Effect of process variables on bulk development of air‐textured poly(trimethylene terephthalate) bulk continuous filaments

Bulk development of air‐textured poly(trimethylene terephthalate) (PTT) bulk continuous filaments was studied by varying two texturing parameters, yarn preheating and texturing hot air temperatures. The yarns were subsequently heat treated from 80 to 160°C. Bulk was found to go through a maximum with increasing heat‐treatment temperature because of two competing mechanisms. Upon heat treatment, the fiber shrunk and developed bulk; heat treatment also simultaneously induced structural reorganization through annealing and stabilized the fiber against shrinkage. When the later mechanism became dominant, bulk development decreased with further increase of heat‐treatment temperature. The temperature at which the maximum occurred increased when the yarn preheating or texturing air temperatures were increased. Depending on the extent of annealing and structural reorganization during yarn preheating and during texturing, fibers with equivalent bulk measured at a single temperature did not behave the same way over a range of heat‐treatment temperatures. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1011–1017, 2004     

Effect of zone drawing on the structure and properties of melt‐spun poly(trimethylene terephthalate) fiber

Melt‐spun poly(trimethylene terephthalate) (PTT) fibers were zone‐drawn and the structures and properties of the fibers were investigated in consideration of the spinning and zone‐drawing conditions. The draw ratio increased up to 4 with increasing drawing temperature to 180°C, at a maximum drawing stress of 220 MPa. Higher take‐up velocity gave lower drawability of the fiber. The PTT fiber taken up at 4000 rpm was hardly drawn, in spite of using maximum drawing stress, because a high degree of orientation had been achieved in the spinning procedure. However, an additional enhancement of birefringence was observed, indicating a further orientation of PTT molecules by zone drawing. The exotherm peak at 60°C disappeared and was shifted to a lower temperature with an increase in the take‐up velocity, which means that the orientation and crystallinity of the fiber increased. The d‐spacing of (002) plane increased with increasing take‐up velocity and draw ratio, whereas those of (010) and (001) planes decreased. In all cases, the crystal size increased with take‐up velocity and draw ratio. The cold‐drawn PTT fiber revealed a kink band structure, which disappeared as the drawing temperature was raised. The physical properties of zone‐drawn PTT fibers were improved as the draw ratio and take‐up velocity increased. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3471–3480, 2001     

Effects of spinning and drawing conditions on the crimp contraction of side‐by‐side poly(trimethylene terephthalate) bicomponent fibers

The crimp properties in the melt‐spinning and drawing processes of side‐by‐side bicomponent fibers with poly(trimethylene terephthalate)s (PTTs) of different viscosities were studied. Two PTTs of different intrinsic viscosities (1.02 and 0.92) were selected to make latent crimp yarn. The spinning and drawing conditions were changed to investigate the relation between the process conditions and crimp contraction. An orthogonal array was used to rule out the weak variables. The draw ratio, heat‐set temperature, and portion of high‐viscosity PTT were selected as variables having an effect on the crimp contraction. An analysis of the effects of the spinning and drawing conditions on the crimp contraction showed that the draw ratio was the most critical variable. Increasing the draw ratio caused a difference in the shrinkage between the two parts of PTT and caused the self‐crimping of the bicomponent fibers. Although changing the heat‐set temperature and the portion of high‐viscosity PTT did not produce a dimensional change, the crimp contraction varied with those variables. As the heat‐set temperature and the high‐viscosity portion increased, the crimp contraction increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1322–1327, 2006     

Study of poly(trimethylene terephthalate) as an engineering thermoplastics material

