Before analyzing the variation of powder properties with environmental exposure, one must first gain a generalized understanding of the characteristics of the Al 5056 and Ta powders studied in this work. A baseline understanding of Al 5056 and Ta particle size and shape was formulated via qualitative analysis using the SEM micrographs of both powder types in
Figure 2. In
Figure 2a, the inertly gas atomized Al 5056 powder can be characterized by a combination of oblong and roughly spherical particles. The Al 5056 powder also displays a combination of larger and smaller particles, owing to the potential for a rather large PSD. In
Figure 2b, the angular morphology of the Ta powder is very evident, as is its relatively wide PSD with the combination of larger and smaller particles; this is logical, given that the Ta powder was likely produced from a hydride-dehydride method. Given this generalized description of the Al 5056 and Ta powders, a more contextualized analysis of the trends in flowability and moisture content can be performed. Further quantitative analysis of particle size and morphology will be discussed in
Section 3.3.
3.3. Influential Factors on Powder Properties and Behavior
From the flowability data in
Figure 3 and
Figure 4 and the moisture content data in
Figure 5 and
Figure 6, one can confidently say that the properties and behavior of the Al 5056 and Ta powders in this study vary inconsistently as they are exposed to different environmental conditions. Given this, it is essential to investigate what powder characterization can reveal about these inconsistencies. While many factors influence metallic powders′ flowability and moisture content, the most important ones considered herein are (1) the laboratory conditions during exposure and (2) particle size and morphology effects.
The average laboratory conditions—specifically, temperature (in °C) and humidity (in %)—were recorded during each exposure day throughout the study and were plotted in
Figure 7. Given that the temperature was controlled in this laboratory, there were minimal changes in temperature across the study, with an average temperature of 21.7 ± 0.5 °C across all exposure days in the study. However, the humidity in the laboratory was not directly controlled, which was evident through the spikes in the humidity curve in
Figure 7; considering all exposure days in the study, the average humidity was 26.4% ± 6.7%. While the humidity levels resided within a typical range for laboratory operation between 20% and 40%, particularly towards the end of the study, several spikes and dips in humidity (such as at Days 35 and 42) may prove concerning for consistent moisture content changes and therefore effects on flowability. Given that the changes in powder moisture content are only anticipated to change based upon the ambient conditions during exposure, the humidity appears to be of great importance.
Given that the humidity naturally varied throughout the study, the scattered patterns and inconsistent changes in moisture content of the Al 5056 and Ta powders can be justified, and thus the flowability along with it. However, neither the changes in temperature nor humidity alone directly correlated with any spikes or dips in flowability or moisture content; therefore, it is essential to investigate other root causes of these inconsistencies in powder properties and behavior, such as particle size and morphology effects. Other aspects of the effects of exposure conditions on flowability and moisture content will be considered in
Section 3.4 and
Section 3.5.
It has been firmly established in the study of powder systems that particle size and morphology greatly influence powder flowability and moisture content. Therefore, the particle size/shape data in
Table 2 were extracted after analyzing all Al 5056 and Ta powder samples in the Microtrac FlowSync system using a combined laser diffraction and dynamic image analysis method. In
Table 2, several measured and calculated parameters are displayed to describe the PSD and morphology of the Al 5056 and Ta powders. To help analyze the size of the powders, the 10th, 50th, and 90th diameter percentiles—labeled
,
, and
, respectively—were reported, which are commonly used in particle analyses for metal powder-based AM processes. Along with the D-values, the values of the volume percent of particles under both 10 μm and 20 μm in size were provided for both powder types, which indicates the relative quantity of fine particles in the samples. Apart from the measured size parameters procured from the Microtrac system, the unitless
parameter was calculated from the
,
, and
values to provide a metric of the breadth of the PSD, with a larger
representing a broader PSD and vice versa.
