metals tubular joints between 2219-T851 aluminum alloy and 304L stainless steel were fabricated and tested to evaluate bonding processes. Joints were fabricated by four processes: (1) inertia (friction) weldings, where the metals are spun and forced together to create the weld; (2) explosive welding, where the metals are impacted together at high velocity; (3) co-extrusion, where the metals are extruded in contact at high temperature to promote diffusion; and (4) swaging, where residual stresses in the metals after a stretching operation maintain forced contact in mutual shear areas. Fifteen joints of each type were prepared and evaluated in a 6.35 cm (2.50 in.) O.D. size, with 0.32 cm (0.13 in.) wall thickness, and 7.6 cm (3.0 in) total length. The joints were tested to evaluate their ability to withstand pressure cycle, thermal cycle, galvanic corrosion and burst tests. Leakage tests and other non-destructive test techniques were used to evaluate the behavior of the joints, and the microstructure of the bond areas was analyzed.

Wakefield, M. E.↗

Investigation of Friction Stir Welding and Laser Engineered Net Shaping of Metal Matrix Composite Materials

The improvement in weld quality by the friction stir welding (FSW) process invented by TWI of Cambridge, England, patented in 1991, has prompted investigation of this process for advanced structural materials including Al metal matrix composite (Al-MMC) materials. Such materials can have high specific stiffness and other potential beneficial properties for the extreme environments in space. Developments of discontinuous reinforced Al-MMCs have found potential space applications and the future for such applications is quite promising. The space industry has recognized advantages of the FSW process over conventional welding processes such as the absence of a melt zone, reduced distortion, elimination of the need for shielding gases, and ease of automation. The process has been well proven for aluminum alloys, and work is being carried out for ferrous materials, magnesium alloys and copper alloys. Development work in the FSW welding process for joining of Al-MMCs is relatively recent and some of this and related work can be found in referenced research publications. NASA engineers have undertaken to spear head this research development work for FSW process investigation of Al-MMCs. Some of the reported related work has pointed out the difficulty in fusion welding of particulate reinforced MMCs where liquid Al will react with SiC to precipitate aluminum carbide (Al4C3). Advantages of no such reaction and no need for joint preparation for the FSW process is anticipated in the welding of Al-MMCs. The FSW process has been best described as a combination of extrusion and forging of metals. This is carried out as the pin tool rotates and is slowly plunged into the bond line of the joint as the pin tool's shoulder is in intimate contact with the work piece. The material is friction-stirred into a quality weld.

Ravinder M. Diwan↗

Deconvoluting the Friction Stir Weld Process for Optimizing Welds

In the friction stir welding process, the rotating surfaces of the pin and shoulder contact the weld metal and force a rotational flow within the weld metal. Heat, generated by the metal deformation as well as frictional slippage with the contact surface, softens the metal and makes it easier to deform. As in any thermo-mechanical processing of metal, the flow conditions are critical to the quality of the weld. For example, extrusion of metal from under the shoulder of an excessively hot weld may relax local pressure and result in wormhole defects. The trace of the weld joint in the wake of the weld may vary geometrically depending upon the flow streamlines around the tool with some geometry more vulnerable to loss of strength from joint contamination than others. The material flow path around the tool cannot be seen in real time during the weld. By using analytical "tools" based upon the principles of mathematics and physics, a weld model can be created to compute features that can be observed. By comparing the computed observations with actual data, the weld model can be validated or adjusted to get better agreement. Inputs to the model to predict weld structures and properties include: hot working properties ofthe metal, pin tool geometry, travel rate, rotation and plunge force. Since metals record their prior hot working history, the hot working conditions imparted during FSW can be quantified by interpreting the final microstructure. Variations in texture and grain size result from variations in the strain accommodated at a given strain rate and temperature. Microstructural data from a variety of FSWs has been correlated with prior marker studies to contribute to our understanding of the FSW process. Once this stage is reached, the weld modeling process can save significant development costs by reducing costly trial-and-error approaches to obtaining quality welds.