Poly(trimethylene terephthalate) (PTT) was systematically studied as an engineering thermoplastics material. Crystallization rates, crystalline degrees, and mechanical properties of two commercial PTT polymers and one glass fiber–reinforced PTT compound were investigated and compared with those of poly(butylene terephthalate) (PBT). PTT raw polymers have crystallization temperature (T_c) values around 152°C, and their kneaded polymers show T_c values of about 177°C, about 15°C lower than the values of PBT polymers used in this study. From the exothermic heat values of DSC measurements, both PTT and PBT show the crystalline degree order greater than 30%. Injection‐molded PTT specimens and PBT specimens exhibit crystalline degrees from 18 to 32% and 23.8 to 30%, respectively. PTT polymers show higher tensile and flexural strengths, but lower impact strengths and elongations than those of PBT polymers. The low elongation behavior of PTT does not change with the intrinsic viscosity and the molder temperature. PTT‐GF30 promotes better mechanical properties than those of PBT‐GF30, close to those of PET‐GF30. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1657–1666, 2004     

Fibers from urea–formaldehyde resins

The preparation of fibers from aqueous urea–formaldehyde resins has been investigated; a dry spinning process has been developed based on the extrusion of catalyzed resin into a drying chamber at 180–220°C, producing a multifilament yarn at spinning speeds of up to 600 m/min. A range of UF filaments was produced with diameters between 10–70 μm; the tenacities of spun filaments were 6–10 cN/tex, initial moduli were 220–340 cN/tex, and elongation at break was 4–10%. The best tensile properties resulted from conditions that produced the smallest diameter fibers. Postspin heat treatment improved the tenacity to 14 cN/tex and the elongation to 20%. Spinnability improved with increased viscosity of the spinning solution and increased cell temperature, while tenacity and elongation increased with increasing cell temperature and spinning stretch. A correlation was found between TGA weight loss (between 105 and 200°C) and fiber tenacity. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 64–74, 2000     

Shrinkage behavior after the heat setting of biaxially stretched poly(ethylene 2,6‐naphthalate) films and bottles

Amorphous preforms of poly(ethylene 2,6‐naphthalate) (PEN) were biaxially drawn into bottles up to the desired volume under industrial conditions. These bottles were used to characterize the shrinkage behavior of the drawn bottles with or without heat treatment and to study structural variations during heat setting. During drawing, a rigid phase structure was induced, and the amount of the induced rigid phase structure was linearly related to the square root of the extra first strain invariant under equilibrium conditions. During the production of these bottles, this equilibrium was not attained because of high stretching conditions and rapid cooling after stretching. The structure after orientation contained a rigid amorphous phase and an oriented amorphous phase. The shrinkage behavior was a function of the temperature and time of heat setting. Long heat‐setting times, around 30 min, were used to characterize the possible structural variations of the oriented PEN after heat setting at equilibrium. Under the equilibrium conditions of heat setting, the start temperature of the shrinkage was directly related to the heat‐setting temperature and moved from 60°C without heat treatment up to a temperature of 255°C by a heat‐setting temperature of 255°C; this contrasted with poly(ethylene terephthalate) (PET), for which the start temperature of shrinkage was always around 80°C. For heat‐setting temperatures higher than 220°C, the structural variations changed rapidly as a function of the heat‐setting time, and the corresponding shrinkage of the heat‐set samples sank below 1% in a timescale of 30–60 s for a film thickness of 500 μm. The heat treatment of the oriented films taken out of the bottle walls with fixed ends stabilized the induced structures, and the shrinkage of these heat‐set films was zero for temperatures up to the heat‐setting temperature, between 220 and 265°C, if the heat‐setting time was sufficient. According to the results obtained, a heat‐setting time of 30 s, for a film thickness of 500 μm, was sufficient at a heat‐setting temperature of 255°C to stabilize the produced biaxially oriented PEN bottles and to take them out the mold without further shrinkage. During the drawing of PEN, two different types of rigid amorphous phases seemed to be induced, one with a mean shrinkage temperature of 151°C and another rigid amorphous phase, more temperature‐stable than the first one, that shrank in the temperature range of 200–310°C. During heat setting at high temperatures, a continuous transformation of the less stable phase into the very stable phase took place. The heat‐set method after blow molding is industrially possible with PEN, without the complicated process of subsequent cooling before the molds are opened, in contrast to PET. This constitutes a big advantage for the blow molding of PEN bottles and the production of oriented PEN films. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1462–1473, 2003     

Reinforcing properties of poly(trimethyleneterephthalate) by a thermotropic liquid crystal polymer