was calculated using Equation (1):
Several particle morphology parameters were also reported from the Microtrac system, which can be found in
Table 2; however, this is not a comprehensive list of the values measured for all powder samples. As an important note, all the shape-related parameters reported from the Microtrac FlowSync system are done utilizing the dynamic image analysis features of the hybrid analysis mode, which provide 2D particle measurements based upon thousands of images taken of various particles in the test sample. For example, the
parameter is a value that ranges from 0 to 1 and measures how circular a particle’s cross-section is, with unity representing a perfect circle. The calculation of
follows Equation (2), based upon the particle’s
and
:
The ratio of the particle’s surface area to volume—denoted by
—was also of interest because this ratio serves as a metric of a powder’s affinity to adsorbing specific compounds on its surface; this is a commonly utilized metric to observe surface energy-related changes associated with the
ratio [
26,
27]. Given that the Microtrac does not provide 3D measurements, the calculations of surface area and volume are solely approximations based upon the particle’s 2D image profile, resulting in an approximation of the
ratio; more accurate estimations of the
ratio could be completed using Brunauer-Emmett-Teller (BET) measurements for surface area quantification and 3D particle size/shape analysis for volume calculations. Using the Microtrac FlowSync data, the
ratio can be calculated based upon Equation (3):
Equation (3) relies on the term
, an area equivalent diameter (calculated from dynamic image analysis data) based upon the diameter measurement of a circle with equivalent area to the 2D image of a specified particle. The calculation for
can be done utilizing Equation (4), which is based upon the particle’s
:
To begin, the particle size data in
Table 2 show a much larger particle size for the Al 5056 powder compared to the Ta powder, with a higher average
,
, and
and lower standard deviation across all Al 5056 samples compared to the Ta samples. Complementary to this, the volume percent of particles under 10 μm and 20 μm is much higher for the Ta samples—7.757% ± 1.128% and 31.418% ± 3.152%, respectively—than the Al 5056 samples—0.155% ± 0.007% and 7.645% ± 0.364%, respectively. Given the tendency of a sample with smaller particles to have trouble flowing and to pick up more moisture, it is not surprising that the Ta powder samples flowed more inconsistently than the Al 5056 samples, particularly with the associated “no flow” conditions [
28]. This disparity in particle size can also be visualized through the PSD histogram line plots in
Figure 8 for both powder types, where the center of the Ta PSD is shifted to a lower value than the Al 5056 PSD. As a note,
Figure 8 was constructed using a single powder sample from one of the Al 5056 and Ta lots, respectively, with a representative PSD.
The spread of the PSD is also an essential factor in determining powder flowability, which is depicted by the histogram line plots in
Figure 8. The PSD for the Ta powder is visually much broader than the Al 5056 powder, with a prominent tail at smaller particle sizes. This broad distribution can be quantified with the
parameter in
Table 2, which is higher for the Ta powder (1.616 ± 0.261) than the Al 5056 powder (1.109 ± 0.065), as expected. Troubles with consistent powder flowability measurements have also been found with powders of broad PSDs, which aligns well with the flowability data reported in
Figure 3 and
Figure 4 [
29]. As a note, while the Ta samples were expected to flow “worse” than the Al 5056 samples given their smaller particle size and wider PSD, the flow rates produced by testing in the Carney Funnel are higher for the Ta powders than the Al 5056 powders; this reaffirms a limitation of the Carney Funnel flow test method, whereby PSD effects are masked by the material density effects on flow rate.
Particle morphology also plays a critical role in moisture content and flowability values observed with the Al 5056 and Ta powders. As listed in
Table 2, the primary morphology parameters considered here for both powder types are
and
ratio. The
of the Ta powder (0.931 ± 0.001) is lower than that of the Al 5056 powder (0.965 ± 0), indicating that the powder is less spherical and thus more irregularly shaped. Moreover, the
ratio of the Ta powder (0.374 μm
−1 ± 0.013 μm
−1) is slightly higher than the ratio for the Al 5056 powder (0.233 μm
−1 ± 0.003 μm
−1), which usually links to a greater tendency to adsorb moisture during exposure. Given the increased particle irregularity and
ratio of the Ta powder compared to the Al 5056 powder, it makes sense that flowability and moisture content values were more inconsistent with the Ta powder than the Al 5056 powder. However, it is important to note that the Al 5056 moisture content values did vary with greater magnitude than the Ta moisture content, which may speak to this apparent material dependence of property and behavior fluctuations with environmental exposure.
