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Synthesis of multihollow polyester particles in supra- and infra-millimeter size ranges by double emulsion process.


Multivesiculated particles (MVPs) are a type of multihollow polymeric particles that have industrial use as opacifying agents in waterborne paints. The large refractive index difference between polymer shell and entrapped air results in scattering of incident light, increasing the opacity of a coating loaded with these particles. MVPs can therefore partially replace the costly titanium dioxide pigment traditionally used [1].

MVPs are produced by a double emulsion process that yields crosslinked polyester particles with diameters between 1 and 10 [micro]m [1-3]. Their interior consists of multiple homogeneously distributed spherical microalveoli separated by thin polymer walls. Considering the mechanical resistance of the thermoset matrix combined with the multivesiculated internal morphology, other applications beyond the context of coating opacification can be envisaged for these particles [4]. This, however, implies producing them with larger sizes, depending on the particular application. Particles with diameters of tens of microns may have uses in encapsulation of active substances [5, 6], low-density fillers in thermoplastic [7], and thermoset matrixes [8] and syntactic foams [9], Larger diameters, in the range of a few millimeters, may be used as low-density fillers in particleboards [10] or as catalyst support [11].

This work studies the feasibility of producing MVPs with different size ranges, using as reference the procedure used for synthesis of the "small" MVPs used in paint formulations. This approach [1] starts with dispersion of an organic phase, comprising unsaturated polyester dissolved in styrene, in an aqueous solution of poly(vinyl alcohol) (PVA) at high stirring rate (dispersion step). Water diffuses into the dispersed organic phase, forming droplets in its interior. This water-in-oil (W/O) emulsion is stabilized by hydrophilic acid-base ion-pairs formed by neutralization of terminal polyester carboxylic groups with an added amine, without need for addition of a surfactant. The whole system is, therefore, a water-in-oil-in-water (W/O/W) double emulsion. The organic phase is then hardened by addition of a radical initiator (cure step). The entrapped water evaporates and originates air-filled vesicles after drying. Figure 1 illustrates the entire synthesis process.

In a previous work, we studied the influence of different factors on MVPs synthesis, namely the time of dispersion of the organic phase in the aqueous medium, and the concentrations of amine, polyester, and protective colloids [1], The role of the type of the amine in the stabilization of the W/O emulsion system has also been studied [2], as well as the effect of curing conditions on the particles properties [3], All these works dealt with average diameters below 10 /an. Larger sizes, in the order of hundreds of micron, have been produced only using a microfluidic system, using a two-step emulsification approach distinct from the one-step batch reactor route described above [12].

This work discusses the influence of several process variables and procedures on the size and internal vesiculation of MVPs. It is shown that homogeneously vesiculated MVPs can be produced in a batch reactor using a double-emulsion approach, with average diameters ranging from tens of microns to a few millimeters.



The unsaturated polyester--obtained by polymerization of maleic anhydride, phtalic anhydride, and propylene glycol monomers--was kindly provided by Resiquimica (Mem Martins, Portugal) in the form of a solution in styrene (weight ratio 70/30, acid value 15-20 mg KOH/g and Brookfield viscosity in the range of 1000-2000 mPa s). Styrene and ammoniacal ferrous sulphate were also provided by Resiquimica. Poly (vinyl alcohol) (Mowiol 47-88, MW > 205,000 g/mol, degree of hydrolysis = 88%) was kindly provided by Archroma (Reinach, Switzerland). Poly (vinyl alcohol) (MW= 13,000 g/mol, degree of hydrolysis = 88%), diethylenetriamine (DETA, 98%), and cumene hydroperoxide (technical grade, 80%) were supplied by Sigma-Aldrich. Dibenzoyl peroxide 75% remainder water was provided by Acros Organics (Geel, Belgium).

