Поверхнева полімерізація мономерів на поліетилентерефталатный мембрані при дії низькотемпературної плазми для обробки води
The plasma-chemical method of track-etched polyethylene terephtalate membranes’ surface modification by monomers with different chemical structure was developed. Physicochemical properties of modified membranes were investigated. The authors showed the possibility of obtaining membranes with the req...
Saved in:
| Date: | 2017 |
|---|---|
| Main Authors: | , , , |
| Format: | Article |
| Language: | English |
| Published: |
Chuiko Institute of Surface Chemistry National Academy of Sciences of Ukraine
2017
|
| Online Access: | https://surfacezbir.com.ua/index.php/surface/article/view/640 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| Journal Title: | Surface |
| Download file: |  |
Institution
Surface| _version_ | 1869291798138978304 |
|---|---|
| author | Trachevskiy, V. Vakuliuk, P. Kartel, M. Bo, W. |
| author_facet | Trachevskiy, V. Vakuliuk, P. Kartel, M. Bo, W. |
| author_institution_txt_mv | [
{
"author": "V. Trachevskiy",
"institution": "Технологічний університет \/ Національний авіаційний університет"
},
{
"author": "P. Vakuliuk",
"institution": "Національний університет «Києво-Могилянська академія»"
},
{
"author": "M. Kartel",
"institution": "Інститут хімії поверхні ім. О.О. Чуйка Національної академії наук України \/ Технологічний університет"
},
{
"author": "W. Bo",
"institution": "Технологічний університет"
}
] |
| author_sort | Trachevskiy, V. |
| baseUrl_str | |
| collection | OJS |
| datestamp_date | 2018-12-01T11:34:24Z |
| description | The plasma-chemical method of track-etched polyethylene terephtalate membranes’ surface modification by monomers with different chemical structure was developed. Physicochemical properties of modified membranes were investigated. The authors showed the possibility of obtaining membranes with the required properties. |
| doi_str_mv | 10.15407/Surface.2017.09.111 |
| first_indexed | 2025-09-24T17:25:25Z |
| format | Article |
| fulltext |
Поверхность. 2017. Вып. 9(24). С. 111–117 111
UDC 544.723 + 678.7
SURFACE POLYMERIZATION OF MONOMERS ON THE
POLYETHYLENE TEREPHTHALATE MEMBRANE IN LOW
TEMPERATURE PLASMA FOR WATER TREATMENT
V. Trachevskiy1,2, P. Vakuliuk3, M. Kartel1,4, W. Bo1.
1Ningbo University of Technology, China;
2National Aviation University, Kyiv, Ukraine;
3National University of ”Kyiv-Mohyla Academy”, Kyiv, Ukraine;
4Chuiko Institute of Surface Chemistry of National Academy of Sciences of Ukraine
17 General Naumov Str., Kyiv, 03164, Ukraine.
The plasma-chemical method of track-etched polyethylene terephtalate membranes’
surface modification by monomers with different chemical structure was developed.
Physicochemical properties of modified membranes were investigated. The authors showed the
possibility of obtaining membranes with the required properties.
Keywords: polyethylene terephthalate membranes, plasma-chemical modification, functional
monomers, surface properties.
Introduction
Membrane filtration is one of the most prospective technological processes of complex
mixtures separation. Track membranes take an important place among the materials used in this
process (TM) [1, 2]. Due to a number of properties, especially low thickness and high
homogeneity of pores, TM have insignificant resistance to the flow through the filtering medium,
high selectivity of separation, low adsorption of solutes and ease regeneration. All this favorably
distinguishes TM from other filtering materials and makes them widely used in medicine and
biotechnology.
A new trend has been developed in technology of track membranes in recent years –
membranes’ surface modification, which refers to a deliberate change in the structure of
membranes’ surface layer, which leads to obtaining of required properties. There are a lot of
physical and chemical methods of modifying the surface properties of polymeric materials.
The plasma-chemical method has the greatest advantage over the others [3 – 6]. Specific
effect of low temperature plasma on different materials defined its widespread use in solving
various technological problems in scientific research practice. This specificity is the combination
of high chemical activity with low gas temperature, which makes plasma an effective tool in
polymer modification. An additional advantage of plasma action is that it only impacts small
depths, not exceeding a few micrometers, keeping the bulk properties of a material unchanged.
Thus, plasma treatment actually converts the polymer into a new composite material.
