Abstract
The appearance of new dangers in the form of harmful aerosols containing nanoparticles has necessitated work on ensuring effective protection of humans’ respiratory systems. So far, there is no uniform method, which would make it possible to classify filtering devices, for evaluating the efficiency of respiratory protective devices against nanoaerosols. The authors assessed the morphology of various nanoaerosols of NaCl, titanium dioxide in two forms, anatase and rutile, and aluminosilicate based on observations using a scanning microscope. Then the efficiency of filtration of meltblown fabrics with surface densities of 30, 50, 70, and 90 g/m2 against those nanoaerosols were tested. The experimental results were subjected to the theoretical analysis based on filtration theory. For all the fabric types, similar filtration efficiencies were obtained irrespective of the morphological structure of the nanoaerosol particles. The theoretical predictions are in good agreement with the experimental results. The conclusion is therefore drawn that equipment can be evaluated based on testing of filtration efficiency against any tested aerosols.
For a number of years there has been rapid growth in the worldwide usage of nanotechnologies. 1 In surface engineering the application of nanocoatings produces significant changes in the properties of a material, such as adhesion, tribology, optics, and electrostatic properties.2,3 In biology and medicine they have led to the development of tissue engineering. 4 Nanoparticles are now also used in less complex technological processes, such as the production of nonscratch spectacle lenses; crack-resistant paints; anti-graffiti wall paints; dirt-resistant materials; self-cleaning windows; the production, processing, and packaging of foodstuffs; and in cosmetology. 5 Nanoparticles are also commonly produced in such processes as combustion, cleaning, and welding. It should be noted, however, that in spite of the significant advantages of using this type of technology, the development of nanotechnology brings with it many not fully identified dangers, most of which involve diseases transmitted to the respiratory system. 6 Hence the effective protection of the respiratory system against nanoaerosols has become an important subject of research in the context of investigating of the mechanisms of the filtration of nanoparticles by filter materials, as well as developing materials for use in respiratory protective devices. 7
In order for it to be used by workers, respiratory protective equipment must be tested according to the relevant procedures. In the European Union the testing of filters and filtering half-masks is conducted in accordance with the methodology described in EN series standards (EN 143:2000 and EN 149:2001 + A1:2009)8,9 harmonized with Directive 89/686/EEC. 10 The efficiency of the protection provided by these materials is evaluated as an index of penetration with the use of two model aerosols: non-neutralized polydisperse NaCl and paraffin oil particles at a flow rate of 95 L min−1. For NaCl aerosol the diameter of the particles varies from 40 to 1200 nm with an MMD of 600 nm. For polydisperse oil the particle size distribution is a log-normal distribution with a number median Stokes diameter of 400 nm and a GSD of 1.82. Although the given particle size distribution values differ significantly from the dimensions of nanoparticles encountered in workplaces, no new testing methodology that would enable the classification of filter equipment with respect to a range of nanosized particles has been established. Owing to the lack of regulations in this area, manufacturers of respiratory protective equipment are not able to provide users with information to properly select equipment appropriate to the level of hazard present in particular workplaces. In spite of the numerous publications available concerning the evaluation of the commercial respiratory protective equipment in common use in workplaces in the European Union and the United States,11, 12 the issue of correct selection of equipment has not been fully addressed.
In order to bring the methodology for filtration efficiency testing against nanoparticles closer to the actual conditions found in workplaces, it is necessary to establish all process dependencies. Numerous studies have been made on the dominant mechanisms of filtration over a wide range of nanoparticles, using the model aerosols of NaCl and silver particles. The authors have undertaken research to determine how the type of aerosol used for testing influences the filtering efficiency of the meltblown filter materials commonly used in respiratory protective equipment. This direction of experimentation is motivated by the conclusions drawn from research 13 on the effect of polystyrene nanoparticles with positive and negative charges and with diameters of 20, 100, and 120 nm and monolayer carbon nanotubes suspended in the air on epithelial cells in rats, which demonstrated disturbance in their functioning. Those authors concluded that the physicochemical properties of the nanoparticles (i.e. their size, structure, shape and superficial charge) are especially significant factors affecting how they act on the barrier provided by the epithelial layer in the lung alveoli. Moreover, the need to carry out tests using aerosols with various morphological structures is also indicated by the results of studies 14 on nanoparticles with diameters <100 nm collected in the vicinity of major freeways around Los Angeles. Such morphological forms as aggregates, spherical particles, irregularly shaped particles, and particles with numerous inclusions were observed in aerosol samples. It was suggested that in the case of many of these particles, a heterogenic internal mixing occurred. One of the most important conclusions from this research was that a reduction in the concentration of particles, for example due to a greater distance from the source of emission of the primary aerosol, does not reduce the intensity of the processes of collision and the joining of nanoparticles into larger conglomerates. Hence a fundamental objective of the present work was to establish if the proper evaluation of the efficiency of filter equipment requires the conduction of simulation tests using real nanoaerosols.