Multivesiculated Particles Production

The formulation of the single-step double emulsion is described in previous works [1, 13] and was adopted as the reference. The unsaturated polyester solution (15 g) was first neutralized with DETA (0.21 g) and then diluted in styrene (6.5 g). Then this mixture was gradually added to an aqueous solution (61.7 g), containing 2.3% wt. PVA, in a jacketed glass reactor (100 ml), under constant mechanical agitation (600 rpm) using a helix impeller (40 mm diameter). After all organic phase being added, stirring was maintained for 20 min. The cross-linking of the unsaturated polyester with styrene was then initiated by adding 0.12 g of cumene hydroperoxide and 0.01 g of ferrous sulphate. The curing stage lasted 2 h at 70[degrees]C. Final particles were washed with distilled water and dried at 80[degrees]C for 2 h.

An alternative cure procedure was also studied, using dibenzoyl peroxide as curing initiator. The organic phase (polyester, styrene, and amine solution) was mixed with 3 wt% of dibenzoyl peroxide and cured at 60[degrees]C for 2 h.

Particle Size Distribution

The particle size distribution (PSD) of the smaller MVPs (<100 pm) was measured on a Beckman Coulter LS230 light scattering system, with Polarization Intensity Differential Scattering (PIDS) assembly and an obscuration of 45%. The particle size distributions were computed by the equipment's software, based on Mie theory for light scattering. The measurements were made after sample collection from the reactor and after particles drying.

Final particle size distributions for larger MVPs (>1 mm) were obtained by sieving (sieves with open mesh of 1 and 2 mm, supplied by Retsch)

Scanning Electron Microscopy

Particle morphology and internal vesiculation were observed by scanning electron microscopy, using an FEI Quanta 400FEG ESEM/EDAX Genesis X4M equipment (SEM) analysis at Centro de Materiais da Universidade do Porto (CEMUP). For this purpose, dried particles (larger and smaller) were encapsulated in epoxy resin, and the resulting composite was fractured in liquid nitrogen after hardening at 90[degrees]C overnight. Before being analyzed, samples were sputtered with gold/platinum using a K575X Sputter Coater by Quorum Technologies.

Mercury Porosimetry

The apparent density of the particles was determined by mercury porosimetry with a Poremaster 60 model from Quantachrome.

The density of the polymer (nonvesiculated polyester reticulated with styrene) was determined by water pycnometry.

Taguchi Method for Design of Experiments

The effect of the following four independent process variables on particle size was studied: stirring rate during the dispersion step ([v.sub.disp]), stirring rate during the curing phase ([v.sub.cure]), PVA concentration, [C.sub.PVA]. and PVA molecular weight ([MW.sub.PVA]). Three levels were set for the first three variables and two for the last, as shown in Table 1.

The minimum number of experiments required by Taguchi method can be calculated based on the degrees of freedom (DOF) approach: 1+3 X (3-1) + (2 -1) = 8. Orthogonal arrays L9 or L18 could therefore be chosen for design of experiments. To improve robustness of results, L18 was chosen. For all experiments, the performance parameters were determined according to the weight of sieved particles for the different sizes considered. For all experiments, the MVPs production process was based on the reference procedure described before, using dibenzoyl peroxide as curing initiator.


Design of Experiments

The complete Taguchi's experimental design is summarized in Table 2. Two distinct goals were defined. One consisted in obtaining particles with diameters smaller than 100 [micro]m, appropriate for incorporation as fillers in thermoplastics or thermosets. The other implied obtaining diameters larger than 1 mm, needed for incorporation in wood particleboards, for instance. Commercial statistical software package JMP was used for data analysis. To evaluate the significance level of the effects of the different factors, an analysis of variance (ANOVA) was performed.

ANOVA Analysis

The analysis of variance (ANOVA) is a powerful technique to explore the relative contribution of factors affecting a response. With ANOVA, the optimal combination of the process variables can be predicted. Figure 2 shows the prediction profiles of the effects of the different factors on particle size. The effects of the several factors on each performance parameter (content of MVPs diameter <100 [micro]m and >1 mm) are presented in Tables 3 and 4, respectively.

