首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 15 毫秒
1.
It is well known that supercritical carbon dioxide (sc-CO2) is soluble in molten polymers and acts as a plasticizer. The dissolution of sc-CO2 leads to a decrease in the viscosity of the liquid polymer, the melting point and the glass transition temperature. These properties have been used in several particle generation processes such as PGSS (particles from gas saturated solutions).It is therefore highly likely that extrusion processes would benefit from the use of sc-CO2 since the rationale of the extrusion processes is to formulate, texture and shape molten polymers by forcing them through a die. Combining these two technologies, extrusion and supercritical fluids, could open up new applications in extrusion.The main advantage of introducing sc-CO2 in the barrel of an extruder is its function as a plasticizer, which allows the processing of molecules which would otherwise be too fragile to withstand the mechanical stresses and the operating temperatures of a standard extrusion process. In addition, the dissolved CO2 acts as a foaming agent during expansion through the die. It is therefore possible to control pore generation and growth by controlling the operating conditions.This review focuses on experimental work carried out using continuous extrusion. A continuous process is more economically favourable than batch foaming processes because it is easier to control, has a higher throughput and is very versatile in the properties and shapes of the products obtained.The coupling of extrusion and supercritical CO2 technologies has already broadened the range of application of extrusion processes. The first applications were developed for the agro-food industry 20 years ago. However, most thermoplastics could potentially be submitted to sc-CO2-assisted extrusion, opening new challenging opportunities, particularly in the field of pharmaceutical applications.This coupled technology is however still very new and further developments of both experimental and modelling studies will be necessary to gain better theoretical understanding and technical expertise prior to industrial use, especially in the pharmaceutical field.  相似文献   

2.
When CO2 is dissolved into a polymer, the viscosity of the polymer is drastically reduced. In this paper, the melt viscosities of low‐density polyethylene (LDPE)/supercritical CO2 solutions were measured with a capillary rheometer equipped at a foaming extruder, where CO2 was injected into a middle of its barrel and dissolved into the molten LDPE. The viscosity measurements were performed by varying the content of CO2 in the range of 0 to 5.0 wt% and temperature in the range of 150°C to 175°C, while monitoring the dissolved CO2 concentration on‐line by Near Infrared spectroscopy. Pressures in the capillary tube were maintained higher than an equilibrium saturation pressure so as to prevent foaming in the tube and to realize single‐phase polymer/CO2 solutions. By measuring the pressure drop and flow rate of polymer running through the tube, the melt viscosities were calculated. The experimental results indicated that the viscosity of LDPE/CO2 solution was reduced to 30% of the neat polymer by dissolving CO2 up to 5.0 wt% at temperature 150°C. A mathematical model was proposed to predict viscosity reduction owing to CO2 dissolution. The model was developed by combining the Cross‐Carreau model with Doolittle's equation in terms of the free volume concept. With the Sanchez‐Lacombe equation of state and the solubility data measured by a magnetic suspension balance, the free volume fractions of LDPE/CO2 solutions were calculated to accommodate the effects of temperature, pressure and CO2 content. The developed model can successfully predict the viscosity of LDPE/CO2 solutions from PVT data of the neat polymer and CO2 solubility data.  相似文献   

3.
In this study, the effect of macromolecular chain‐branching on poly(lactic acid) (PLA) rheology, crystallization, and extrusion foaming was investigated. Two PLA grades, an amorphous and a semi‐crystalline one, were branched using a multifunctional styrene‐acrylic‐epoxy copolymer. The branching of PLA and its foaming were achieved in one‐step extrusion process. Carbon dioxide (CO2), in concentration up to 9%, was used as expansion agent to obtain foams from the two PLA branched using chain‐extender contents up to 2%. The foams were investigated with respect to their shear and elongational behavior, crystallinity, morphology, and density. The addition of the chain‐extender led to an increase in complex viscosity, elasticity, elongational viscosity, and in the manifestation of the strain‐hardening phenomena. Low‐density foams were obtained at 5–9% CO2 for semi‐crystalline PLA and only at 9% CO2 in the case of the amorphous PLA. Differences in foaming behavior were attributed to crystallites formation during the foaming process. The rheological and structural changes associated with PLA chain‐extension lowered the achieved crystallinity but slightly improved the foamability at low CO2 content. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers  相似文献   

