Selective laser sintering of polymer blends: Bulk properties and process behavior

Physically mixed powderous polymer blends consisting of at least two different thermoplastic materials with complementary properties could allow the successful fabrication of components with tailored and graded properties. In this work, powderous polymer blends of the partially miscible and chemically reactive blend system PBT/PC were produced from wet grinded powders at different weight ratios of 90/10, 80/20, 70/30 and 60/40, respectively. The PBT/PC is used as a model system for a blend with a semi-crystalline and amorphous component, while being relevant for industrial use, such as automotive applications. Before the implementation into the selective laser sintering process (SLS), the bulk properties of the powders were analyzed. The quadratic monolayer test specimens were generated with different energy densities by variating the laser power. The specimens' geometrical and microstructural properties were studied. The investigations showed that an improvement of geometric properties in terms of layer development can be achieved by increasing the PC content and that it is possible to generate polymer blends with matrix and dispersed phase from PBT/PC blends.     

Automated image analysis to characterize the melt densification stage of polymer sintering processes

Knowledge of melt densification during sintering is generally acquired by visualization methods, recording bubble formation and dissolution with time. Only manual visualization methods have been reported for polymer studies, which restrict the availability of data to a few discrete moments in time for the overall process. An automated vision system is presented in this paper to provide an improved level of analysis on densification, validated against a manual method. The machine vision technique was applied in the analysis of sintering for various polyethylenes of differing melt flow index and particle size. The automated technique was found to be very accurate and capable of collecting bubble size distributions on a timescale of seconds, which is an improvement in data collection. The method was prone to underestimate bubble numbers (∼20% error), especially those less than 100 μm in size, till the bed temperature rose significantly above the melting temperature of the polymer.     

On the visco-elasto-plastic response of additively manufactured polyamide-12 (PA-12) through selective laser sintering

This work presents an in-depth study on the mechanical behavior of selective laser sintered (SLS) nylon (PA-12). The entire visco-elasto-plastic response is determined based on experimental data obtained through tensile, compression, shear and relaxation testing. In addition, ultrasonic non-destructive testing is proposed as an alternative to conventional testing for the derivation of the elastic properties of this material. An isotropic elastic behavior was observed, while a clear orthotropic and non-linear response was found for both the plastic curves and the relaxation behavior. Strength data suggests laser sintered PA-12 will fail in tension rather than in shear. The ultrasonic tests correspond well to conventional tensile data (at high rates), and represent a cost-effective alternative to extensive conventional tensile testing. The presented test data can potentially be used to derive a detailed material model suitable for modelling static, fatigue and impact applications using 3D printed PA-12.     

The effect of short glass fibers on the process behavior of polyamide 12 during selective laser beam melting

In additive manufacturing, polymer composites are used for setting tailored properties. Short glass fibers can be used as fillers for polyamide 12 for enhancing stiffness or tensile strength as well as for reducing shrinkage. In this paper, the effects of short glass fibers on polyamide 12 concerning powder properties, process behavior and part properties in laser beam melting of polymers (SLS) are investigated. It could be shown that by increasing the short glass fiber content powder properties as well as part properties are immensely affected. By adding glass fibers, powder properties, like flowability and diffuse reflection decrease. The isothermal crystallization changes resulting in a narrower processing window. Concerning mechanical properties, short glass fibers allow for a higher stiffness until a critical limit of filler concentration within this study is reached, after which the tensile strength decreases. The elongation of break decreases by rising the filler content.     

Mechanical properties of PA6/PA12 blend specimens prepared by selective laser sintering

The use of polymeric blends can increase the range of structures and properties of selective laser sintering (SLS) parts. This study investigates the processing of a binary polar system using polyamide 6 (PA6) and polyamide 12 (PA12) by SLS. The mixture composition and processing conditions, and their influence on the dynamic mechanical properties of the specimens manufactured were evaluated. The maximum tan δ values suggest that PA6 and PA12 have similar visco-dissipative behavior. The PA6/PA12 blends behavior varied according to the relaxation phenomena of the pure components, proportionally to the blend composition. The creep test showed that blends with a higher amount of PA6 had greater plastic deformation and less elastic recovery. In the fatigue test the 20/80 and 50/50 blends presented good fatigue resistance under the test conditions.     