As shown in Table 3, ANOVA results reveal that the stirring rate during the dispersion step ([v.sub.disp]) has no significant effect in defining the particle size of MVPs. PVA concentration ([C.sub.PVA]) and molecular weight ([MW.sub.PVA]), on the other hand, are seen to be very significant for production of small particles. Concerning obtaining particles larger than 1 mm (Table 4), this is not affected by PVA concentration, while its molecular weight and the stirring rate during curing ([v.sub.cure]) can be considered very significant factors.

The fact that the stirring speed during dispersion of the organic phase in water does not have a relevant effect on the final particle sizes can be easily interpreted. The double emulsion droplets will tend to coalesce and form larger droplets if the stirring in the curing the step is lower than in the dispersion step. It is therefore in the initial stage of curing, while the organic phase is still sufficiently fluid, that the final particle sizes are defined, largely independently on the intensity of dispersion in the previous step. Stirring rate during cure, [v.sub.cure], is therefore a much more relevant factor for particle size, especially when large particles are the target. This is because shear tensions in the liquid medium must be minimized to allow for the dispersed phase to coalesce into sufficiently large droplets.

PVA acts as protective colloid, stabilizing the double emulsion droplets by adsorbing onto their surface [1], It is understandable that its concentration has a major influence on the fraction of smaller particles, since small droplets can only survive up to the final curing process if steric stabilization is effective. When large particles are intended, on the other hand, [C.sub.PVA] does not play a significant role, as the colloid concentration in the droplet surface is sparse and the droplet sizes are mainly controlled by shear rates.

The molecular weight of PVA showed to be a variable with a major influence. Increasing [MW.sub.PVA] simultaneously increases the fraction of small particles and decreases the fraction of large particles. On one hand, larger molecular weight originates significantly higher viscosity in the aqueous medium, increasing shear forces and causing rupture of larger organic droplets. On the other hand, it ensures more effective steric stabilization and reduces coalescence induced by droplet collision.

Figure 3 shows the examples of weight-based particle size distributions measured for Experiments 1, 5, 6 and 18. In the first case, a large mass fraction corresponds to particles with diameters above 1 mm. Almost 30%, however, still present sizes between 0.1 and 1 mm. The way how these remaining smaller particles can be minimized will be discussed below. Experiments 5 and 6 yielded an intermediate distribution, as expected from the operation variables used. In Experiment 18, all variables have maximum values, except for [v.sub.cure], and all particles fall within the small particle range, with sizes below 0.1 mm.

The particle size distribution of the particles produced in Experiment 18 was determined in more detail using a light scattering system. The result is shown in Fig. 4. The distribution is relatively broad, with diameters in the range 5-55 [micro]m. A narrower distribution, also shown, was possible by using a 20 [micro]m sieve. Figure 5a shows the SEM image of MVPs produced in Experiment 18, after sieving. As seen in Fig. 5b, the particles interior is uniformly vesiculated, with homogeneously distributed spherical alveoli separated by thin polymeric walls.

Effect of Dispersion Stirring Rate on Particle Vesiculation and Density

The previous section was focused on adjusting synthesis conditions for maximizing production of MVPs within an intended size range. However, in addition to particle diameter, the quality of internal vesiculation has also to be taken into consideration as this directly influences particle density and other properties like light diffraction/opacity. The formation of the internal alveoli occurs by water diffusion from the continuous aqueous phase toward the interior of the organic droplets, forming a double emulsion during the dispersion step. It is not a priori clear whether this process can effectively lead to uniform vesiculation of organic droplets with diameters above 100 [micro]m.