Experimental method
Tested materials
The tests were carried out on nonwoven filter fabrics produced by a meltblown method, at an experimental stand at the Central Institute for Labour Protection National Research Institute. The production of meltblown fabrics involved blowing off a molten polymer into elementary fibers with various thicknesses and lengths, which settle on the collecting device to form a compact porous nonwoven fabric. The pneumothermal technique enables the formation of filter fabrics used for respiratory protection with surface densities between 10 and 150 g/m2. Since low-density fibers have insufficient strength, and those of a high density produce too great resistance to air flow, the following values of nominal densities were selected for use in the experiments: 30—70—50—90 g/m2.
Properties of Malen P F401 polypropylene granulate
Characteristics of meltblown filter media
The filter materials were produced from a granulate of F 401 polypropylene, with basic properties given in Table 1.
The surface density of the filter material produced was dependent on the traverse speed of the receiving device where the material was formed. The surface density of the samples was calculated by weighing samples with an area of 500 cm2. The standard deviation of the mean value was 10% for each thickness of the nonwoven fabric. The thicknesses of the respective variants of nonwoven fabrics are given in Table 2.
The filtration parameters for produced, nonwoven fabrics were set at the level of first-class protection in respect to European standards EN 143 and EN 149.9,10 For these standards, the maximum value of the penetration of paraffin oil vapor is 20% at a breathing resistance up to 210 Pa.
Figures 1 and 2 show a polypropylene filter material with a surface density of 90 g/m2. The fibers shown in the figures are twisted and form a three-dimensional structure. Their surface is smooth. The study of the porosity and dimensional distribution of the fibers indicates that the structure of the filtration materials tested was identical for all surface densities.
Polypropylene filter material with a surface density of 90 g/m2 at a magnification of 1000. Polypropylene filter material with a surface density of 90 g/m2 at a magnification of 5000.

Dimensional distribution and porosity of filtering materials of surfaces densities 50 g/m2 and 90 g/m2
Test aerosols
The tests used four aerosols obtained from an aqueous solution or suspension of the following substances: sodium chloride, titanium dioxide in anatase form, titanium dioxide in rutile form, and aluminosilicate (marked in Figures 12–15 as Al-Si), which contained nanoparticles over a particle size range from 7 to 300 nm. The aerosols differed in terms of the density of the material and the morphological structure of the particles. The lightest was sodium chloride with a density of 2.1 g/cm3, the aluminosilicate aerosol had a density of 2.8 g/cm3, and the heaviest was titanium dioxide at 4.2 g/cm3.
The sodium chloride was generated from 0.1% aqueous solution and the other aerosols from a suspension with analogous concentration. All aerosols were produced using a TSI atomizer, at an input air pressure of 2.5 bar.
Figures 3–6 show the particle size distributions of the test aerosols used.
Size distribution of NaCl aerosol. Size distribution of rutile aerosol. Size distribution of anatase aerosol. Size distribution of aluminosilicate aerosol.



Figures 7–10 show atomic force microscope photographs of the nanoparticles of the tested aerosols, enabling their shape and dimensions to be determined. The aerosols were selected in such a way that they comprised nanoparticles of different shapes. This was to reflect the impact of the different tendencies the particles could exhibit in adhering to the surface of fibers, which depends on their nature and morphology.
NaCl aerosol particle: (a) surface image, (b) 3-D image. Rutile aerosol particle: (e) surface image, (f) 3-D image. Anatase aerosol particle: (c) surface image, (d) 3-D image. Aluminosilicate aerosol particle: (g) surface image, (h) 3-D image.



The nanoparticles of the sodium chloride aerosol (Figure 7) have a cubic shape. The anatase particles (Figure 8) are oval, and the rutile particles are shaped like prisms with rhomboid bases, while the aluminosilicate particles are cylindrical.
The nanoaerosol particles analyzed, therefore, differ in morphology and shape but maintain the fractal dimension at a similar level: 3.