A thermotropic liquid crystalline copolymer (TLCP) having a trimethylene terephthalate (TT) unit and a triad terephthaloyl mesogenic unit was synthesized and its blends with poly(trimethylene terephthalate) (PTT) were prepared for TLCP‐reinforced fiber spinning. The TLCP, PTT, and their blends were characterized in terms of their thermal, mechanical, and morphological properties. In the hot‐drawn fibers of 20 wt % TLCP/PTT blend, the well‐oriented fibrils were observed at higher temperature (>T_m) than the PTT melt by polarizing optical microscope. With scanning electron microscopy images of cryogenically fractured surfaces of the blends, the TLCP were well dispersed in 0.3 to 0.5 µm in domain size. Interfacial adhesion between the TLCP and PTT seemed fairly good. The TLCP acted effectively as a reinforcing material in PTT matrix, it led to an increase of initial modulus and tensile strength of the blend fibers as TLCP's content increased. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41408.     

Structure development during crystallization and solid‐state processing of poly(glycolic acid)

DSC and time‐resolved WAXS and SAXS are used to study the structure development during isothermal crystallization of poly(glycolic acid) (PGA) in the temperature range 180–195°C. It is shown that the crystallization rate increases with degree of supercooling in the temperature range of consideration. WAXS and DSC crystallinity measurements agree well and a final crystallinity of 50% is found independently of the crystallization temperature. In‐situ SAXS measurements indicate that for PGA the final crystal thickness approaches a limiting value of 70 Å independent of the crystallization temperature in the range 195–180°C. The material develops a well‐defined lamellar structure during crystallization at the highest crystallization temperature under study (195°C). We show that by increasing the degree of supercooling it is possible to hinder the formation of the lamellar structure and crystals, resulting in a less ordered structure. We report that PGA fibers with elastic modulus in the range 20–25 GPa can be prepared by adequate control of the structure before solid‐state plastic deformation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of spinning speed and heat treatment on the mechanical properties and biodegradability of poly(lactic acid) fibers

We undertook this study to suggest the optimal spinning process conditions that provide a proper range of tenacity and biodegradability in textile fibers. The effect of melt‐spinning speed and heat treatment on the mechanical properties and biodegradability of poly(lactic acid) (PLA) fibers were investigated. PLA was spun at a high spinning speed of 2000–4000 m/min, and each specimen was heat‐treated. Mechanical properties were estimated by measurement of the breaking stress, and the degree of crystallinity was evaluated with wide‐angle X‐ray scattering. Biodegradability was estimated from the decreases in breaking stress, weight loss, and degree of crystallinity after soil burial. The results of the experiment reveal that heat treatment of the PLA fibers increased the breaking stress and crystallinity. With increasing spinning speed, breaking stress and crystallinity also increased. An increase in spinning speed was more effective than an increase in heat treatment for enhancing the breaking stress within the range of this study. From the soil burial test, it was revealed that an increase in spinning speed and heat treatment decreased the biodegradability of the fibers. X‐ray analysis of the soil‐buried fibers showed that fibers with higher crystallinities began to degrade more slowly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3099–3104, 2007     

Structure and properties of thermotropic liquid crystal polymer and poly(ethylene 2,6‐naphthalate) blend fibers

BACKGROUND: The melt blending of thermotropic liquid crystal polymers (TLCPs) using conventional thermoplastics has attracted much attention due to the improved strength and tensile modulus of the resulting polymer composites. Moreover, because of their low melt viscosity, the addition of small amounts of TLCPs can reduce the melt viscosity of polymer blends, thereby enhancing the processability. RESULTS: In this study, TLCP/poly(ethylene 2,6‐naphthalate) (PEN) blend fibers were prepared by melt blending and melt spinning to improve fiber performance and processability. The relation between the structure and the mechanical properties of TLCP/PEN blend fibers and the effect of annealing on these properties were also investigated. The mechanical properties of the blend fibers were improved by increasing the spinning speed and by adding TLCP. These properties of the blend fibers were also improved by annealing. The tensile strength of TLCP5/PEN spun at a spinning speed of 2.0 km h^?1 and annealed at 235 °C for 2 h was about three times higher than that of TLCP5/PEN spun at a spinning speed of 0.5 km h^?1. The double melting behavior observed in the annealed fibers depended on the annealing temperature and time. CONCLUSION: The improvement of the mechanical properties of the blend fibers with spinning speed, by adding TLCP and by annealing was attributed to an increase in crystallite size, an increase in the degree of crystallinity and an improvement in crystal perfection. The double melting behavior was influenced by the distribution in lamella thickness that occurred because of a melt‐reorganization process during differential scanning calorimetry scans. Copyright © 2007 Society of Chemical Industry     