Schneider, Judy↗

Friction Stir Weld Tooling Development for Application on the 2195 Al-Cu-Li Space Transportation System External Tank

Friction Stir Welding (FSW) is a new and innovative solid-state joining process which can be applied to difficult-to- weld aluminum alloys. However, the large forces involved with the process have posed a production tooling challenge. Lockheed Martin Michoud Space Systems has overcome many of these challenges on the Super Lightweight External Tank (ET) program. Utilizing Aluminum-Copper-Lithium alloy 2195 in the form of plate and extrusions, investigations of FSW process parameters have been completed. Major loading mechanisms are discussed in conjunction with deflection measurements. Since the ET program is a cryogenic application, a brief comparison of cryogenic material properties with room temperature material properties is offered for both FSW and fusion welds. Finally, a new approach to controlling the FSW process from a load perspective is introduced. Emphasis will be put on tooling development, as well as the impact of tooling design and philosophy on Friction Stir Weld success probability.

Loftus, Zachary↗

Mechanistic Models of Friction Stir Welding

Friction stir welding is a welding process developed at The Welding Institute (TWI) in England. The method uses very large strain plastic deformation of the material to join two pieces of metal together. The material is deformed using a tool which is forced between the two pieces which rotates causing a bond. Beyond this, very little is actually known although many people working in the field are willing to speculate on the detailed mechanisms involved. Some measurements made using sacrificial thermocouples at the weld joint indicate that the maximum temperature during the weld process is on the order of 370C - well below the melting temperature of the material. However, at this temperature, the material properties are highly temperature dependent, and the yield stress is approximately an order of magnitude less at this temperature than it is at room temperature. As expected, there are many interpretations of the physical mechanisms occurring during the weld process. Although there is very little published concerned with FSW, some of the anecdotal theories will be described. One describes the primary mechanism as frictional heating at the front of the tool caused by slip between the tool and the material. At elevated temperatures, the weld material becomes soft and deforms around the tool but not essentially altered by the tool rotation, similar to an extrusion. As the material meets again at the rear of the tool, the temperatures and pressures are sufficient to cause the material to bond. All other structures seen are secondary and unimportant. Another theory examined last summer at NASA's Marshall Space Flight Center (MSFC) was that there was no slip between the tool and the material resulting in a rotating mass of plastic weld material traveling at a variety of angular velocities - the greatest at the tool surface diminishing to zero at the outer edge of the plastic mass surrounding the tool. This conceptual model was followed by simplified calculations which showed that the balance of moments through the weld plug was not possible under steady state conditions and realistic temperature profiles. This led to some consideration of a quasi-steady oscillating process. Later when force measurements became available some models were modified and new ones were proposed.

Stewart, Michael B.↗

Flow Trajectories in Friction Stir Welding

In the Friction Stir Welding (FSW) process, a rotating, shouldered tool with a threaded pin is inserted under pressure along the seam of two pieces of metal which are tightly clamped together, and secured against a rigid anvil underneath. The rotating pin travels along the seam and through a combination of pressure and friction heating produces a zone of plastic deformation around the pin within the workpiece on either side of the seam. As the pin is moved in the direction of welding, the plasticised material moves around the tool and bonds together behind it. The elements of the material flow behavior are a combination of three elements. There is a rotational transport of material being carried around the tool, extrusion of material being forced around the pin on both sides into the cavity created behind it, and a lifting and dropping of material as it is stirred and mixed by the rotating action of the pin. It was assumed that rotational motion of the plastic zone is the primary mechanism for transport of material around the welding tool. A kinematic mathematical model was used to compute trajectories of material movement for various distributions of rotational slip within the plastic zone. These trajectories were then compared with the results of an experiment that produced radiographs of markers embedded in a workpiece that was welded with the FSW process. It was assumed that the copper wire markers retained their original length as the aluminum material flowed around them. The kinematic model included a constraint so that the displacements were such that the total length of the wire markers did not increase after deformation. There was good agreement between the calculated trajectories for the case of localized slip at the outer surface of the plastic deformation zone and the radiographs of the copper wire markers. The trajectories differed markedly from the radiograph traces when a distributed slip zone was assumed. It was concluded that the flow field could be described generally by a rotating plug model with slip occurring on the surface at the outer boundary of the plastic zone.

Bernstein, Edward L.↗

Continuous extrusion of coal

A feeding method for use with bituminous coals that exhibit plasticity at elevated temperatures is described and demonstrated on a small screw extruder previously used to extrude polyethylene. A metered feed of coal heated to a temperature just below that of incipient caking (approximately 450 C) is used. Modifications to the extruder consisting of ceramic band heaters, auxiliary cooling coils on the thrust bearing and special quick opening dies are detailed. Coals successfully extruded include high volatile A bituminous coals, high volatile B bituminous coals, a high volatile C bituminous coal and a coal with high ash content. The computer program, EXTRUD, used to simulate the extruder is described. Predicted power consumption exhibits 30% scatter, which is explained by the sensitivity of the coal friction coefficient to temperature profiles. Detailed analysis reveals some discrepancies in the program that need to be resolved.

England, C.↗

Neotectonics of Asia: Thin-shell finite-element models with faults

As India pushed into and beneath the south margin of Asia in Cenozoic time, it added a great volume of crust, which may have been (1) emplaced locally beneath Tibet, (2) distributed as regional crustal thickening of Asia, (3) converted to mantle eclogite by high-pressure metamorphism, or (4) extruded eastward to increase the area of Asia. The amount of eastward extrusion is especially controversial: plane-stress computer models of finite strain in a continuum lithosphere show minimal escape, while laboratory and theoretical plane-strain models of finite strain in a faulted lithosphere show escape as the dominant mode. We suggest computing the present (or neo)tectonics by use of the known fault network and available data on fault activity, geodesy, and stress to select the best model. We apply a new thin-shell method which can represent a faulted lithosphere of realistic rheology on a sphere, and provided predictions of present velocities, fault slip rates, and stresses for various trial rheologies and boundary conditions. To minimize artificial boundaries, the models include all of Asia east of 40 deg E and span 100 deg on the globe. The primary unknowns are the friction coefficient of faults within Asia and the amounts of shear traction applied to Asia in the Himalayan and oceanic subduction zones at its margins. Data on Quaternary fault activity prove to be most useful in rating the models. Best results are obtained with a very low fault friction of 0.085. This major heterogeneity shows that unfaulted continum models cannot be expected to give accurate simulations of the orogeny. But, even with such weak faults, only a fraction of the internal deformation is expressed as fault slip; this means that rigid microplate models cannot represent the kinematics either. A universal feature of the better models is that eastern China and southeast Asia flow rapidly eastward with respect to Siberia. The rate of escape is very sensitive to the level of shear traction in the Pacific subduction zones, which is below 6 MPa. Because this flow occurs across a wide range of latitudes, the net eastward escape is greater than the rate of crustal addition in the Himalaya. The crustal budget is balanced by extension and thinning, primarily within the Tibetan plateau and the Baikal rift. The low level of deviation stresses in the best models suggests that topographic stress plays a major role in the orogeny; thus, we have to expect that different topography in the past may have been linked with fundamentally different modes of continental collision.

Kong, Xianghong↗

Flow in the Proximity of the Pin-Tool in Friction Stir Welding and Its Relation to Weld Homogeneity

In the Friction Stir Welding (FSW) process a rotating pin inserted into a seam literally stirs the metal from each side of the seam together. It is proposed that the flow in the vicinity of the pin-tool comprises a primary rapid shear over a cylindrical envelope covering the pin-tool and a relatively slow secondary flow taking the form of a ring vortex about the tool circumference. This model is consistent with a plastic characterization of metal flow, where discontinuities in shear flow are allowed but not viscous effects. It is consistent with experiments employing several different kinds of tracer: atomic markers, shot, and wire. If a rotating disc with angular velocity w is superposed on a translating continuum with linear velocity omega, the trajectories of tracer points become circular arcs centered upon a point displaced laterally a distance v/omega from the center of rotation of the disc in the direction of the advancing side of the disc. In the present model a stream of metal approaching the tool (taken as the coordinate system of observation) is sheared at the slip surface, rapidly rotated around the tool, sheared again on the opposite side of the tool, and deposited in the wake of the tool. Local shearing rates are high, comparable to metal cutting in this model. The flow patterns in the vicinity of the pin-tool determine the level of homogenization and dispersal of contaminants that occurs in the FSW process. The approaching metal streams enfold one another as they are rotated around the tool. Neglecting mixing they return to the same lateral position in the wake of the tool preserving lateral tracer positions as if the metal had flowed past the tool like an extrusion instead of being rotated around it. (The seam is, however, obliterated.) The metal stream of thickness approximately that of the tool diameter D is wiped past the tool at elevated temperatures drawn out to a thickness of v/2(omega) in the wiping zone. Mixing distances in the wiping zone are multiplied in the unfolded metal. Inhomogeneities on a smaller scale than the mixing length are obliterated, but structure on a larger scale may be transmitted to the wake of a FSW weld.

Nunes, Arthur C., Jr.↗