The main advantage of the plasma-chemical method is the possibility to use it for
modification of a wide range of chemical compounds (both organic and inorganic). Chemical
reactions that take place in plasma discharge and determine the polymers’ surface modification
are mainly defined by the composition of the plasma gas. When monomers of organic
compounds are injected into plasma, the following processes are observed: monomer
polymerization and deposition of polymer film onto the polymers’ surface. New surface
properties largely depend on the type of chemical compound used as the plasma gas. The process
of applying a thin polymer layer on the membrane’s surface in plasma is particularly interesting,
as it allows obtaining a membrane with predetermined functional characteristics.
112
It can thus be concluded that polymerization initiated by plasma is a highly effective
method of polymers’ and polymer membranes’ surface modification. This method allows for
very precise and purposeful modification by plasma processing of polymers or plasma-initiated
polymerization. It is worth noting, that this method is applicable for almost any polymeric
material.
The purpose of our study was:
‐ to study track membranes’ surface modification in low-temperature plasma;
‐ to develop a way of modifying PET membranes by plasma with monomers of different
chemical nature to obtain membranes with predetermined functional characteristics.
Experimental part
2.1 Materials
Track-etched polyethylene terephthalate (PET) membranes with pore diameter of 0.05
mm and thickness of 10 microns (production of JINR Dubna, Russia) were used in this work.
Functional monomers for modification are methacrylic acid (MAC), vinylpyrrolidone
(VP), tetrafluoroethane (TFE).
2.2 Methods
Grafting of monomers to the polyethylene terephthalate (PET) membrane’s surface was
conducted in the developed plasma-chemical installation using high-frequency (HF) discharge of
13.56 MHz. The conditions of membranes’ surface plasma-chemical modification were
experimentally chosen: pressure 13.32 Pa., temperature 40-50 oC, monomer flow rate 8 – 10
cm3/min, power 25 – 30 W (Fig. 1)
The efficiency of plasma-chemical modification was estimated by measuring: membrane
surface contact angle, grafting degree of functional monomers, and volumetric water flow
through the membrane by the standard methods [7].
Results and their discussion
Physicochemical modification of hydrophobic membrane allows:
‐ to make the surface hydrophilic (including the surface of pores), which reduces their
susceptibility to contamination (such as proteins, humic substances, etc.),
‐ to provide specific separation characteristics of membranes due to the formation of
certain functional groups on membranes’ surface. Plasma-induced graft polymerization is one of
the most effective and easy methods membranes surface hydrophilisation among many others.
The following chemical reactions occur in oxygen plasma during membrane’s
modification: the C−O bond is broken, radicals are formed and then oxidized, and, as a result, a
carboxyl group and a double bond are formed (Fig. 1).
Fig. 1. Chemical transformations in oxygen plasma.
During the plasma-chemical modification of membrane with methacrylic acid, radicals of
acrylic acid and radicals on the membrane’s surface are formed, Carbon chain is grafted and
growing, and polymethylmethacrylate is formed (Fig. 2).
During the membrane surface modification with vinylpyrrolidone (Fig. 3) and
tetrafluoroethane (Fig. 4) similar chemical reactions occur, by radical addition and formation of
respective polymer on membrane’s surface.
113
Fig. 2. Chemical changes in methacrylic acid plasma.
Fig. 3. Chemical changes in vinylpyrrolidone plasma.
Fig. 4. Chemical changes in tetrafluoroethane plasma.
The structural changes of membrane surface were studied by IR-spectroscopy. Spectrum
of the membrane, modified in oxygen plasma, shows an increase of a peak at 1708.33 cm-1,
which confirms that during modification the bonds are broken and carboxyl groups are formed.
Analysis of the IR-spectrum of the membrane surface, modified with polymethacrylic
acid, indicates the intensity of stretching vibrations of the C=O carboxyl group (1706.42 cm-1)
compared to unmodified membrane. New absorption band also appears at 3423.10 cm-1, which
corresponds to the stretching vibrations of O−H bond; at 2964.17 cm-1, which corresponds to the
asymmetric stretching vibrations of polymethacrylic acid’s CH3-group; and at 1178.44 cm-1,
which corresponds to the stretching vibrations of C−O bond.
Grafting of polymethacrylic acid is additionally confirmed by the increasing intensity of
O−H deformation vibration in carboxyl group at frequency of 1408.41 cm-1.Analysis of the IR-
spectrum of membrane surface modified with vinylpyrrolidone revealed the appearance of a new
absorption peak with a wavelength of 1655 cm-1, which corresponds to fluctuations of amide-
carbonyl group in the N-vinyl-2-pyrrolidone ring. Furthermore, when increasing the degree of
PVP grafting, the intensity of these peaks increased as well. Absorption at 1713 cm-1 is typical
114
for aromatic compounds with C−H and C=O bonds. Also, there is an increase of peak intensity at
3394 cm-1 in the IR-spectrum. It also indicates that grafting is actually happening.