The aerosol particles were neutralized using an ionization neutralizer, but they exhibited different dielectric constants, which for sodium chloride was 5.9, for aluminum silicate 6.8, and for titanium dioxide about 100.
Experimental setup
Penetration tests with aerosols containing nanoparticles, for the produced filter materials and selected aerosols, were carried out using the equipment illustrated and explained in Figure 11.
Schematic diagram of the experimental set-up: 1. Nanoaerosol generator, 2. Desiccant, 3. Electrostatic charge neutralizer, 4. Testing chamber, 5. Sample holder, 6. Electrostatic classifier of particles, 7. Condensation nanoparticle counter, 8. Personal computer, 9. Compressed air valves, 10. Flow meters, 11. High-efficiency filter, 12. Test sample.
Compressed air was pumped via filters, dryers, and flow meter10 to a particle generator1. The generated aerosol was then passed to a desiccant2 and a particle electrostatic charge neutralizer3. To obtain a flow rate of 90 l/min, corresponding to the ventilation of the lungs when the human body is under significant physical strain, the aerosol was mixed with an additional air stream through an additional flow meter10. After mixing, the dried and neutralized aerosol was passed to a chamber4 in which the tested filter material12 was fastened. From the chamber the aerosol was discharged via highly effective industrial filters11. The aerosol samples were collected from the chamber before and after passing through the tested filter and were passed to a TSI 3080 electrostatic particle classifier6 and a TSI 3775 condensation nanoparticle counter7. With these instruments an analysis of the size distribution and concentration of nanoparticles was made. The measurement range of the system enabled testing of the particles from 7 to 270 nm, divided into 90 measurement classes.
The procedure of the study of the penetration of nanoparticles through filter materials consisted of
the measurement of the particles concentration at the outlet of the empty test (chamber without filter sample), the measurement of particles concentration in the air after the test chamber with the filter installed, and a comparison of these two values to calculate the penetration.
The test time was set at seven minutes to obtain an average concentration and distribution of particles in three measurement cycles of 120 seconds each, with a 15-second pause between cycles to allow for the resetting of the electrostatic particle classifier.
The stability of the background had been checked and verified in previous studies involving repeated tenfold measurements of the background. The results confirmed its stability over time and that there were no changes in both the concentration and the dimensional distribution of the nanoparticles of the generated aerosol. A diagram of the measuring stand is shown in Figure 11.
Comparison of theoretical calculations with experimental data
For the experimental data obtained, a comparative analysis was performed using classic filtration theory as described in many research papers.3,15,16
The equation for the filter penetration P, used to calculate the theoretical curve, had the classical form
The filter surface density
Considering that the diameters of the tested nanoparticles ranged from 7 to 270 nm, it was assumed that the basic mechanisms of deposition of particles on the filter fibers were diffusion
The efficiency of a single fiber based on the diffusion mechanism is found from an equation based on Peclet’s number, which is defined as follows:
The coefficient of diffusion is defined as
The Cunningham slip factor Cc was computed on the basis of the equation for dp within a limit of 100 nm
The efficiency of a single fiber for the diffusion mechanism was calculated from the equation given by Davies
16
The efficiency of a single fiber for the mechanism of direct interception was found from
The Kuwabara hydrodynamic factor, Ku, was computed from
The efficiency of a single fiber based on the mechanisms of diffusion and direct interception, assuming that the two mechanisms are independent, is computed using
The diffusion mechanisms, which affect nanoparticles most intensely, were included in the theoretical computations (based on the data in the literature 3 ) on the model process of the filtration of nanoaerosol particles. This is a direct attachment mechanism, which exerts a significant effect on particles of diameters more than 200 nm. The inertia mechanism, which for particles of diameters up to 200 nm is negligible, was not included. For the high flow rate applied and the small mass of aerosol particles, the gravity mechanism was not included in the analysis, since gravity becomes significant only in respect to particles with diameters greater than 5 µm.
Because the nonwoven fabric used for the tests was produced without the application of an electrostatic charge and the charge of the aerosol particles was neutralized, the electrostatic field forces were not taken into consideration and, hence, neither was the mechanism of deposition involving electrostatic field forces.
Results and discussion
The results of the tests are presented in graphic form. The graphs in Figures 12–15 show the calculated penetrations of an aerosol containing nanoparticles of the various tested materials depending on the diameter of particles for a selected filter fabric. It was found that there were no significant differences between the penetration results obtained for different aerosols in all of the investigated cases. This is confirmed by the theoretical curve obtained for particular thicknesses of filter material, which fits well with the experimental data and the scanning microscope photographs showing the shape of the aerosol particles (Figures 7–10).
