NL2034161B1 - method for manufacturing a silicon carbide ceramic membrane - Google Patents
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- NL2034161B1 NL2034161B1 NL2034161A NL2034161A NL2034161B1 NL 2034161 B1 NL2034161 B1 NL 2034161B1 NL 2034161 A NL2034161 A NL 2034161A NL 2034161 A NL2034161 A NL 2034161A NL 2034161 B1 NL2034161 B1 NL 2034161B1
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- membrane
- sic
- support substrate
- source gas
- silicon carbide
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- 239000012528 membrane Substances 0.000 title claims abstract description 116
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 85
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000000919 ceramic Substances 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 14
- 238000000151 deposition Methods 0.000 claims description 30
- 230000008021 deposition Effects 0.000 claims description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- 239000011148 porous material Substances 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 14
- 238000000108 ultra-filtration Methods 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- 239000003651 drinking water Substances 0.000 claims description 3
- 235000020188 drinking water Nutrition 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052863 mullite Inorganic materials 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 22
- 238000004140 cleaning Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 230000032683 aging Effects 0.000 description 9
- 230000001590 oxidative effect Effects 0.000 description 7
- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 6
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000005708 Sodium hypochlorite Substances 0.000 description 5
- 239000000356 contaminant Substances 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 101150071434 BAR1 gene Proteins 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000009285 membrane fouling Methods 0.000 description 2
- 238000001471 micro-filtration Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 238000004375 physisorption Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- BUMGIEFFCMBQDG-UHFFFAOYSA-N dichlorosilicon Chemical compound Cl[Si]Cl BUMGIEFFCMBQDG-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000000572 ellipsometry Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0072—Inorganic membrane manufacture by deposition from the gaseous phase, e.g. sputtering, CVD, PVD
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/0215—Silicon carbide; Silicon nitride; Silicon oxycarbide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/025—Aluminium oxide
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to a method for manufacturing a silicon carbide ceramic membrane via a chemical vapour deposition process, as well as to a silicon carbide ceramic membrane thus obtained. The present invention also relates to the use of such a silicon carbide ceramic membrane in a method for the treatment of water.
Description
Title: method for manufacturing a silicon carbide ceramic membrane
The present invention relates to a method for manufacturing a silicon carbide ceramic membrane via a chemical vapour deposition process, as well as to a silicon carbide ceramic membrane thus obtained. The present invention also relates to the use of such a silicon carbide ceramic membrane in a method for the treatment of water.
Ceramic membranes, especially microfiltration (MF) and ultrafiltration (UF), have been used for drinking water production and wastewater treatment. The mechanical, chemical, and thermal stability of ceramic membranes favours their durable applications in high temperature and corrosive environments where polymeric membranes may not be applicable.
Wastewaters consist of complex contaminants in the form of organic matter and colloidal particles. These contaminants are susceptible to attach to membranes’ surface either via physisorption or chemisorption. In both cases, a significant decline in flux and increase in trans-membrane pressure is observed. If the physisorption of contaminants can be alleviated by back-washing the membrane, this phenomenon is called reversible fouling. On the other hand, if the contaminants are chemisorbed on the membrane surface, then chemical cleaning is performed to get rid of contaminants and restore membrane flux. Thus, ceramic membranes can be chemically cleaned under extreme conditions, after severe fouling, to recover their performance. For organic foulants oxidative cleaning with for instance chlorine or ozone is used in practice. SiC membranes exhibit lower reversible and irreversible fouling for surface water and, especially, produced water treatment, when compared with other ceramic and polymeric membranes. Specific characteristics of SiC UF membranes include: (i) high permeate volumes (Flux) due to their hydrophilic nature; {ii} high quality permeate irrespective of variation in feed quality; (iii) good hydrothermal stability; (iv) good stability across pressure and pH gradients; and (iv) high porosity and uniform pore size distribution.
Pure SiC membranes can be synthesized with various methods such as liquid phase sintering and sintering at low-pressures. However, to form strong covalent Si-C bonds, a high sintering temperature up to 2000 °C in an argon atmosphere and the addition of sintering aids such as Al.O3 and templates are usually necessary for the production of SiC membranes.
According to a publication “Separation and Purification Technology 253 (2020) 117496”, Mingliang Chen et.al, low-pressure chemical vapor deposition (LPCVD) was used to deposit a thin layer of SiC in the pores of commercial ceramic alumina membranes with the objective to use them for oil-in-water emulsion filtration with reduced membrane fouling. The deposition parameters temperature and pressure were selected to obtain a thin and continuous amorphous SiC layer on the membrane surface. The depositions were performed at a temperature of 750 °C, a pressure of 60
Pa and a deposition time between 0 and 150 min to tune layer thickness and membrane pore size.
EP 0 538 143 relates to an inorganic ultrafiltration or nanofiltration membrane comprising a porous support in contact with a ceramic separating layer, wherein the ceramic layer, substantially free of oxygen, is formed from a combination of least two elements selected from silicon, boron, aluminum, titanium, tungsten, phosphorus, zirconium, nitrogen and carbon and in that such layer is deposited by a chemical vapour deposition process, wherein the chemical vapour deposition process is followed by a heat treatment at a temperature of between 250 and 850°C in order to modify its textural characteristics.
Membrane fouling, which is clogging of the membrane pores by foreign materials, is an inevitable phenomenon. It is occurrence during the membrane operations degrades the properties of the membrane and limits the efficiency of the membrane separations processes. To restore the properties of a membrane after it has been completely fouled, it is cleaned with an oxidizing chemical (sodium hypochlorite) for 30-40 mins to alleviate the foreign species present on the surface of the membrane. Depending on the concentration of the oxidizing chemical, the cleaning also deteriorates the performance of the membrane over the number of cleaning cycles. Therefore, membrane suppliers determine the service life of a membrane on the basis of total number of cleaning cycles a membrane can undergo.
Sodium hypochlorite (NaClO) is commonly employed for chemical cleaning of membranes. The highly oxidative nature of NaCIO can selectively leach out inorganic and organic fouling, e.g. biological fouling, and restore primary properties of membrane. Inorganic fouling is most of the time not mitigated by chlorine. The active species present in NaCIO solution depend on the pH of the solution. The cleaning efficiency of NaClO is contingent on the concentration of hypochlorite ion (OCI), and ~OCI concentration is highest in the pH range of 10-12. