The Rheology of Polyether Ether Ketone Concentrated Suspensions for Powder Molding and 3D Printing.

The main goal of the work was to use rheological methods for assessing the properties of a composition based on polyether ether ketone (PEEK) to determine the concentration limits of the polymer in the composition and select the optimal content of this composition for powder molding. The rheological properties of highly filled suspensions based on PEEK and paraffin, as well as in paraffin-polyethylene mixtures at various component ratios, were studied. These materials are designed for powder injection molding and 3D printing. Suspensions with a PEEK powder content above 50% are not capable of flow and, with increasing pressure, slide along the surface of the channel. For compositions with a higher content (60 and 70 vol.%) PEEK, independence of the storage modulus from frequency is observed, which is typical for solids and confirms the assignment of such suspensions to elastic-plastic media. The introduction of high-density polyethylene into the composition helps improve the technological properties of suspensions, expanding the range of fluidity, although it leads to an increase in viscosity. In suspensions with a mixed composition of the liquid phase, with increasing temperature, a decrease in the storage modulus is observed at 120 °C and, on the contrary, an increase at 180 °C. The latter may be a consequence of the evaporation of paraffin and the softening of PEEK due to the approach to the glass transition temperature of the polymer. Suspensions with 40% PEEK content have an optimal set of rheological properties for powder injection molding. A 3D printing filament was also obtained from a composition with 40% PEEK, which had good technological properties for FDM 3D printing. Products of satisfactory quality from suspensions with 50% PEEK can be produced by powder injection molding, but not by 3D printing. The selected compositions were used to obtain real PEEK products for practical applications.

Comparison between Micro-Powder Injection Molding and Material Extrusion Additive Manufacturing of Metal Powders for the Fabrication of Sintered Components.

Original compositions based on iron micro-powders and an organic binder mixture were developed for the fabrication of sintered metallic elements with micro-powder injection molding (µPIM) and material extrusion additive manufacturing of metal powders (MEX). The binder formulation was thoroughly adjusted to exhibit rheological and thermal properties suitable for µPIM and MEX. The focus was set on adapting the proper binder composition to meet the requirements for injection/extrusion and, at the same time, to have comparable thermogravimetric characteristics for the thermal debinding and sintering process. A basic analysis of the forming process indicates that the pressure has a low influence on clogging, while the temperature of the material and mold/nozzle impacts the viscosity of the composition significantly. The influence of the Fe micro-powder content in the range of 45-60 vol.% was evaluated against the injection/extrusion process parameters and properties of sintered elements. Different debinding and sintering processes (chemical and thermal) were evaluated for the optimal properties of the final samples. The obtained sintered elements were of high quality and showed minor signs of binder-related flaws, with shrinkage in the range of 10-15% for both the injection-molded and 3D printed parts. These results suggest that, with minor modifications, compositions tailored for the PIM technique can be adapted for the additive manufacturing of metal parts, achieving comparable characteristics of the parts obtained for both forming methods.

Micro-Injection Molding and Debinding Behavior of Hydroxyapatite/Zirconia Bi-Materials Fabricated by Two-Component Micro-Powder Injection Molding Process.

The micro-scale joining of two different materials using two-component micro-powder injection molding (2C-µPIM) is an intriguing technique. The formation of defects in bi-materials at different processing stages makes this technique challenging. This study presents the fabrication of defect-free bi-material micro-parts containing hydroxyapatite (HA) and 3 mol% yttria-stabilized zirconia (3YSZ) via 2C-µPIM. Critical powder volume concentrations (CPVCs) of 61.7 vol% and 47.1 vol% were obtained for the HA and 3YSZ powders, respectively. Based on the CPVCs, the optimal loadings for the HA and 3YSZ powders were selected as 60 vol% and 45 vol%, respectively. The HA and 3YSZ feedstocks were prepared by separately mixing the optimal powder contents with low-density polyethylene (LDPE) and palm stearin binders. The feedstocks displayed pseudoplastic behavior, and the lowest ranges of viscosity for the HA and 3YSZ at a temperature of 180 °C were 157.1-1392.5 Pa·s and 726.2-985.5 Pa·s, respectively. The feedstocks were injected to produce green HA/3YSZ micro-sized components. It was found that a solvent debinding temperature of 70 °C removed 60.6% of the palm stearin binder from the sample. In the thermal debinding stage, the open channels that formed in the bi-material sample's solvent debound at 70 °C and contributed to the removal of 93 to 95% of the binder system. When the debound bi-materials were sintered at 1300 °C, the highest relative density of 96.3% was obtained. The sintering operation revealed a linear shrinkage between 13 and 17% in the sintered HA/3YSZ micro-parts.