The microstructural characterization of PA6/PA12 blend specimens fabricated by selective laser sintering

This study investigates the processing of blends of polyamide 6 (PA6) and polyamide 12 (PA12) by selective laser sintering (SLS) using a CO₂ laser. Powder properties of undiluted polymers, mixture composition, and processing parameters, as well as their influence on the microstructure of the specimens manufactured, were evaluated. Polyamides showed higher absorption of laser energy during the sintering of blend specimens, with subsequent thermal energy transfer to the melting of the polymeric phases. The structure of parts obtained by SLS is dependent on the process parameters and the characteristics of the powder material to be processed. The microstructures of PA6/PA12 blend specimens were heterogeneous, with co-continuous and disperse phases depending on the quantity of PA12. The porosity and crystallinity also changed as a function of the component proportions. The use of polymeric blends can increase the range of structures and properties of SLS parts.     

Multiscale characterization and constitutive parameters identification of polyamide (PA12) processed via selective laser sintering

This study is focused on multiscale characterization and constitutive parameters identification of selectively laser sintered PA12 specimens. The process parameters and change in crystallinity due to 3D printing were identified via differential scanning calorimetry (DSC). Tension, compression, shear, flexural and fracture tests performed on samples fabricated, both in 0° and 90° directions reveal that the tensile toughness of samples printed in 0° orientation, outperform samples printed in 90° orientation by an average of 24%. Cryogenically fractured samples were analyzed via SEM and micro-computed tomography to analyze 2D/3D defects and correlate the microstructure with macroscopic properties. The constitutive parameters for a strain-rate and temperature-dependent Three Network (TN) material model were identified using the measured mechanical properties. Furthermore, mechanical response of micro-architected Kelvin lattice structure was analyzed by Finite Element Method employing the TN constitutive model and the predictions were corroborated with measurements.     

Analytical characterization of polyamide 11 used in the context of selective laser sintering: Physico-chemical correlations

Polyamide 11 is an attractive material for additive manufacturing, however, in the selective laser sintering process it is subject to significant thermally induced stress. Suitable analytical methods are necessary to indicate any changes in the material properties. In this work, thermally stressed powder samples and printed tensile bars were analyzed by size exclusion chromatography-multi angle laser light scattering and differential scanning calorimetry. Based on the molecular weight distribution, crystallization and melting temperatures, ageing states of the investigated powders can be defined and transferred to the particles of the printed components. As a result, thermal stress led to an increase in molar mass and polydispersity. Moreover, calorimetric measurements indicated a delayed nucleation process as well as a decrease in polymorphism. Additionally, polymeric material with lower polydispersity values across the tensile bars could lead to decreasing elongation at break (ε_B) values. For the crystallization onset temperature the opposite effect on ε_B was observed.     

Fast FTIR imaging: A new tool for the study of semicrystalline polymer morphology

The distribution of chemical species and the degree of orientation in semicrystalline polymer systems have been studied using fast Fourier transform infrared (FTIR) imaging. A variety of poly(ethylene glycol) systems, including pure polymer, high and low molecular weight blends, and blends with amorphous polymers, were studied. It is shown that fast FTIR imaging can be used to determine the distribution of species with different molecular weights and can be used to determine the degree of segregation of different components in blends with amorphous polymers. Additionally, by employing an infrared polarizer, the degree of orientation was determined in these systems by the generation of spatially‐resolved dichroic ratio images. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2353–2359, 1999     

The effect of processing conditions on the mechanical properties of polyethylene produced by selective laser sintering

A study was performed to explore the feasibility of processing a polyethylene by selective laser sintering. The polyethylene powder was characterised by scanning electron microscopy, particle size analysis and differential scanning calorimetry. The laser sintering processing conditions, especially powder bed temperature, laser power and laser scan counts, were studied. Well defined tensile testing specimens of the polyethylene were produced successfully by double laser scanning. The effect of the thermal history during the laser sintering process on the mechanical properties of the laser sintered parts is discussed for the first time.     