4.
We investigated , by visual observation and numerical calculations , the foaming behavior of polypropylene within a foam injection mold cavity with the environmentally benign physical blowing agents nitrogen (N2) and carbon dioxide (CO2) . An 85‐ton core‐back injection‐molding machine with temperature and pressure monitoring systems as well as a high‐pressure view cell was used for the investigation . The experiments showed a prominent difference in bubble nucleation and growth between N2 and CO2 injection foaming . Even when the weight concentration of N2 dissolved in polymer was one‐third that of CO2 , N2 injection foaming provided a bubble number density that was 30 times larger and a bubble size that was one‐third smaller compared to CO2 injection foaming . Classical bubble nucleation and growth models developed for batch foaming were employed to analyze these experimental results . The models reasonably explained the differences in injection foaming behavior between N2 and CO2 . It was clearly demonstrated by both experiments and numerical calculations that N2 provides a higher number of bubbles with a smaller bubble size in foam injection molding compared to CO2 as a result of the lower solubility of N2 in the polymer and the larger degree of super‐saturation . POLYM. ENG. SCI., 2011. ©2011 Society of Plastics Engineers  相似文献   

5.
The purpose of this study is to determine under what conditions it is possible to use CO2 to plasticize and, thereby, reduce the viscosity of an acrylonitrile (AN) copolymer in an extrusion process and render it melt processable. To assess whether it was possible to absorb adequate amounts of CO2 in short residence times by injection into a single screw extruder, a slit‐die rheometer was attached to the end of the extrusion system for the purpose of directly assessing the viscosity reduction. A chemorheological analysis was performed on 65 and 85% AN copolymers to establish the temperature at which the 85% material would be as stable as the melt‐processable 65% material at its recommended extrusion temperature. This, coupled with studies correlating the degree of Tg and viscosity reduction with the amount of absorbed CO2, and comparison to previous data obtained in batch processes allowed one to predict conditions for melt extrusion of the 85% AN. Preliminary studies using a pressurized chamber attached to the exit of the die allowed one to assess the conditions under which suppression of foaming is possible. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers  相似文献   

6.
A simulation of simultaneous bubble nucleation and growth was performed for a batch physical foaming process of polypropylene (PP)/CO2 system under finite pressure release rate. In the batch physical foaming process, CO2 gas is dissolved in a polymer matrix under pressure. Then, the dissolved CO2 in the polymer matrix becomes supersaturated when the pressure is released. A certain degree of supersaturation produces CO2 bubbles in the polymer matrix. Bubbles are expanded by diffusion of the dissolved CO2 into the bubbles. The pressure release rate is one of the control factors determining number density of bubbles and bubble growth rate.To study the effect of pressure release rate on foaming, this paper developed a simple kinetic model for the creation and expansion of bubbles based on the model of Flumerfelt's group, established in 1996 [Shafi, M.A., Lee, J.G., Flumerfelt, R.W., 1996. Prediction of cellular structure in free expansion polymer foam processing. Polymer Engineering and Science 36, 1950-1959]. It was revised according to the kinetic experimental data on the creation and expansion of bubbles under a finite pressure release rate. The model involved a bubble nucleation rate equation for bubble creation and a set of bubble growth rate equations for bubble expansion. The calculated results of the number density of bubbles and bubble growth rate agreed well with experimental results. The number density of bubbles increased with an increase in the pressure release rate. Simulation results indicated that the maximum bubble nucleation rate is determined by the balance between the pressure release rate and the consumption rate of the physical foaming agent by the growing bubbles. The bubble growth rate also increased with an increase in the pressure release rate. Viscosity-controlled and diffusion-controlled periods exist between the bubble nucleation and coalescence periods.  相似文献   