3.4. Statistical Analysis
To complement the semi-quantitative analysis presented in
Section 3.3 of the alternative factors affecting powder flowability and moisture content, including laboratory conditions and particle size and shape, correlational statistical methods were employed to provide quantitative insights into powder property–behavior linkages. By identifying these connections, powder users will better understand which factors—from powder handling and storage conditions to powder characteristics and pre-processing treatments—affect powder behavior more than others.
In the present statistical analysis, OLS regression (facilitated by Python-based programming) was used as the principal analytical technique, performed on multiple datasets previously mentioned in
Section 2.4. The features utilized in the regression-based models, considered for each lot of powder in all three datasets, were based upon the features presented previously in
Table 1. However, several features were eliminated from analytical scrutiny, given that their inclusion in the regression model compromised model performance and interpretability. Specifically, the “Median Convexity,” “Number of Exposures,” and “Exposure Duration” were eliminated, as the models overfitted to match these values, given their uniformity across powder lots with “Median Convexity” and their strong linear increase between samples for “Number of Exposures” and “Exposure Duration.” Additionally, the “Average Exposure Temperature” and “Average Exposure Humidity” were removed from consideration as predictive features for flowability; ultimately, the temperature and humidity associated with specific environmental exposures would affect moisture content directly, rather than flowability. Therefore, only the “Moisture Content” variable was considered to account for these temperature and humidity effects, as they are effectively embedded within this feature value; this was done to maintain the physical significance of the implications of this regression-based analysis. Once these features mentioned above were initially eliminated, the ten remaining features in
Table 1 were utilized in subsequent analysis.
To ensure that the implemented OLS regression model produced robust and interpretable results, the predictive features utilized first needed to be screened to check for multicollinearity. Hypothetically, if several independent variables were used in the regression with a high degree of linear dependence, model performance would decline with the increased variance associated with the calculated regression coefficients. Ultimately, the VIF metric was calculated to identify multicollinearity between predictive variables, which were eliminated one-by-one iteratively if their values were higher than the threshold value of 10, removing only the highest VIF greater than 10 each time. As a note, if the manner of feature elimination was changed—meaning, if the features were not eliminated in the order of the highest VIF greater than 10 first, with others afterward—then the resulting VIF values may be changed for each dataset and the resulting parameters considered suitable for OLS regression may be altered.
Upon carrying out this feature elimination process for each dataset, the VIF values in
Table 3 were produced for each predictive feature. All the features presented in
Table 3 for each dataset pass the VIF criterion of being less than 10 and appear to be less than 5, meaning that multicollinearity will most certainly not hinder the predictive nature of the subsequent regression-based analysis. Of the ten features considered for each dataset, only six parameters passed the VIF criterion for the Al 5056 Only and Ta Only datasets, whereas only three passed for the combined Al 5056 + Ta dataset. Interestingly so, the same six features passed for the Al 5056 and Ta datasets but were ordered differently in terms of their VIF statistics, given how linearly independent they were from one another for that specific powder. Accordingly, the “
”, “
”, “Volume Percent of Particles Under 20 μm in Size”, and “Surface Area to Volume Ratio” were all neglected in subsequent regression models, based upon their calculated VIF values. It is worth noting that the “
”, “Moisture Content”, and “
” were considered suitable features for regression in all three datasets.