Effect of Particle Size and Shape on Wall Slip of Highly Filled Powder Feedstocks for Material Extrusion and Powder Injection Molding.

A necessity to distinguish between the influence of powder shape and size (particle size distribution) is especially demanding for highly filled metal powder feedstocks employed in additive manufacturing and powder injection molding. As their processability is evaluated through rheological behavior, the study focuses on the effect of powder size/shape on a wall slip, which is a typical phenomenon determining flow performance of these materials. Water and gas atomized 17-4PH stainless steel powders with D 50 of about 3 and 20 µm are admixed into a binder containing low-density polyethylene, ethylene vinyl acetate, and paraffin wax. Mooney analysis to intercept the slip velocity of 55 vol. % filled compounds reveals that wall slip effect appears to vary significantly with size and shape of metal powders-round shaped and large particles are the most prone to the wall slip. However, the evaluation is affected by the type of the flow streams resulting from the geometry of the dies-conical dies reduce the slip up to 60% in case of fine and round particles.

Characterization of Mechanical Properties and Grain Size of Stainless Steel 316L via Metal Powder Injection Molding.

The metal powder injection molding process is completed by mixing a metal powder and a binder, performing an injection molding and degreasing process, and then performing a sintering process for high density. The disadvantage of metal powder injection molding is that defects occurring during the process affect mechanical properties, which are worse in mechanical properties than in products manufactured by cold-rolling. In this study, the mechanical properties and microstructure of stainless steel 316L manufactured by the metal powder injection molding process were analyzed. Mechanical properties such as density, tensile strength, and fatigue life were analyzed. The density was measured using Archimedes' principle, and a relative density of 94.62% was achieved compared to the theoretical density. The tensile strength was approximately 539.42 MPa and the elongation to fracture was approximately 92%. The fatigue test was performed at 80% of maximum tensile strength and a stress ratio of R = 0.1. The fatigue life was found in 55% (297 MPa) of maximum tensile strength that achieved 106 cycles. The microstructure was observed through scanning electron microscope after etching, and as a result, the average grain size was 88.51 µm. Using electron backscatter diffraction, inverse pole figure map, image quality map, and kernel average misorientation map of the specimen were observed in three different areas which were undeformed, uniformly deformed, and deformed. Based on these results, it is expected that research is needed to apply the metal powder injection molding process to the manufacture of agricultural machinery parts with complex shapes.

Sintering Behavior of Bi-Material Micro-Component of 17-4PH Stainless Steel and Yttria-Stabilized Zirconia Produced by Two-Component Micro-Powder Injection Molding Process.

In this research, we investigated the influence of the sintering temperature on the physical and mechanical properties of micro-sized bi-material components of 17-4PH stainless steel and 3 mol% yttria-stabilized zirconia fabricated using a two-component micro-powder injection molding (2C-µPIM) process. First, 17-4PH and zirconia powders were separately mixed with binders to obtain feedstocks, which were then injection-molded into the dumbbell shape, followed by the binder extraction process. Subsequently, the debound micro-specimens were subjected to sintering between 1250 °C and 1350 °C for 3 h. Per the observations of the microstructures using scanning electron microscopy (SEM), a strong bond between metal and ceramic in micro-sized 17-4PH/zirconia components was formed when the sintering temperature exceeded 1300 °C. The maximum relative density of 99% was achieved when the bi-material micro-part was sintered at 1350 °C. The linear shrinkage increased from 9.6% to 17.4% when the sintering temperature was increased from 1250 °C to 1350 °C. The highest hardness value of 1439.6 HV was achieved at 1350 °C along the bi-material bonding region. Moreover, a maximum tensile strength of 13.7 MPa was obtained at 1350 °C.