7.
This study examines the foaming behaviour of polystyrene (PS) blown with supercritical CO2–N2 blends. This is achieved by observing their foaming processes in situ using a visualization system within a high-temperature/high-pressure view-cell. Through analyzing the cell nucleation and growth processes, the foaming mechanisms of PS blown with supercritical CO2–N2 blends have been studied. It was observed that the 75% CO2–25% N2 blend yielded the highest cell densities over a wide processing temperature window, which indicates the high nucleating power of supercritical N2 and the high foam expanding ability of supercritical CO2 would produce synergistic effects with that ratio in batch foaming. Also, the presence of supercritical CO2 increased the solubility of supercritical N2 in PS, so the concentration of dissolved supercritical N2 was higher than the prediction by the simple mixing rule. The additional supercritical N2 further increased the cell nucleation performance. These results provide valuable directions to identify the optimal supercritical CO2–N2 composition for the foaming of PS to replace the hazardous blowing agents which are commonly used despite their high flammability or ozone depleting characteristics.  相似文献   

8.
Viscoelastic simulations of bubble growth in polypropylene (PP) physical foaming were performed. A multimode Phan‐Thien Tanner (PTT) model was used to analyze the dynamic growth behavior of spherically symmetric bubbles with the diffusion of a foaming agent (CO2). Changes in the dissolved foaming agent concentration in the polymer and in the strain of the polymer melt surrounding the bubbles were simulated with the Lagrangian FEM method. The simulation technique was validated by comparison with the bubble growth data, which were experimentally obtained from visual observations of the PP/CO2 batch foaming system. The simulation results demonstrated that the strain‐hardening characteristic of polymer does not strongly affect the bubble growth rate. The linear viscoelastic characteristic is more influential, and the relaxation mode around 0.01 s is the most important factor in determining the bubble growth rate during the early stage of foaming. A multivariate analysis for the simulation results was also carried out. This clarified that bubble nucleus population density, surrounding pressure, initial dissolved foaming agent concentration, and diffusion coefficient are more important factors than the viscoelastic characteristics. POLYM. ENG. SCI., 45:1277–1287, 2005. © 2005 Society of Plastics Engineers  相似文献   

9.
Reinforcing the cavity cell walls of polymer foams using nanoparticles can offer a new era for the property‐structure‐processing field in the development of functionalized ultra‐light components and devices manufactured from foam. When the nanoparticles are exfoliated in polymers, the viscosity substantially increases and thus mixing or foaming usually becomes almost impossible. We use CO2 supercritical fluid (CO2 SCF) for the mixing and foaming of poly(ethylene‐vinyl acetate) copolymer (EVA) with montmorillonite (MMT) nanoplatelets. The in situ evaporation of CO2 induces robust cavity cells of the EVA/MMT nanocomposite foam in a stable form of spherical shapes, which are seldom achieved by other methods. As the bubble grows and becomes stabilized in CO2 SCF, the exfoliated MMT nanoparticles are aligned at the cell walls by the Gibbs adsorption principle to minimize the surface energy at the gas–liquid interface and increase the rupture strength of the cavity walls. It is demonstrated that the developed methodology can be successfully used for foaming EVA containing high vinyl acetate (VA) content (>40%). Since EVA is too soft to construct cell walls of foam using conventional methods, the applicability of the developed methodology is extensively broadened for superior adhesion and compatibility with other materials. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46615.  相似文献   