Research of the tetrafluoroethane-modified membrane surface structure by IR
spectroscopy, shows the presence of several bands that are characteristic for polytetrafluoro-
ethylene. These are bands with wavelengths of 1160 and 1220 cm-1, which correspond to
symmetric and asymmetric −CF2− stretching vibrations of polytetrafluoroethylene; absorption
bands at 513 and 555 cm-1 are associated with −CF2− circular and polygonal deformation
vibrations; absorption bands in the 1400-1450 cm-1 region correspond to C−C stretching
vibrations in main polymer chain and band with wavelength of 990 cm-1 corresponds to −CF3
symmetric stretching vibrations. IR spectroscopy data confirm the fact that polymer, which was
synthesized by plasma discharge of 1,1,1,2-tetrafluoroethane, consists of −CF2− groups.
While studying modification of track-etched membranes with monomers, it was found
out that increase of processing time leads to sample mass growth due to the grafting of
monomers to the membrane’s surface (Fig. 5). The opposite effect is observed while using
oxygen as the aerogenous gas – the sample weight decreases due to the destruction and etching
of the track-etched membrane’s surface.
The surface properties of PET membranes modified with oxygen, methacrylic acid and
vinylpyrrolidone using the plasma-chemical method were studied by water contact angle
measuring. The results are shown in Table 1.
Table 1. The membranes’ surface contact angles
Duration(sec)
Plasma gas
30 sec 120 sec 210 sec 300 sec
Oxygen 28 23 23 23
Methacrylic acid 57 49 45 45
Polyvinylpyrrolidone 47 39 34 34
Fig. 5. Dependence between the grafting degree and the time.
The extrapolation of data was shown using the graphs, which represented the dependence
between the membrane surface contact angle and plasma processing time. Summary of
membrane hydrophilicity is also given (Fig. 6 − 7).
The investigation of the process of track-etched membrane modifications has shown that
the hydrophilicity of all membranes, except when using TFE (Fig. 7), increases. This graph also
represents that the optimal time for sample modification is 80 sec, because all significant
changes in the values of contact angles occur up to 80 sec and then almost no change take place.
Protein adsorption on plasma-modified membrane surface was also studied in a variety of
conditions.
115
Fig. 6. Dependence between the
surface contact angle and
plasma processing time of
the track-etched
membranes.
Fig. 7. The contact angles obtained at the optimal time of modification by low-temperature
plasma.
Plasma graft polymerization leads to the decrease in the effective radius of membrane
pores, which causes transmembrane volumetric water flow value to drop. Thus, the degree of
grafting can be characterized by the change of volumetric water flow through the membrane
before and after modification.
As shown in Fig. 8, there was a strong decrease of the volumetric water flow through the
membranes, which were plasma-treated for 30 and 120 sec, which can be explained by monomer
grafting to the surface. In case of longer modification time the gradual decrease of the volumetric
water flow occurs. After 120 sec of treatment, the decrease becomes less visible, which can be
explained by surface saturation with monomers. Considering the results above, the optimal
duration of modification is 120 sec.
Fig. 8. Dependence between the volumetric water flow through the membrane and the duration of
plasma-chemical modification.
116
Conclusions
In this study, the plasma-chemical methods of the PET track-etched membrane surface
modification were developed with the purpose of changing their hydrophilic/hydrophobic
characteristics. Optimal modification parameters to obtain the membranes with predetermined
functional properties of their surface (pressure 10 − 20 Pa, frequency 13.56 MHz, temperature
40-60 oC, power 25 − 30 W, gas flow rate 8.10 sm3/hv) were experimentally obtained. The
presence of characteristic absorption bands for modifiers was proven by infrared spectroscopy
(C=O 1706.42 cm-1; −CF2− 1160 cm-1 and 1220 cm-1). The authors showed the possibility of
plasma-chemical surface modification of PET track-etched membranes with the purpose to
obtain the required properties.
References
1. Ulbricht M., Belfort G. Surface modification of ultrafiltration membranes by low temperature
plasma: I. Treatment of polyacrylonitrile // J. Appl. Polym. Sci., 1995. – Vol. 56, №2. - Р. 325-
343
2. Ulbricht M., Belfort G. Surface modification of ultrafiltration membranes by low temperature
plasma II. Graft polymerization onto polyacrylonitrile and polysulfone // J. Membr. Sci., 1996. –
Vol. 111, №1. - Р. 193-215.