Rheology of Highly Concentrated Suspensions with a Bimodal Size Distribution of Solid Particles for Powder Injection Molding.

Powder injection molding (PIM) is one of the modern and prospective technologies in processing different materials. We proposed to use bimodal compositions of particles for increasing their content in the final products. A set of model suspension of Al with low-molecular-weight poly (ethylene glycol) as a binder based on theoretical arguments concerning the filling capacity of bimodal suspensions was prepared. Studying the rheological properties of these compositions showed that they demonstrate elasto-viscous behavior with significant plasticity that is favorable for the technological process. Using compositions with bimodal distributions allows for increasing the content of the solid phase up to 75 vol. % for PIM technology, which is significantly higher than the standard practical limit. This rheological approach developed for model formulations was applied to processing compositions containing aluminum oxide as typical ceramics and polyolefines as a binder widely used in technological practice. The obtained sintered ceramic samples have quite acceptable mechanical properties of the usual corundum articles.

Injection Molding and Near-Complete Densification of Monolithic and Al2O3 Fiber-Reinforced Ti2AlC MAX Phase Composites.

Near-net shape components composed of monolithic Ti2AlC and composites thereof, containing up to 20 vol.% Al2O3 fibers, were fabricated by powder injection molding. Fibers were homogeneously dispersed and preferentially oriented, due to flow constriction and shear-induced velocity gradients. After a two-stage debinding procedure, the injection-molded parts were sintered by pressureless sintering at 1250 °C and 1400 °C under argon, leading to relative densities of up to 70% and 92%, respectively. In order to achieve near-complete densification, field assisted sintering technology/spark plasma sintering in a graphite powder bed was used, yielding final relative densities of up to 98.6% and 97.2% for monolithic and composite parts, respectively. While the monolithic parts shrank isotropically, composite assemblies underwent anisotropic densification due to constrained sintering, on account of the ceramic fibers and their specific orientation. No significant increase, either in hardness or in toughness, upon the incorporation of Al2O3 fibers was observed. The 20 vol.% Al2O3 fiber-reinforced specimen accommodated deformation by producing neat and well-defined pyramidal indents at every load up to a 30 kgf (~294 N).

Structure and Properties of Co-Cr-Mo Alloy Manufactured by Powder Injection Molding Method.

Cobalt-chromium-molybdenum alloys samples were obtained by the powder injection molding method (PIM). PIM is dedicated to the mass production of components and can manufacture several grades of dental screws, bolts, stabilizers, or implants. As a skeleton component, ethylene-vinyl acetate (EVA copolymer) with a low temperature of processing and softening point was used. The choice of a low-temperature binder made it necessary to use a coarse ceramic powder as a mechanical support of the green sample during sintering. The injection-molded materials were thermally degraded in N2 or Ar-5%H2 and further sintered in N2-5%H2 or Ar-5%H2 at 1300 or 1350 °C for 30 min. The structure of the obtained samples was characterized by X-ray diffraction and electron microscopy. Mechanical properties, including hardness and three-point bending tests, confirmed that a nitrogen-rich atmosphere significantly increases the bending strength compared to the material manufactured in Ar-5%H2. This is due to the precipitation of numerous fine nitrides and intermetallic phases that strengthen the ductile γ-phase matrix.

Effects of Bonding Treatment and Ball Milling on W-20 wt.% Cu Composite Powder for Injection Molding.