10.
Current-voltage characteristics of limiting current-type oxygen sensors were investigated. The sensor showed a two-stage current plateau in current-voltage characteristics in H2O–O2–N2 and CO2–O2–N2 mixtures. The sensor current in the first stage corresponded to O2 concentration and was practically independent of H2O and CO2 concentration in the gas mixtures. The sensor current in the second stage increased linearly with the H2O or CO2 concentration, for a sensor with high electrode activity. The behavior of the sensor suggests that the deoxidization of H2O or CO2 occurs at the sensor cathode. For nonequilibrium gas mixtures containing combustible gas and O2, the sensor current in the first stage decreased linearly with combustible gas concentration. The decrease of the sensor current differed from that corresponding to the O2 concentration consumed by the reaction of these gases in the ambient gas, depending on the kind of combustible gas. The reduction of the sensor current is explained by a model assuming that the reaction of these gases occurs at the cathode, and the diffusion of the combustible gas in the porous coating is a rate-limiting step.  相似文献   

11.
Nanocellular foaming of polystyrene (PS) and a polystyrene copolymer (PS‐b‐PFDA) with fluorinated block (1,1,2,2‐tetrahydroperfluorodecyl acrylate block, PFDA) was studied in supercritical CO2 (scCO2) via a one‐step foaming batch process. Atom Transfer Radical Polymerization (ATRP) was used to synthesize all the polymers. Neat PS and PS‐b‐PFDA copolymer samples were produced by extrusion and solid thick plaques were shaped in a hot‐press, and then subsequently foamed in a single‐step foaming process using scCO2 to analyze the effect of the addition of the fluorinated block copolymer in the foaming behaviour of neat PS. Samples were saturated under high pressures of CO2 (30 MPa) at low temperatures (e.g., 0°C) followed by a depressurization at a rate of 5 MPa/min. Foamed materials of neat PS and PS‐b‐PFDA copolymer were produced in the same conditions showing that the presence of high CO2‐philic perfluoro blocks, in the form of submicrometric separated domains in the PS matrix, acts as nucleating agents during the foaming process. The preponderance of the fluorinated blocks in the foaming behavior is evidenced, leading to PS‐b‐PFDA nanocellular foams with cell sizes in the order of 100 nm, and bulk densities about 0.7 g/cm3. The use of fluorinated blocks improve drastically the foam morphology, leading to ultramicro cellular and possibly nanocellular foams with a great homogeneity of the porous structure directly related to the dispersion of highly CO2‐philic fluorinated blocks in the PS matrix. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

12.
In this study, we explore the use of solid‐state nucleation in polymer pellets as a means to create microcellular PLA foams in extrusion. This is achieved by using gas‐saturated PLA pellets as input to the extruder. Foam density, bubble size, and bubble density is reported and compared with microcellular foams created in the gas‐injection extrusion process. PLA pellet gas concentrations between 17 and 29 mg CO2/g PLA was found to produce quality microcellular foams in this process. Gas concentrations within this range were achieved by varying methods that included partial saturation, desorption from full saturation, and blending saturated with unsaturated pellets. This gas concentration window that produced microcellular foams was found to be independent of the saturation and desorption process used to achieve the desired concentration. We further compare the pressure drop and pressure drop rate of the gas‐saturated pellet extrusion process showing that similar foams can be produced at pressures orders of magnitude lower than the alternative gas‐injection extrusion processes. Investigations into extrusion pressures support the hypothesis that the gas‐saturated pellet extrusion process utilizes solid‐state nucleation in the feed section of the extruder to achieve high bubble density foams. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

13.
Microcellular polymeric foam structures have been generated using a pressure‐induced phase separation in concentrated mixtures of supercritical CO2 and styrene‐co‐acrylonitrile (SAN). The process typically generates a microcellular core structure encased by a non‐porous skin. Pore growth occurs through two mechanisms: diffusion of CO2 from polymer‐rich regions into the pores and also through CO2 gas expansion. The effects of saturation pressure, temperature and swelling time on the cell size, cell density and bulk density of the porous materials have been studied. Higher CO2 pressures (hence, higher fluid density) provided more CO2 molecules for foaming, generated lower interfacial tension and viscosity in the polymer matrix, and thus produced lower cell size but higher cell densities. This trend was similar to what was observed in swelling time series. While the average cell size increased with increasing temperature, the cell density decreased. The trend of bulk density was similar to that of cell size. © 2000 Society of Chemical Industry  相似文献   