After the VIF analysis was completed for each dataset, OLS regression was performed according to the details presented in
Section 2.4. The regression coefficients calculated were not crucial in this study; however, the resultant MAE and RMSE metrics were necessary for evaluating predictive success and model robustness for the test and train datasets. The MAE values and the RMSE values for the test and train sets are presented in
Table 4. With a multivariate linear regression model, the MAE value represents the average of the absolute value of the residuals, denoting the model’s predictive success; this metric is based upon a perfect predictive model with an MAE of zero and larger values indicating worse predictive capacity. Here, for each of the three datasets considered, the MAE values are less than 2, highlighting that the regression models can successfully predict flowability using the selected features. The Al 5056 Only and Ta Only datasets have a slightly lower MAE than the Al 5056 + Ta dataset, suggesting that the material-specific predictions are more accurate than with the dataset consisting of multiple material types. In this statistical analysis, the RMSE values for the test and train sets are also of interest, which corresponds to the standard deviation of the residuals. As this value measures the degree of scattering associated with the predictive errors of all data points in a given dataset, an RMSE of zero indicates a perfectly consistent predictive error, and higher values indicate increasingly scattered error. The RMSE values produced were calculated for both the test and train datasets to ensure that the predictive capacity associated with the test set was comparable to the train set. For the powders analyzed, the RMSE values of both the test and train sets for each dataset are less than 3, indicating relative success in consistently predicting flowability values for each sample. Of utmost importance is that within each dataset, the test and train RMSE values are comparable; this means that the model′s predictive capacity is sound when new data is introduced into the model with the training dataset. It is also worth noting that, again, like the MAE values, the Al 5056 + Ta dataset has higher values than the single material datasets, potentially suggesting that the material-specific flowability predictive models are the most successful.
Given the MAE and RMSE values in
Table 4, one can be confident in the success of the regression model implemented. Therefore, the features considered in the regression model can be ranked based upon their importance in predicting the target variable, owing to the features’ significance in influencing powder flowability on a larger scale. Using the “sklearn.feature_selection.f_regression” package of scikit-learn 1.0.1, the F-statistics for each feature of the Al 5056 Only, Ta Only, and Al 5056 + Ta datasets were calculated, which are presented in
Table 5.
For each of the three datasets in
Table 5, the features are ordered in descending order of their associated F-statistic values. Higher values correspond to an increased importance for model predictions and, therefore, more significant influence on predicting powder flowability. As a generalized observation, it appears that the F-statistic values for the features of the Al 5056 Only dataset are similar to one another. In contrast, the values are much further separated for individual features than others with the Ta Only dataset and the Al 5056 + Ta dataset. This may be a material-dependent property or at least a powder-dependent property, whereby the degree of F-statistic separation for different features may change if another Ta powder was considered, for instance.
With these three datasets, there appears to be some variation in the feature ranking based upon the material type and/or qualitative particle characteristics. For example, with the Al 5056 Only dataset, morphology parameters appear to be most influential in influencing flowability, with the “Median Surface Area” and “Median ” as the highest-ranking features for that powder type. This is contrasted by the results of the Ta Only dataset, where “Moisture Content” and several size parameters, such as “” and “Volume Percent of Particles Under 10 μm in Size”, are ranked the highest. The increased weight of particle morphology in flowability determination versus particle size and moisture content may be a material-dependent phenomenon when considering the innate differences between Al 5056 and Ta. However, it is also plausible that this depends on more holistic differences in the powder characteristics, such as the semi-spherical Al 5056 with a narrower PSD, compared to the angular Ta with a broad PSD. While this reasoning is not clearly distinguishable from the results of this study, the observations from the present work may be used to guide future experimentation to achieve these answers.
Another key observation from the feature ranking results is the importance of the “” parameter in the three datasets, particularly in the Al 5056 + Ta dataset. In this combined material dataset, the “” feature was by far considered the most important parameter in predicting flowability with an F-statistic nearly ten times as large as the next highest F-statistic. This is in stark contrast to the Al 5056 Only and Ta Only datasets, where the “” parameter was considered the least influential of the six features analyzed in both datasets, with the lowest F-statistic compared to the other features. From the results presented here alone, it is not entirely evident why “” ranked so much higher in the Al 5056 + Ta dataset compared to the other two. This is likely a by-product of the significantly reduced number of features considered in the regression models after VIF analysis and feature elimination; because only three features were considered and particle morphology was neglected with these features, it is reasonable to expect that subsequent flowability predictions would be altered. While the rankings from each material-based subset varied quite substantially, the results are all logical, intuitive, and based on fundamental concepts of particle dynamics, owing to the physical interpretability and statistical significance of the regression models after adequate feature selection.