Molecular structures and physical properties of heat‐drawn conjugate fibers

As‐spun poly(trimethylene terephthalate) (PTT)/poly(ethylene terephthalate) (PET) side‐by‐side conjugate fibers were drawn to investigate the effects of drawing conditions on structure development and physical properties. Effects of draw ratio and heat‐set temperature were observed. In the state of an as‐spun fiber, the molecular orientation of PTT was higher than PET, whereas PET molecular orientation increased remarkably over PTT with increasing draw ratio. Crimp contraction increased sharply at a draw ratio over 2.0, where the crystalline structure of the PET developed sufficiently. A heat‐set temperature of at least 140°C was required to develop sufficient crimp contraction. The crystallinity and orientation of the PET were attributed mainly to the crimp contraction of the drawn fiber. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

pH‐responsive fibers based on acrylonitrile acrylic acid block copolymers: Effect of spinning conditions and postspinning operations on response and mechanical properties

pH sensitive poly(acrylonitrile‐co‐acrylic acid) having ～50 mol % acrylic acid with block type structure (AA50B) was synthesized by controlled dosing method of free radical polymerization. The polymer was converted into fibers by wet solution spinning technique in DMF‐water system. The resulting block type copolymer could generate a domain type morphology with segregated domains of acrylonitrile and acrylic acid on heat‐setting. The drawing ratio and heat‐setting temperature had a significant effect on the formation of these domains and their stability. The domain formation was more pronounced when the fibers could be drawn to higher draw ratios during coagulation or heat‐set at higher temperature. The stability of the fibers, which is influenced by domain formation, was lowest (at few cycles of transitions) when the fibers were heat‐set at 100°C, while it is improved significantly to more than 50 cycles as the heat‐setting temperature was increased to 150°C. The coagulation conditions, drawing and the heat‐setting also greatly influenced the mechanical properties, transition behavior, and retractive stresses of the responsive fibers. The tenacity improved by 6.6 times in swollen state and 1.4 times in deswollen state, while the retractive stresses during deswelling were significantly increased to about 4.7 times. However, the increased heat‐setting temperature was also found to have a negative effect on the equilibrium swelling values as well as the response rate. The effect of heat‐setting on chemical structure of the copolymer was also investigated. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Melt spinning and drawing of 2‐methyl‐1,3‐propanediol‐substituted poly(ethylene terephthalate)

The structure and properties of fibers prepared from copolymers of poly(ethylene terephthalate) (PET) in which 2‐methyl‐1,3‐propanediol (MPDiol® Glycol is a registered trademark of Lyondell Chemical Company) at 4, 7, 10, and 25 mol% was substituted for ethylene glycol were studied and compared with those of PET homopolymer. Filaments were melt spun over a range of spinning conditions, and some filaments that were spun at relatively low spinning speeds were subjected to hot drawing. The filaments were characterized by measurements of birefringence, differential scanning calorimetry (DSC) crystallinity, melting point, glass transition temperature, wide‐angle X‐ray diffraction patterns, boiling water shrinkage, tenacity, and elongation to break. Filaments containing 25 mol% MPDiol did not crystallize in the spinline at any spinning speed investigated, whereas the other resins did crystallize in the spinline at high spinning speeds. However, compared with PET homopolymer, increasing substitution of MPDiol reduced the rate at which the crystallinity of the melt spun filaments increased with spinning speed and reduced the ultimate crystallinity that could be achieved by high‐speed spinning. The rate of development of molecular orientation, as measured by birefringence, also decreased somewhat with increasing MPDiol content. Shrinkage in boiling water decreased at high spinning speeds as the amount of crystallinity increased; however, the shrinkage decreased more slowly with increase in spinning speed as MPDiol content increased. Tenacity also decreased slightly at any given spinning speed as MPDiol content increased, but there was no significant effect on elongation to break. The addition of MPDiol in amounts up to 7 mol% increased the maximum take‐up velocity that could be achieved at a given mass throughput. This result indicates that the use of higher spinning speeds could potentially increase the productivity of melt spun yarns. Copolymer filaments spun at low speeds were readily drawn to produce highly oriented fibers with slightly less birefringence, crystallinity, and tenacity than similarly processed PET homopolymer. Preliminary dyeing experiments showed that the incorporation of MPDiol improved the dyeability of the filaments. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2598–2606, 2003     