14.
Minor components present in feed gas streams can have a significant influence on the separation performance of polymeric membranes. Hydrogen sulfide is present in many of the processes where CO2 capture is possible and can therefore undergo competitive sorption with CO2 for transport through the membrane, as well as influence the membrane morphology inducing plasticization. This study investigates the change in CO2 permeability and CO2/N2 selectivity of two glassy polymeric membranes; polysulfone and 6FDA‐TMPDA, when 500 ppm H2S is present in the gas mixture. The outcomes of this study reveal that H2S in trace amounts has a strong influence on the separation performance of both membranes. For both membranes, a plasticization partial pressure ~0.5–0.6 kPa H2S is observed. H2S competitive sorption is also observed and is modeled by competitive dual‐sorption theory. Results suggest that mixed gas permeation influences the amount of each gas immobilized within the Langmuir voids in addition to the expected competitive sorption effects. © 2011 American Institute of Chemical Engineers AIChE J, 2012  相似文献   

15.
To improve the rheological behaviors of gun propellants, SC‐CO2 was injected into the gun propellant substitute in extrusion processing. A slit die rheometer was used to investigate the in‐line rheological behaviors of CA solution. A Power model was applied to describe the rheological behaviors of CA/SC‐CO2 mixtures. The viscosity and pressure of CA solution obviously decrease with the assistance of SC‐CO2. The viscosity of CA solution reduces by 16.64 % at 55 °C and 10 s−1 with the presence of SC‐CO2. Increasing the processing temperature makes the viscosity of CA/SC‐CO2 mixture decrease remarkably, but it weakens the plasticization of SC‐CO2 to CA. Although the increasing solvent content improves the flow of the CA/SC‐CO2 mixture, it lowers the strength of CA/SC‐CO2 mixture, which is not in favor of the quality of product. The investigation of the in‐line rheological behaviors of CA/SC‐CO2 mixture is fundamental and important for the safe extrusion of gun propellants assisted with SC‐CO2.  相似文献   

16.
The equation of state model developed by Lacombe and Sanchez (J Phys Chem 1976, 80, 2352) is used in the form proposed later by Sanchez and Stone (Polymer Blends, Vol. 1: Formulation, 2000; Chapter 2) to correlate experimental vapor‐liquid equilibrium (VLE) data for the three binaries and the ternary systems. Experimental data from the binary systems carbon dioxide‐isopropyl alcohol (CO2‐IPrOH), isopropyl alcohol‐polystyrene (IPrOH‐PS), and carbon dioxide‐polystyrene (CO2‐PS) are used to calculate VLE properties for the ternary system CO2‐IPrOH‐PS. Two‐dimensional VLE‐phase diagrams were calculated and used to describe from a thermodynamic point of view the pressure, volume, and temperature values that characterize a thermoplastic foam evolution process, from the extruder to the foaming die. For different initial mixture CO2 + IPrOH concentrations, pressure reduction produces liquid foaming until the vitrification curve arrests the final foam volume expansion. The dependence of the vitreous transition with the system CO2 + IPrOH concentration while foaming is represented by the Chow (Macromolecules 1980, 13, 362) equation. The calculation procedure is proposed as a design tool to reduce the amount of experimental data usually needed as a requirement previous to the design stage. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2663–2671, 2007  相似文献   