Comparison of micromechanical models for the prediction of the effective elastic properties of semicrystalline polymers: Application to polyethylene

In this paper, we discuss the application of different micromechanical composite models to compute the effective elastic properties of semicrystalline polymers. The morphology of these two-phase materials consists of crystalline lamellae and amorphous domains which may form a spherulitic microstructure. The selected models are the Mori-Tanaka type models, the Double-Inclusion models, and the Self-Consistent models. We applied these composite estimates to both fully isotropic and transverse isotropic transcrystalline polyethylene. The results from these different models are compared to the experimental results for different crystallinities. The Generalized Mori-Tanaka (GMT) model and the Self-Consistent Composite-Inclusion (SCCI) model give the best predictions of the effective elastic constants compared to the other models. Published in Russian In Vysokomolekulyarnye Soedineniya, Ser. A, 2008, Vol. 50, No. 5, pp. 809–820. This article was submitted by the authors in English.     

Application of fourier transform infrared spectroscopy to the study of semicrystalline polymers: Poly(ethylene terephthalate)

An infrared absorbance subtraction technique has been used to “isolate” bands in the composite spectrum of semicrystalline polymers according to their crystalline or amorphous character. Amorphous and crystalline spectra for annealed, melt-quenched, and solution-cast poly(ethylene terephthalate) have been separated. The spectra of the amorphous component show an increased intensity of bands associated with the trans configuration of oxygen about the C? C bond when the polymer is annealed. This increased “trans” band intensity reflects the increased proportion of trans structures as a result of annealing. The amorphous trans bands are shifted approximately 1–3 cm^?1 from their positions in the crystalline “trans” spectrum. The frequency shift of these bands can be attributed to the differences in chain interactions that exist in the amorphous phase and the crystalline lattice. We have also found that under identical anealing conditions the amorphous phase of the melt-quenched polymer contains an increased intensity of conformational trans bands compared to the sample cast from solution.     

On the difference in material structure and fatigue properties of nylon specimens produced by injection molding and selective laser sintering

This paper describes the influence of dynamic tension/compression loading on notched and unnotched nylon specimens fabricated by Injection Molding (IM) and Selective Laser Sintering (SLS). The main objective of this work is to analyze and describe the differences in material structure and fatigue properties of as-built nylon parts produced by IM and SLM from the same polyamide 12 powder. The differences in dimensional quality, density, surface roughness, crystal structure and crystallinity are systematically measured and linked to the mechanical fatigue properties. The fatigue properties of the unnotched SLS specimens are found to be equal to those of the unnotched IM specimens. The presence of pores in the sintered samples does not lead to rapid failure, and the microvoid coalescence failure mechanism is delayed. The notched specimens show more brittle failure and increased fatigue resistance which is caused by local notch-strengthening. The results enable improved understanding of the difference in material structure and fatigue behavior of selective laser sintered and injection molded polyamide.     

Thermal characteristics and analysis of pyrolysis effects during the mechanical alloying process of Astaloy CrM powders

Mechanical alloying processes are carried out usually with addition of some lubricants, referred to also as a process control agents (PCA). About 1–2 wt% of a PCA (usually stearic acid) is normally added to prevent excessive cold welding amongst the powder particles, especially when powders of ductile metals are milled. However, lubricants (maybe disintegrated after MA process) must be removed in the early stages of heating during the sintering process. The aim of the present study was to determine the effect of the MA process especially (i) milling time and (ii) influence of lubricant addition on thermal effects during heating of iron powder (Astaloy CrM) with the addition of 1 wt% stearic acid measured by differential scanning calorimeter (DSC) and thermogravimetry (TG) techniques. Removal of the lubricants during heating of the blended powders and exhaust gases from the furnace were monitored by quadruple mass spectrometry (QMS). Determination of the physical and technological properties of the powder mixture obtained from MA was performed with a laser particle sizer. Distribution of particle sizes, flow and apparent density were also measured. Furthermore, the shape and morphology of the powders were characterised by a light optical microscope (LOM) and scanning electron microscope (SEM).     