W-20 wt.% Cu pseudo-alloys were produced via powder injection molding (PIM) with powders prepared thermochemically. Bonding treatment and ball milling (BTBM) were used, and the effects of BTBM on the characteristics of the powders, rheological properties of the feedstock, shrinkage and properties of the sintered samples were studied. The morphology of the powder changed from extremely agglomerated small particles to pebble-shaped smooth large particles which were composed of several small particles combined tightly. The tap density increased from 3.25 g/cm3 to 7.22 g/cm3, and the specific surface area decreased from 0.86 m2/g to 0.45 m2/g. The critical powder loading of the feedstock increased from 45 vol.% to 56 vol.% due to the change in powder characteristics, thereby improving densification and dimension precision. For the PIM samples sintered at 1290 °C for 120 min in a hydrogen gas, the oversizing factor decreased from 1.297 to 1.216, and the dimension fluctuation ratio decreased from ±0.61% to ±0.33%. At the same time, the relative density increased from 97.8% to 98.6%, the thermal conductivity increased from 218 W/(m·K) to 233 W/(m·K), and the average coefficients of thermal expansion were roughly similar, within the range of 8.43-8.52 × 10-6/K.

Hybrid Taguchi-Gray Relation Analysis Method for Design of Metal Powder Injection-Molded Artificial Knee Joints with Optimal Powder Concentration and Volume Shrinkage.

Artificial knee joints play a critical role in improving the quality of life of the elderly and those with knee injuries. Such knee joints are fabricated using a composite material consisting of metal alloy particles and polymer resin and are generally produced using the metal powder injection molding (MIM) process. However, if the local powder concentration of the molded product is too low, the mechanical properties and aesthetic appearance of the joint are severely degraded. Similarly, if the product undergoes excessive shrinkage following removal from the mold, the dimensional accuracy will fail to meet the design specifications. Accordingly, the present study applies a hybrid approach based on the Taguchi robust design methodology and gray relation analysis (GRA) theory to determine the optimal MIM processing conditions that simultaneously maximize the powder concentration uniformity while minimizing the volume shrinkage. The feasibility of the proposed approach is demonstrated by means of CAE (Computer Aided Engineering) mold flow simulations. The results show that while the robust Taguchi design method enables the optimal processing parameters that maximize the powder concentration uniformity and minimize the volume shrinkage to be individually determined, the hybrid Taguchi-GRA method enables both quality measures to be optimized simultaneously.

Environmentally Efficient 316L Stainless Steel Feedstocks for Powder Injection Molding.

In this study, environmentally convenient highly metal powder filled feedstocks intended for powder injection molding is presented. The composition of 60 vol % 316L stainless steel gas atomized powder feedstocks containing semicrystalline waxes: acrawax or carnauba wax and paraffin wax, combined with polyethylene glycol and modifier, was optimized to provide defect-free parts. Rheological as well as thermogravimetric analyses supported with scanning electron microscopy and metallography were employed to set up optimum conditions for molding, debinding and sintering. The performance of the novel feedstock was compared with currently available polyolefines-based materials, and results showed an efficiency enhancement due to the substantially lower (about 100 °C) mixing and molding temperatures as well as a reduction of debinding and sintering times at the simultaneous achievement of better mechanical properties in terms of elongation and tensile strength, in comparison to the mass production feedstock.

Online Rheometry Investigation of Flow/Slip Behavior of Powder Injection Molding Feedstocks.

Wall slip in the flow of powder injection molding (PIM) compounds can be the cause of unrealistically low viscosity values, and can lead to a failure of flow simulation approaches. Regardless of its importance, it has been considered only scarcely in the rheological models applied to PIM materials. In this paper, an online extrusion rheometer equipped with rectangular slit dies was used to evaluate the slip velocity of commercial as well as in-house-prepared PIM feedstocks based on metallic and ceramic powders at close-to-processing conditions. The tested slit dies varied in their dimensions and surface roughness. The wall-slip effect was quantified using the Mooney analysis of slip velocities. The smaller gap height (1 mm) supported the wall-slip effect. It was shown that both the binder composition and the powder characteristic affect slip velocity. Slip velocity can be reduced by tailoring a powder particle size distribution towards smaller particle fractions. The thickness of the polymer layer formed at the channel wall is higher for water-soluble feedstocks, while in the case of the catalytic polyacetal feedstocks the effect of surface roughness was manifested through lower viscosity at smooth surfaces.