3. Gilman A.B. Plazmohimicheskaia modifikacyia poverhnosti polimernyh materialov. RF GNC
“Nauchno-issledovatel’skiy physico-khimicheskiy institute im. L.Y. Karpova” 2004.
4. Roudman A.R., DiGiano F.A. Surface energy of experimental and commercial nanofitration
membranes: effects of wetting and natural organic matter fouling // Department of Environmental
Sciences and Engineering, University of North Carolina, Chapel Hill, 2000, 65.
5. Fortov V.E. Encyklopediia nizkotemperaturnoi plasmy. - Moskva: Nauka, 2000, 393 p.
6. Kulovaara M., Metsamuuronen S. Effects of aquatic humic substances on a hydrophobic
ultrafiltration membrane // Chemosphere, 1999. – Vol. 38, №15. – P. 3485-3496.
7. Frolov Y.G., Grodskoi A.S. Practicheskie raboty po kolloidnoi khimii. -
Moskva: Khimiia, 1986, 216 p.
ПОВЕРХНОСТНАЯ ПОЛИМЕРИЗАЦИЯ МОНОМЕРОВ НА
ПОЛИЭТИЛЕНТЕРЕФТАЛАТНОЙ МЕМБРАНЕ ПРИ
ВОЗДЕЙСТВИИ НИЗКОТЕМПЕРАТУРНОЙ ПЛАЗМЫ ДЛЯ
ОБРАБОТКИ ВОДЫ
В. Трачевский1,2, П. Вакулюк3, Н. Картель1,4, В. Бо1
1Технологический университет, Нангбо Китай;
2Национальный авиационный университет, Киев, Украина;
3Национальный университет «Киево-Могилянская академия», Киев, Украина;
4Институт химии поверхности им. А.А. Чуйко Национальной академии наук Украины,
ул. Генерала Наумова, 17, Киев, 03164, Украина.
Разработана плазмохимическая методика модификации поверхности полиэтилен-
терефталатной мембраны мономерами различной химической структуры. Исследованы
физико-химические свойства модифицированных мембран. Авторы продемонстрировали
возможность получения мембран с требуемыми свойствами.
117
ПОВЕРХНЕВА ПОЛІМЕРІЗАЦІЯ МОНОМЕРІВ НА
ПОЛІЕТИЛЕНТЕРЕФТАЛАТНЫЙ МЕМБРАНІ ПРИ ДІЇ
НИЗЬКОТЕМПЕРАТУРНОЇ ПЛАЗМИ ДЛЯ ОБРОБКИ ВОДИ
В. Трачевський1,2, П. Вакулюк3, Н. Картель1,4, В. Бо1
1Технологічний університет, Нангбо Китай;
2Національний авіаційний університет, Київ, Україна;
3Національний університет «Києво-Могилянська академія», Київ, Україна;
4Інститут хімії поверхні ім. О.О. Чуйка Національної академії наук України
вул. Генерала Наумова, 17, Київ, 03164.
Розроблена плазмохімічна методика модифікації поверхні поліетиленте-
рефтальної мембрани мономерами різної хімічної структури. Вивчено фізико-хімічні
властивості модифікованих мембран. Автори продемонстрували можливість отримання
мембран з потрібними властивостями.
|
| id | oai:ojs.pkp.sfu.ca:article-640 |
| institution | Surface |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2025-09-24T17:45:45Z |
| publishDate | 2017 |
| publisher | Chuiko Institute of Surface Chemistry National Academy of Sciences of Ukraine |
| record_format | ojs |
| resource_txt_mv | surfacezbircomua/fb/556d47e7a3b8da96c06f380762fa1cfb.pdf |
| spelling | oai:ojs.pkp.sfu.ca:article-6402018-12-01T11:34:24Z Surface polymerization of monomers on the polyethylene terephthalate membrane in low temperature plasma for water treatment Поверхностная полимеризация мономеров на полиэтилентерефталатной мембране при воздействии низкотемпературной плазмы для обработки воды Поверхнева полімерізація мономерів на поліетилентерефталатный мембрані при дії низькотемпературної плазми для обробки води Trachevskiy, V. Vakuliuk, P. Kartel, M. Bo, W. polyethylene terephthalate membranes plasma-chemical modification functional monomers surface properties The plasma-chemical method of track-etched polyethylene terephtalate membranes’ surface modification by monomers with different chemical structure was developed. Physicochemical properties of modified membranes were investigated. The authors showed the possibility of obtaining membranes with the required properties. Разработана плазмохимическая методика модификации поверхности полиэтилентерефталатной мембраны мономерами различной химической структуры. Исследованы физико-химические свойства модифицированных мембран. Авторы продемонстрировали возможность получения мембран с требуемыми