Transdermal drug transfer from a polymer device: study of the polymer and the process

Special polymer devices containing a drug are able to deliver the drug to the patient through transdermal delivery. Two points are of interest: the nature of the polymer device, and the process of drug delivery. The polymer device considered in this paper is able to maintain a constant drug concentration on the patient's skin surface. The process of drug delivery is studied through in vitro and in vivo tests. In vitro tests show that the skin plays the role of a membrane, with a steady state for the drug transfer following a non-steady state. The parameters of diffusion through the skin are thus calculated from this test. In vivo tests are described by a process of drug transfer consisting of two stages: the stages of absorption into, and elimination out of, the blood. The polymer device plays a major role, as it should maintain a constant concentration of drug on the skin.     

On the influence of inter-layer time and energy density on selected critical-to-quality properties of PA12 parts produced via laser sintering

Laser Sintering (LS) of polymers is an Additive Manufacturing technique progressively used to produce functional parts. However, LS parts still present a certain quality variability. Efficient consolidation of the polymeric powder, necessary to obtain a dense part, mainly depends on the viscosity of the molten polymer and on the time given for the polymer to coalesce. The polymer viscosity is a function of the temperature and, consequently, of the energy density (ED) input by the laser. The sintering time strongly depends on the surface area to be laser-scanned in each layer, which in turn is strongly related to the product complexity and the number of parts within one build. The aim of this work is to investigate how this thermo-temporal effect, influenced by the ED and the inter-layer time, influences the resulting LS PA12 part quality at both micro-level (e.g., porosity, crystallinity) and macro-level (e.g., dimensional accuracy, mechanical performance).     

Increased spherulitic growth rates of semicrystalline polymer due to enhanced limited local chain segmental mobility at the interface of double-layer thin films

In this work the nucleation and growth of spherulites for the below polylactide (PLA) layer in poly(ε-caprolactone)/polylactide (PCL/PLA) double-layer films during isothermal crystallization at various temperatures above the melting point of PCL have been investigated by using polarized optical microscopy (POM). It is revealed that two types of spherulitic morphologies are observed in PCL/PLA double-layer films. One is the well defined highly birefringent spherulites, and the other one is the coarse spherulites. It is interesting to find that the spherulitic growth rate of the coarse spherulites is higher than that of the well defined spherulites. It is thought that the coarse spherulites nucleate and grow with the assistance of the interfaces between the PCL and PLA layers, and the well defined highly birefringent spherulites only nucleate and grow in the PLA layer.     

Approach to improving the toughness of TGMDA/DDS epoxy resin by blending with thermoplastic polymer powders

A series of hot-melt processable thermosetting compositions was prepared by blending N,N,N′,N′-tetraglycidyl-4,4′ -diaminodiphenyl-methane/4,4′-diaminodiphenylsulfone (TGMDA/DDS) epoxy resin and thermoplastic polymer powders with average particle size below 30 μm. The basic thermoplastic polymers were either a high T_g amorphous cardo polyimide (T_g=350°C) or commercial semicrystalline PA6 and PA12 polyamides. The resulting heterogeneous mixtures showed viscosity values below 5000 cps suitable for prepregging process. After cure, phase-separated morphologies were maintained with a rather limited interphase miscibility as demonstrated by thermomechanical analysis. Scanning electron microscope examination of fracture surfaces pointed out a strong adhesion between the powder particles and the surrounding polyepoxy network, particularly for the potentially reactive polyamide structures. Moreover, as shown by differential scanning calorimeter analysis, the crystallinity ratio of the PA6 and PA12 powders was lowered due to melting during thermal polymerization. The fracture toughness properties of the powder-containing materials were compared with those of a fully miscible cardo polyimide–TGMDA/DDS blend coming from an homogeneous resin composition. The best improvement in fracture energy was obtained for the powder-modified resins. The most effective composition filled with 16 wt% of powdered polyimide exhibited a fourfold increase in G_IC (388 J/m² versus 100 J/m²) without compromising the epoxy thermomechanical stability (T_g=227°C versus 223°C).