Fabrication of Micro-Patterned Surface for Pool-boiling Enhancement by Using Powder Injection Molding Process.

In this study, two kinds of copper micro-patterned surfaces with different heights were fabricated by using a powder injection molding (PIM) process. The micro-pattern's size was 100 µm, and the gap size was 50 µm. The short micro-pattern's height was 100 µm, and the height of the tall one was 380 µm. A copper powder and wax-polymer-based binder system was used to fabricate the micro-patterned surfaces. The critical heat flux (CHF) and heat transfer coefficient (HTC) during pool-boiling tests were measured with the micro-patterned surfaces and a reference plain copper surface. The CHF of short and tall micro-patterned surfaces were 1434 and 1444 kW/m², respectively, and the plain copper surface's CHF was 1191 kW/m². The HTC of the plain copper surface and the PIM surface with short and tall micro-patterned surfaces were similar in value up to a heat flux 1000 kW/m². Beyond that value, the plain surface quickly reached its CHF, while the HTC of the short micro-patterned surface achieved higher values than that of the tall micro-patterned surface. At CHF, the maximum values of HTC for the short micro-pattern, tall micro-pattern, and the plain copper surface were 68, 58, and 57 kW/m² K.

Fabrication of Micro-Parts with High-Aspect Ratio Micro-Hole Array by Micro-Powder Injection Molding.

The present study investigated high-aspect ratio micro-hole array parts which were made by ZrO2 micro-powder with different particle sizes and micro-powder injection molding technology. It analysed the influence of particle sizes on feedstock, debinding and sintering of ceramic nozzles with multi-micro-holes. The forming quality of ceramic nozzles with multi-micro-holes was discussed in this paper. The results show that the two mixed ZrO2 feedstocks have fine uniformity. The average deviation of the feedstock made with 200 nm powder was -2%, and the average deviation of the feedstock made with 100 nm powder was -7.1%. The sample showed certain sintering characteristics which provided better strength (11.10 MPa) to parts after debinding. The linear shrinkage and the density of the two powder samples at different sintering temperatures increased as the sintering temperature increased. If the temperature continued to increase, the linear shrinkage and the density decreased. The highest hardness and flexural strength values of the ZrO2 sample with 200 nm powder used were: 1265.5 HV and 453.4 MPa, and the crystalline particle size was 0.36 µm. The highest hardness and flexural strength values of the ZrO2 sample with 100 nm powder used were: 1425.8 HV and 503.6 MPa, and the crystalline particle size was 0.18 µm. The ceramic nozzles with multi-micro holes shrunk to nearly the same axial, radial and circumferential directions during sintering. After sintering, the roundness of ceramic micro-hole met the user requirements, and the circular hole had a high parallelism in the axial direction. The micropore diameter was 450 ± 5 µm, and it was possible to control the dimensional accuracy within 1.5% after sintering. The study presented a superior application prospect for high-aspect ratio micro hole array parts in aerospace, electronics and biomedicine.

Evaluation of the safety and efficiency of novel metallic implant scaler tips manufactured by the powder injection molding technique.

BACKGROUND: Although many studies have compared the properties of ultrasonic scaling instruments, it remains controversial as to which is most suitable for implant scaling. This study evaluated the safety and efficiency of novel metallic ultrasonic scaler tips made by the powder injection molding (PIM) technique on titanium surfaces. METHODS: Mechanical instrumentation was carried out using four types of metal scaler tips consisting of copper (CU), bronze (BR), 316 L stainless steel (316 L), and conventional stainless steel (SS) tips. The instrumented surface alteration image of samples was viewed with scanning electron microscope (SEM) and surface profile of the each sample was investigated with confocal laser scanning microscopy (CLSM). Arithmetic mean roughness (Ra) and maximum height roughness (Rmax) of titanium samples were measured and dissipated power of the scaler tip was estimated for scaling efficiency. RESULTS: The average Ra values caused by the 316 L and SS tip were about two times higher than those of the CU and BR tips (p < 0.05). The Rmax value showed similar results. The efficiency of the SS tip was about 3 times higher than that of CU tip, the 316 L tip is about 2.7 times higher than that of CU tip, and the BR tip is about 1.2 times higher than that of CU tip. CONCLUSIONS: Novel metallic bronze alloy ultrasonic scaler tip minimally damages titanium surfaces, similar to copper alloy tip. Therefore, this bronze alloy scaler tip may be promising instrument for implant maintenance therapy.