3.6. Future Considerations
In this preliminary study, meaningful data has been generated thus far related to metallic powder flowability and moisture content that metal powder-based AM users can leverage to enhance their powder processing. However, from this study, several avenues of future exploration can be capitalized upon to help guide metallic powder handling and storage protocols.
It is critical to acknowledge that powder flowability and moisture content are incredibly nuanced properties. While this study provided a glimpse into understanding the ramifications of environmental exposure on powder properties and behavior, other factors not considered here were found to be rather impactful and should be incorporated in future work. For example, electrostatic charge buildup, usually through tribo-charging, has been shown to negatively impact a material’s flowability, mainly when the material contacted is nonconductive [
28]. This would be rather pertinent to metal powder-based AM, as most processes involve the contact of a powder sample with system components as it moves throughout the processing environment, where charge buildup can occur. Moreover, studies have indicated that electrostatic charge can be interdependent with powder moisture content, introducing another factor into this complex field of study that is necessary to acknowledge [
30].
In future studies, several design elements of the environmental exposure can be considered to invoke different material responses in both properties and behavior. In this study, the environmental exposure of the Al 5056 and Ta powders was completed in “standard” laboratory conditions, which involved controlled temperature and naturally varied humidity. The exposure conditions here do not necessarily represent the variety of powder handling and storage conditions experienced worldwide, where more “extreme” temperatures and humidity may be observed. Given the gravity of the effect of temperature and humidity on powder properties, such as moisture content, it would be prudent to explore how higher temperatures and humidity would influence subsequent characterization results. By the same token, the exposure duration could also play an important role, which warrants the variation of exposure time to more prolonged periods past 2 min and 10 min.
Additionally, future studies would benefit from adopting alternative methods to measure powder flowability and moisture content. In the present work, the Carney Funnel was used in place of the Hall Flowmeter Funnel to measure particle flowability; this was done to match the methods commonly utilized in the industry to capture particle flow behavior. However, it is important to consider that metal powder-based AM processes are often quite dynamic, which necessitates a dynamic powder measurement technique that can gain insights into the in-process behavior of a powder sample. A promising approach to simulate powder flowability in an AM process is through powder rheology, which mimics AM processing conditions so that AM powder users can understand how the powder will act during processing [
31]. TGA was utilized in this study to provide loss-on-drying measurements as a method of moisture determination. While TGA systems can produce extremely sensitive gravimetric measurements, the small quantity of each powder sample analyzed brings into question the representative nature of each powder tested, even if the powder is adequately sampled. Other test methods enable the measurement of larger quantities of powder yet still maintain sensitivity and precision, providing consistently repeatable results for quality moisture determination. One method that has proven relatively successful for moisture analysis of metallic powders is coulometric Karl Fischer titration coupled with oven desorption [
12]. It is worth noting that if these measurement methods were to change, it is inevitable that slight variations in the trends of flowability and moisture content with environmental exposure would be observed due to the innate differences between measurement methods. This could have significant ramifications on the results of future studies from a statistical analysis perspective, for instance, whereby the results of feature selection and feature ranking could be dramatically different from those demonstrated in the present work.
Finally, to increase the applicability of a future study to metal powder-based AM processing, it is important to consider several factors directly related to material processing. For example, the composition of the metallic powder can be monitored after exposure to ambient conditions. Given the elemental makeup of water, changes in oxygen and hydrogen may be observed during exposure, as well as the formation of hydroxides and other compounds on the surface of the powder [
14]. If any substantial composition changes occur, the material’s processability may be in question, given the association of mechanical, thermal, or electrical properties with composition. Another natural avenue to relate a future study to metal powder-based AM is to utilize the exposed powders in an AM process, which would enable the direct determination of the effect of environmental exposure on powder processability, given the changes in powder properties and behavior.