свойствами. Розроблена плазмохімічна методика модифікації поверхні поліетиленте-рефтальної мембрани мономерами різної хімічної структури. Вивчено фізико-хімічні властивості модифікованих мембран. Автори продемонстрували можливість отримання мембран з потрібними властивостями. Chuiko Institute of Surface Chemistry National Academy of Sciences of Ukraine 2017-10-08 Article Article application/pdf https://surfacezbir.com.ua/index.php/surface/article/view/640 10.15407/Surface.2017.09.111 Surface; No. 9(24) (2017): Surface; 111-117 Поверхность; № 9(24) (2017): Поверхность; 111-117 Поверхня; № 9(24) (2017): Поверхня; 111-117 3154-8091 3154-8083 10.15407/Surface.2017.09 en https://surfacezbir.com.ua/index.php/surface/article/view/640/640 Авторське право (c) 2017 V. Trachevskiy, P. Vakuliuk, M. Kartel, W. Bo |
| spellingShingle | Trachevskiy, V. Vakuliuk, P. Kartel, M. Bo, W. Поверхнева полімерізація мономерів на поліетилентерефталатный мембрані при дії низькотемпературної плазми для обробки води |
| title | Поверхнева полімерізація мономерів на поліетилентерефталатный мембрані при дії низькотемпературної плазми для обробки води |
| title_alt | Surface polymerization of monomers on the polyethylene terephthalate membrane in low temperature plasma for water treatment Поверхностная полимеризация мономеров на полиэтилентерефталатной мембране при воздействии низкотемпературной плазмы для обработки воды |
| title_full | Поверхнева полімерізація мономерів на поліетилентерефталатный мембрані при дії низькотемпературної плазми для обробки води |
| title_fullStr | Поверхнева полімерізація мономерів на поліетилентерефталатный мембрані при дії низькотемпературної плазми для обробки води |
| title_full_unstemmed | Поверхнева полімерізація мономерів на поліетилентерефталатный мембрані при дії низькотемпературної плазми для обробки води |
| title_short | Поверхнева полімерізація мономерів на поліетилентерефталатный мембрані при дії низькотемпературної плазми для обробки води |
| title_sort | поверхнева полімерізація мономерів на поліетилентерефталатный мембрані при дії низькотемпературної плазми для обробки води |
| topic_facet | polyethylene terephthalate membranes plasma-chemical modification functional monomers surface properties |
| url | https://surfacezbir.com.ua/index.php/surface/article/view/640 |
| work_keys_str_mv | AT trachevskiyv surfacepolymerizationofmonomersonthepolyethyleneterephthalatemembraneinlowtemperatureplasmaforwatertreatment AT vakuliukp surfacepolymerizationofmonomersonthepolyethyleneterephthalatemembraneinlowtemperatureplasmaforwatertreatment AT kartelm surfacepolymerizationofmonomersonthepolyethyleneterephthalatemembraneinlowtemperatureplasmaforwatertreatment AT bow surfacepolymerizationofmonomersonthepolyethyleneterephthalatemembraneinlowtemperatureplasmaforwatertreatment AT trachevskiyv poverhnostnaâpolimerizaciâmonomerovnapoliétilentereftalatnojmembraneprivozdejstviinizkotemperaturnojplazmydlâobrabotkivody AT vakuliukp poverhnostnaâpolimerizaciâmonomerovnapoliétilentereftalatnojmembraneprivozdejstviinizkotemperaturnojplazmydlâobrabotkivody AT kartelm poverhnostnaâpolimerizaciâmonomerovnapoliétilentereftalatnojmembraneprivozdejstviinizkotemperaturnojplazmydlâobrabotkivody AT bow poverhnostnaâpolimerizaciâmonomerovnapoliétilentereftalatnojmembraneprivozdejstviinizkotemperaturnojplazmydlâobrabotkivody AT trachevskiyv poverhnevapolímerízacíâmonomerívnapolíetilentereftalatnyjmembranípridíínizʹkotemperaturnoíplazmidlâobrobkivodi AT vakuliukp poverhnevapolímerízacíâmonomerívnapolíetilentereftalatnyjmembranípridíínizʹkotemperaturnoíplazmidlâobrobkivodi AT kartelm poverhnevapolímerízacíâmonomerívnapolíetilentereftalatnyjmembranípridíínizʹkotemperaturnoíplazmidlâobrobkivodi AT bow poverhnevapolímerízacíâmonomerívnapolíetilentereftalatnyjmembranípridíínizʹkotemperaturnoíplazmidlâobrobkivodi |