SEM images shown in Fig. 6 illustrate the influence of different stirring rates during the dispersion step on internal particle morphology. For producing these particles, PVA concentration was 2.3 wt% and molecular weight 13,000 g/mol, cure temperature was 60[degrees]C during 2 h, under a stirring rate of 200 rpm. The studied stirring rates during dispersion were 200, 600, 750, 1000, and 1400 rpm. As the stirring rate is increased from 200 to 750 rpm, the concentration of vesicles in the center of the particles visibly increases, maintaining an average diameter of about 2 [micro]m (Fig. 6a-c). At 750 rpm, the particles are fully vesiculated. As the stirring rate is increased to 1000 rpm (Fig. 6d), larger vesicles are observed, with diameters of about 10 pm, but most are still within 2 [micro]m average size. At 1400 rpm, the particles remain fully vesiculated, but the alveoli are uniformly large, with about 15 [micro]m diameter. These results provide information on how the dispersion step determines particle vesiculation. The operation conditions used were the same as for Experiment 6 in the Taguchi method (Table 2), except that [v.sub.disp] assumed a set of distinct values. As discussed before, the particles produced under these conditions have diameters in the order of several hundred microns. For organic phase droplets in this size range, water diffusion becomes a limiting step that significantly delays formation of the water-in-oil-in-water double emulsion and hence inner vesiculation. When stirring rate is kept low during this step, the droplets remain with relatively large sizes until hardening, and water penetration is not rapid enough to fully form a homogeneous double emulsion within the dispersed organic phase. Figure 7 shows the SEM image of the periphery of a cured particle produced under [v.sub.disp] = 200 rpm. The concentration of vesicles is higher close to the external surface, forming a gradient relatable to the extent of water diffusion into the organic droplet. As rate of stirring is increased, the organic phase undergoes frequent rupture as a consequence of higher shear stresses, forming smaller droplets. Full emulsification of water within these droplets can therefore be effectively attained within the dispersion time for [v.sub.disp] = 750 rpm. The droplet size ends up increasing again during the beginning of the curing step, where low stirring rates are used (200 rpm in this case), due to coalescence under lower shear. But the double emulsion is already fully established, and uniform vesiculation is achieved. If stirring is increased further, the droplet rupture/collision processes intensify, and coalescence of the water droplets emulsified within the organic phase occurs. Larger vesicles start to form at 1000 rpm, and at 1400 rpm, most vesicles present large sizes of about 15 [micro]m.

It can be concluded that the rate of stirring during the dispersion step, while not having a relevant effect on final particle size, has a major influence on the homogeneity of internal vesiculation, and on vesicle size.

The apparent density of the cured MVPs depends directly on vesiculation as this originates the air-filled void space within the dry particles. As expected, Fig. 8 shows that increasing stirring rate during dispersion leads to a reduction on apparent density. The effect is less significant for the higher stirring rates, since the particles are already fully vesiculated and only vesicle size increases. The lowest density of 0.52 x [10.sup.3] kg/[m.sup.3] was obtained for 1400 rpm. Note that the density of the unvesiculated cross-linked polyester is 1.2 x [10.sup.3] kg/[m.sup.3].

Effect of the Type of Curing Initiator on Mechanical Stability of Large Particles

The reference MVPs formulation uses cumene hydroperoxide as free radical initiator, in combination with a metal redox activator (aqueous solution of ferrous sulphate and diethylenetriamine), to promote cross-linking between polyester and styrene at relatively low temperatures [3], This cure initiator system is added to the aqueous phase at the beginning of the curing step. However, when the larger particles were produced, with diameters above 1 mm, it was observed that all became fractured during drying. This occurred even when gentle drying conditions were used, like 80[degrees]C for 2 h. Figure 9 shows the resulting cracked particles. This phenomenon can be attributed to evaporated water not being able to diffuse fast enough toward the exterior in large particles, rising internal pressure and causing fracture. Residual stresses, accumulated within the particle during polymer hardening, facilitate this type of structural failure. Since cure-initiating radicals are formed in the aqueous phase and then diffuse into the organic droplets, polymer hardening starts from the periphery toward the center of the particles. Therefore, the fact that the initiator is water soluble may actually contribute to development of residual stresses upon cure.