PBT/PET conjugated fibers: Melt spinning,fiber properties,and thermal bonding

This work examines the PBT/PET sheath/core conjugated fiber, with reference to melt spinning, fiber properties and thermal bonding. Regarding the rheological behaviors in the conjugated spinning, PET and PBT show the smallest difference between their melt‐viscosity at temperatures of 290°C and 260°C respectively, which has been thought to represent optimal spinning conditions. The effect of processing parameters on the crystallinity of core material‐PET was observed and listed. In order of importance, these factors are the draw ratio, the heat‐set temperature, and the drawing temperature. The crystallinity of sheath material‐PBT, however, can be considered to be constant, independent of any processing parameters. The bulk orientation, rather than the crystallinity of PET core, dominates the tenacity of PBT/PET sheath/core fiber. Moreover, heat‐set treatment after drawing is recommended to yield a highly oriented conjugated fiber. With respect to thermal bonding, PBT/PET conjugated fibers processed via high draw ratio but low‐temperature heat setting can form optimal thermal bonds at a constant bonding temperature of 10°C above the T_m of PBT.     

Structural and thermal property changes of plasticized spinning polyacrylonitrile fibers under different spinning speeds

The effect of the spinning speed on structural and thermal properties of polyacrylonitrile (PAN) fibers prepared by plasticized spinning was investigated. The PAN fibers were characterized by scanning electron microscopy, X‐ray diffraction, differential scanning calorimetry, and thermogravimetric analysis. We found that the surface morphology of the fibers was relatively smooth. The presence of a small amount of surface defects was caused by the instability of spinning process. The final fibers may have had two tensile fracture modes, that is, cluster breaking and axial split fracture. The structure of the as‐spun fibers was destroyed when the spinning speed was up to 500 m/min; this led to chain scission in the amorphous region. The final fibers exhibited mechanical properties that were roughly comparable to those of commercial PAN fibers. The changing trend in the cyclization temperature of the final fibers was consistent with that of crystallinity, which first increased and then decreased. The decomposition temperature in the amorphous region increased with increasing spinning speed. The decomposition temperature in the crystalline region increased with increasing crystallinity. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45267.     

Preparation of poly(lactic acid) fiber by dry‐jet‐wet‐spinning. I. Influence of draw ratio on fiber properties

Poly(lactic acid) fiber was prepared by dry‐jet‐wet spinning of the polymer from chloroform solution and with methanol as the precipitating medium. The as‐spun fiber was subsequently made into high strength fiber by two‐step process of drawing at a temperature of 90°C and subsequent heat setting in the temperature range of 120°C. The draw ratio had significant influence on the crystallinity and the tensile strength of the fiber. The fiber with the tenacity of 0.6 GPa and modulus of 8.2 GPa was achieved at a draw ratio of 8. The differential scanning calorimetry revealed an increase in the glass‐transition temperature with the increase in the draw ratio, which suggests the orientation of chains during the drawing process. The surface morphology of the filament as revealed by scanning electron microscopy shows that fibers are porous in nature, but a significant reduction in the porosity and pore size of the fiber was observed with the increase in the draw ratio. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1239–1246, 2006     