Effect of Zr, Nb and Ti addition on injection molded 316L stainless steel for bio-applications: Mechanical, electrochemical and biocompatibility properties.

The research investigated the effect of Zr, Nb and Ti additions on mechanical, electrochemical properties and biocompatibility of injection molded 316L stainless steel. Addition of elemental powder is promoted to get high performance of sintered 316L stainless steels. The amount of additive powder plays a role in determining the sintered microstructure and all properties. In this study, 316L stainless steel powders used with the elemental Zr, Nb and Ti powders. A feedstock containing 62.5 wt% powders loading was molded at different injection molded temperature. The binders were completely removed from molded components by solvent and thermal debinding at different temperatures. The debinded samples were sintered at 1350°C for 60 min. Mechanical, electrochemical property and biocompatibility of the sintered samples were performed mechanical, electrochemical, SBF immersion tests and cell culture experiments. Results of study showed that sintered 316L and 316L with additives samples exhibited high corrosion properties and biocompatibility in a physiological environment.

Particle morphology influence on mechanical and biocompatibility properties of injection molded Ti alloy powder.

Titanium and Titanium alloys exhibits properties that are excellent for various bio-applications. Metal injection molding is a processing route that offers reduction in costs, with the added advantage of near net-shape components. Different physical properties of Titanium alloy powders, shaped and processed via injection molding can achieve high complexity of part geometry with mechanical and bioactivity properties, similar or superior to wrought material. This study describes that the effect of particle morphology on the microstructural, mechanical and biocompatibility properties of injection molded Ti-6Al-4V (Ti64) alloy powder for biomaterials applications. Ti64 powders irregular and spherical in shape were injection molded with wax based binder. Binder debinding was performed in solvent and thermal method. After debinding the samples were sintered under high vacuum. Metallographic studies were determined to densification and the corresponding microstructural changes. Sintered samples were immersed in a simulated body fluid (SBF) with elemental concentrations that were comparable to those of human blood plasma for a total period of 15 days. Both materials were implanted in fibroblast culture for biocompatibility evaluations were carried out. The results show that spherical and irregular powder could be sintered to a maximum theoretical density. Maximum tensile strength was obtained for spherical shape powder sintered. The tensile strength of the irregular shape powder sintered at the same temperature was lower due to higher porosity. Finally, mechanical tests show that the irregular shape powder has lower mechanical properties than spherical shape powder. The sintered irregular Ti64 powder exhibited better biocompatibility than sintered spherical Ti64 powder. Results of study showed that sintered spherical and irregular Ti64 powders exhibited high mechanical properties and good biocompatibility properties.

Progress in Titanium Metal Powder Injection Molding.

Metal powder injection molding is a shaping technology that has achieved solid scientific underpinnings. It is from this science base that recent progress has occurred in titanium powder injection molding. Much of the progress awaited development of the required particles with specific characteristics of particle size, particle shape, and purity. The production of titanium components by injection molding is stabilized by a good understanding of how each process variable impacts density and impurity level. As summarized here, recent research has isolated the four critical success factors in titanium metal powder injection molding (Ti-MIM) that must be simultaneously satisfied-density, purity, alloying, and microstructure. The critical role of density and impurities, and the inability to remove impurities with sintering, compels attention to starting Ti-MIM with high quality alloy powders. This article addresses the four critical success factors to rationalize Ti-MIM processing conditions to the requirements for demanding applications in aerospace and medical fields. Based on extensive research, a baseline process is identified and reported here with attention to linking mechanical properties to the four critical success factors.