The former hypothesis was tested by replacing the original water-soluble initiator with dibenzoyl peroxide, BPO, which is directly soluble in the organic phase. BPO was therefore added to the polyester solution before its dispersion into the aqueous phase. Radical formation is in this case initiated by rising temperature (to 80[degrees]C or above), therefore preventing premature hardening before double emulsion formation. This implied investigating the appropriate BPO concentration in the polyester + styrene organic phase, in order to obtain a short curing time. Table 5 shows the gel time obtained for BPO concentrations of 1, 2, and 3 wt%. For 3 wt%, the organic solution begins to form a gel after about 5 min. This concentration was tested in MVP production. The obtained MVPs were uniformly vesiculated and did not fracture upon drying in the same conditions as before.

Effect of the Second Stirring Step During Dispersion on Particle Size

As discussed in the section "ANOVA Analysis", the "optimal" operating conditions for producing large MVPs still yield a significant fraction of particles with smaller sizes (lower than 1 mm). In an attempt to minimize this, the second dispersion step was introduced, in which the stirring speed was reduced to 200 rpm for 15 min prior to initiating cure. Figure 10 shows the results obtained, for two initial dispersion speeds (750 and 1000 rpm). The lower stirring in the second step allows for coalescence of the organic droplets, leading to a significant shift of the final distribution toward the right. Interestingly, when stirring speed in the first step is increased to 1000 rpm, the final fraction of particles below 1 mm decreases even further. The higher initial shear in the aqueous medium produces a large number of smaller droplets that then coalesce into much larger ones when stirring decreases. Figure 11a shows the particles obtained using this new approach, while Fig. 11b shows the surface and interior of a particle fractured manually, showing the high degree of vesiculation.


Multivesiculated particles (MVPs) were successfully synthesized in two different size ranges (<100 [micro]m and >1 mm). The concentration and molecular weight of PVA, used as protective colloid, have a very significant influence in the production of small particles. MVPs with diameters below 100 [micro]m were obtained with PVA of 205,000 g/mol molecular weight and 3.45 wt% concentration.

Concerning production of large particles, the effect of some process variables was identified. Sufficiently high stirring rate during the dispersion of polyester droplets in water is essential to guarantee good vesiculation and thus minimum density. If organic droplet size is not reduced during this step, water is unable to diffuse into it to achieve full vesiculation. The yield of particles above 1 mm was determined mainly by PVA molecular weight and stirring rate during the curing step. This was further improved when a period of low stirring speed was added to the dispersion step, allowing for droplet coalescence before curing. Large particles with diameter above 1 mm and about 90 wt% yield was produced with PVA molecular weight of 13,000 g/mol, initial stirring in dispersion step were of 1000 rpm for 20 min followed by 200 rpm for 15 min, and curing under the same stirring rate for 2 h.

The large particles fractured during drying due to water evaporation generating internal pressure build up. Residual stresses originated by polymer hardening being started at the outer shell and progressing toward the interior facilitated this tendency to fracture. This problem was eliminated by using an organic-soluble cure initiator instead of a water-soluble system.


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Sandra Monteiro, (1) Angela Dias, (1) Jorge Martins, (1,2) Luisa Carvalho, (1,2) Fernao D. Magalhaes (1)

(1) LEPABE--Faculdade de Engenharia, Universidade do Porto, Rua Dr. Porto, Roberto Frias 4200-465, Portugal

(2) DEMAD--Department of Wood Engineering, Polytechnic Institute of Viseu, Campus Politecnico De Repeses, Viseu 3504-510, Portugal

Correspondence to: F.D. Magalhaes; e-mail: Contract gram sponsor: FEDER (Fundo Europeu de Desenvolvimento RegionalVQREN (project Lightfillers); contract grant sponsor: Project UID/EQU/00511/2013-LEPABE (Laboratory for Process Engineering, Environment, Biotechnology and Energy; contract grant number: EQU/ 00511 ; contract grant sponsor: Programa Operacional Competitividade e Internacionalizacao; contract grant number: COMPETE2020; contract grant sponsor: FCT, Fundacao para a Ciencia e a Tecnologia.