17.
The sorption behavior of water vapor and CO2 gas in photocrosslinked poly(vinyl cinnamate) (PVCA) film was examined at 30°C under atmospheric pressure. Both the water sorption isotherm and the CO2 sorption isotherm obtained with quartz crystal microbalance (QCM) method obeyed the simple Langmuir's equation. Water vapor/CO2 mixed‐gas sorption isotherms were also obtained. Total amount of sorbed mixed gases was clearly influenced by the partial pressure of water vapor (pw) and CO2 gas (pc) in the atmosphere. A modified Langmuir's equation based on a dual‐site model was employed for predicting the competitive adsorption isotherm, and the isotherm was clearly described by the equation. The theoretically estimated amount of adsorbed water at the constant pw decreased slightly with increasing pc. The effect of this phenomenon on the sensitivity of the capacitive‐type relative humidity sensor was examined. As expected, the electrical capacitance of the sensor at the constant relative humidity decreased because of the coexistence of CO2 gas. However, the influence was quite small in the CO2 concentration range in the ordinary environment. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 401–407, 2002  相似文献   

18.
The Freeze‐Purged‐Desorption (FPD) method was developed for the experimental measurement of gas permeability coefficients as a new technique using a desorption curve of gas immobilized in polymeric films. The FPD method was effectively used to evaluate four gas permeation parameters (CD, CH, DD, and DH) of glassy polymeric films (polycarbonate and polystyrene) by using CO2. The modes of the CO2 gas desorption response curve (D‐curve) obtained were sensitively characterized by the proportion of sorption in the Henry and Langmuir modes in the polymeric films accompanied by their own gas diffusivity. A graphical analysis of the D‐curve of CO2 reasonably proposed a linear relation between the desorption rate and the sorption amount of CO2, which was strongly influenced by the kind of sorption gas, film, temperature, and other factors. The desorption rate of sorbed CO2 gas for the PC and PS films gave a characteristic straight line with an inflection point indicating a shift in the gas‐diffusion mechanism from the complex type of the Henry and the Langmuir modes to the Langmuir mode. The characteristic D‐curves obtained were graphically analyzed, and they clearly discriminated the Henry mode part and the Langmuir mode part. This discrimination process quantitatively and individually evaluated CD, CH, DD, and DH. By using the four parameters evaluated, a mathematical model to describe the D‐curve was proposed, and it consistently explained the experimental D‐curves. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 934–941, 2004  相似文献   

19.
Extrusion foaming using supercritical carbon dioxide (CO2) as the blowing agent is an economically and environmentally benign process. However, it is difficult to control the foam morphology and maintain its high thermal insulation comparing to the conventional foams based on fluorocarbon blowing agents. In this study, we demonstrated that polystyrene (PS) foams with the bimodal cell morphology can be produced in the extrusion foaming process using CO2 and water as co-blowing agents and two particulate additives as nucleation agents. One particulate is able to decrease the water foaming time so both CO2 and water can induce foaming simultaneously, while the other increases the CO2 nucleation rate with little effect on the CO2 foaming time. Our experimental results showed that a dual particulate combination of nanoclay and activated carbon provided the best bimodal structure. The bimodal foams exhibited much better compressive properties and slightly better thermal insulation for PS foams.  相似文献   

20.
An energy‐efficient absorbent formulation for separating acid gases (e.g. CO2, H2S) from gas streams such as natural gas, syngas or flue gas is important for a number of industrial applications. In many cases, a substantial share of their costs is driven by the operational expenditure (OPEX) of the CO2 separation unit. One possible strategy for reducing OPEX is the improvement of the absorbent performance. Although a number of absorbents for the separation of CO2 from gas streams exist, there is still a need to develop CO2 absorbents with an improved absorption performance, less corrosion and foaming, no nitrosamine formation, lower energy requirement and therefore less OPEX. Selected performance results of a new family of amine‐based CO2 absorbents are summarized. High cyclic capacities in the range of 2.9 to 3.2 mol CO2 kg–1 absorbent and low absorption enthalpies of about –30 kJ mol–1 allow for significant savings in the regeneration energy of the absorbent. Calculations with the modified Kremser model indicated a reduction in the specific reboiler heat duty of 45 %. Furthermore, the absorbents developed show much lower corrosion rates than state‐of‐the‐art solutions that are currently employed.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号