Orthogonal design preparation of phenolic fiber by melt electrospinning

Through orthogonal experimental methods, the melt electrospinning of pure phenolic fibers has been achieved. The preparation is based on an orthogonal experimental method, which was designed to investigate the optimal conditions for production through integrated effects of spinning temperature, gap between spinneret and collector, as well as applied voltage. We found that optimal spinning conditions at 160°C, a spinneret‐to‐collector gap of 8 cm, and applied voltage at 40 kV produce an average electrospun fiber diameter reaching 4.44 ± 0.76 μm, with narrow variance distribution. The fibers were cured in a solution with 18.5% formaldehyde and 12% hydrochloric acid, heated from room temperature to 80°C and maintained 1h. In this report, the morphology, structural changes, and heat resistance of the fibers are characterized. Obtained results reveal that curing the fiber reduces crystallization and improves heat resistance. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42574.     

Morphology and structure changes of aromatic copolysulfonamide fibers heat‐drawn at various temperatures

Pre‐drawn aromatic copolysulfonamide (co‐PSA) fibers were prepared by wet spinning and then heat drawing at temperatures varying from 350 to 390 °C, which are below the decomposition temperature. The fibers were then characterized using tensile testing, dynamic mechanical analysis, wide‐angle X‐ray diffraction and small‐angle X‐ray scattering. The relationship between structure and properties of the co‐PSA fibers drawn at different temperatures was investigated. The heat‐drawn co‐PSA fibers displayed similar glass transition temperature of about 355 °C, which was higher than that of pre‐drawn co‐PSA fibers of 345 °C. The crystal orientation was high as a crystalline structure formed during heat drawing and the crystallinity increased with the heat‐drawing temperature. However, the tenacity of the co‐PSA fibers did not increase linearly with the draw temperature. When the drawing temperature was higher than the glass transition temperature, a decrease in tenacity was observed, which could be attributed to an increase of crystallite size of the (100) plane and a decrease of the long period of the lamellar structure. © 2014 Society of Chemical Industry     

Preparation of poly(lactic acid) fiber by dry–jet–wet spinning. II. Effect of process parameters on fiber properties

The dry–jet–wet spinning process was employed to spin poly(lactic acid)(PLA) fiber by the phase inversion technique using chloroform and methanol as solvent and nonsolvent, respectively, for PLA. The as spun fiber was subjected to two‐stage hot drawing to study the effect of various process parameters, such as take‐up speed, drawing temperature, and heat‐setting temperature on the fiber structural properties. The take‐up speed had a pronounced influence on the maximum draw ratio of the fiber. The optimum drawing temperature was observed to be 90°C to get a fiber with the tenacity of 0.6 GPa for the draw ratio of 8. The heat‐setting temperature had a pronounced effect on fiber properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3774–3780, 2006     

Effect of processing parameters of the continuous wet spinning system on the crystal phase of PVDF fibers

Poly(vinylidene difluoride) (PVDF) has been widely used in piezoelectric applications as films and nanofiber mats, but there are limited publications on piezoelectric wet‐spun fibers. In this work, PVDF fibers were prepared using the wet spinning method, and the processing parameters, including the drawing ratio and heat setting temperature, were controlled in the continuous wet spinning system to increase the β‐phase crystallinity of the fibers. In addition, the wet‐spun PVDF fibers were compressed by a rolling press to eliminate voids in the fibers. Then, the compressed PVDF fibers were poled to align the molecular dipoles. The crystal structures of the PVDF fibers were investigated using X‐ray diffraction and Fourier‐transform infrared spectroscopy. Single filament tensile tests were performed to measure the tensile strength of the fibers. The morphologies of the PVDF fibers with respect to the processing parameters were observed by scanning electron microscope (SEM) and polarization optical microscopy. The piezoelectric constant of the prepared PVDF fibers was then measured using a d₃₃ meter. The wet‐spun PVDF fibers showed the highest β‐phase and piezoelectric constants when the drawing ratio and heat setting temperature were 6 and 150 °C, respectively. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45712.