DOI 10.1002/pen.24284

Published online in Wiley Online Library (

TABLE 1. Process variables (factors) and set levels.

Factors                Level 1   Level 2   Level 3

[v.sub.disp] (rpm)       250       500       750
[v.sub.cure] (rpm)       200       350       500
[C.sub.PVA] (%)         1.15       2.3      3.45
[MW.sub.PVA] (g/mol)   13,000    205,000

The factors studied were stirring rate during the dispersion
step ([v.sub.disp]) stirring rate during the curing phase
([v.sub.cure]), PVA concentration ([C.sub.PVA]), and PVA
molecular weight ([MW.sub.PVA]).

TABLE 2. L18 orthogonal array used for design of experiments,
according to Taguchi method, and particle weight fractions
obtained in each experiment.


             [v.sub.disp]   [v.sub.cure]   [C.sub.PVA]   [MW.sub.PVA]
Experiment      (rpm)          (rpm)           (%)         (g/mol)

1                250            200           1.15          13,000
2                500            350           1.15          13,000
3                750            500           1.15          13,000
4                250            350            2.3          13,000
5                500            500            2.3          13,000
6                750            200            2.3          13,000
7                250            500           3.45          13,000
8                500            200           3.45          13,000
9                750            350           3.45          13,000
10               250            500           1.15         205,000
11               500            200           1.15         205,000
12               750            350           1.15         205,000
13               250            200            2.3         205,000
14               500            350            2.3         205,000
15               750            500            2.3         205,000
16               250            350           3.45         205,000
17               500            500           3.45         205,000
18               750            200           3.45         205,000

                      Performance parameters

              Particles diameter    Particles diameter
Experiment   < 100 [micro]m (wt%)      > 1 mm (wt%)

1                     0                     72
2                     0                     17
3                     0                     45
4                     0                     3
5                     0                     22
6                     0                     36
7                     0                     2
8                     0                     46
9                     0                     50
10                    0                     72
11                    0                     0
12                    1                     0
13                    4                     0
14                    0                     0
15                    32                    0
16                    32                    0
17                   100                    0
18                   100                    0

TABLE 3. ANOVA by factor using the mean: statistical significance
level of the effects of the different factors on MVPs with diameter
<100 [micro]m.

                 of       Sum of                         Significance
Factor         freedom    squares   F ratio   p-value       level

[v.sub.disp]      2      0.1253980   2.6043    0.1118        NS
[v.sub.cure]      2      0.2582725   5.3638    0.0240        *
[C.sub.PVA]       2      0.6200788  12.8778    0.0007        ***
[MW.sub.PVA]      1      1.0152945  21.0857   <0.0001        ***

NS, not significant; * 5%; ** 1%; *** 0.1%.

TABLE 4. ANOVA by factor using the mean: statistical significance level
of the effects of the different factors on MVPs with diameter larger
than 1 mm.

                      of      Sum of                       Significance
Factor              freedom   squares   F ratio  p-value      level

[v.sub.disp] (rpm)     2     0.0703360   4.2407   0.0438       *
[v.sub.cure] (rpm)     2     0.1808906  10.9064   0.0016       ***
[C.sub.PVA]            2     0.0418143   2.5211   0.1176       NS
[MW.sub.PVA]           1     1.5714778  94.7486  <0.0001       ***

NS, not significant; * 5%; ** 1%; *** 0.1%.

TABLE 5. Gel time for different concentrations
of BPO in organic phase at 60[degrees]C.

BPO concentration (wt%)   Gel time (min)

1                             30-40
2                             8.5-9
3                             5.2-54
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Author:Monteiro, Sandra; Dias, Angela; Martins, Jorge; Carvalho, Luisa; Magalhaes, Fernao D.
Publication:Polymer Engineering and Science
Article Type:Report
Date:May 1, 2016
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