In Figures 12, 13, and 14, the theoretical curve marked as “Model” is in agreement with the experimental curves within a particle diameter range from 7 to 100 nm. At more than 100 nm, the theoretical curve moves slightly upward, which may be due to a high degree of non-uniformity in the structure of the experimentally obtained fabric and a slight excess electrostatic charge produced during the formation of the fabric. In the case of the fabric of density 90 g/m2 (see Figure 15), the theoretical curve agrees with the experimental curves over the entire particle size range from 7 to 250 nm.
Comparison of experimental data for change in penetration of aerosol nanoparticles through a filter material of area density 30 g/m2 and theoretical calculations for the model adopted. Comparison of experimental data for change in penetration of aerosol nanoparticles through a filter material of area density 50 g/m2 and theoretical calculations for the model adopted. Comparison of experimental data for change in penetration of aerosol nanoparticles through a filter material of area density 70 g/m2 and theoretical calculations for the model adopted. Comparison of experimental data for change in penetration of aerosol nanoparticles through a filter material of density 90 g/m2 and theoretical calculations for the model adopted.



For a fabric with density 30 g/m2 (see Figure 12), the maximum value of penetration is at a level of 60% for particles in the range of 150–200 nm. For fabric with density 50 g/m2 the maximum penetration value is around 45%; for density 70 g/m2, it is at a level of 35%; and for density 90 g/m2, it is 20%. In all cases there is a clear relationship between penetration and the thickness of the filter material; thus an increase in area density causes an increase in the resistance to air flow and a decrease in penetration, the two basic parameters that determine a material’s filtration properties. These relationships are confirmed by earlier research. 17 – 20
In order to confirm the lack of differences between the experimental curves and the theoretical curve, a statistical analysis was performed. All data obtained for a given aerosol was included in the analysis and checked for statistically significant differences among the range of aerosols examined.
Both the analysis of variance ANOVA and the multiple comparisons tests (Scheffe’s and Dunnett's) indicated no statistically significant differences in penetration values for different variants of filter materials (probability >0.05) between the aerosols examined.
Mean value of penetration of anatase nanoaerosol for tested filtering materials
The results of the tests show that penetration is not dependent on the shape and size of the particles or on the density of the material from which they are made. This has also been confirmed by tests on the filtration efficiency of polypropylene fibers, carried out using spherical PSL particles and cubic MgO particles, in a diameter range of 50 to 300 nm and at linear velocities of 10 and 20 cm/s. 21 It was found that, irrespective of their shape, both types of particles had analogous filtration efficiency, which was confirmed in the described experiments for a linear velocity of 15 cm/s.
Filter materials capture particles with sizes between 7 and 250 nm due to two principal mechanisms: diffusion and direct interception. The contribution of other mechanisms, such as gravitation and inertia, is negligibly small. The best fit of the theoretical curve to the experimental data was obtained for particles with diameters in the range from 7 to 100 nm. This applied to all tested nanoaerosols. The results agree with other experimental data for silver nanoparticles. 22 This confirms that penetration is independent of the type of nanoaerosol used to evaluate the efficiency of filtration. The dominance of the diffusion mechanism in the filtration of nanoparticles has also been shown in tests of penetration by particles in the range from 4 nanometers to 10 micrometers 23 and in studies of the effect of the uniformity of the filter material for nanoparticle penetration. 24
Conclusions
The experiments show that, when evaluating the efficiency of filter materials used in respiratory protective devices against the hazard caused by nanoparticles, it is not significant which test aerosol is selected. Within a particle size range from 7 to 250 nm, the test aerosol may be any of those used in this research. In all cases, penetration was at an analogous level in the range from 7 to 100 nm and was in accordance with theoretical predictions. In this case the shape of particles with nanometric dimensions is not significant for penetration what is in accordance with classical filtration theory cited in this paper.
Footnotes
Acknowledgments
Publication based on results obtained under Operational Programme Innovative Economy (POIG) 2007–2013, Priority 1: “Research and development of modern technologies”; Submeasure 1.1.2: “Strategic programmes of scientific research and development”.
POIG Project 01.01.02-10-018/09 titled: “Innovative polymer and carbon materials for protection of respiratory system against nanoparticles, vapours and gases.”
Funding
This research received no specific grant from any funding agency in the public, commercial, or not-for-profit sectors.
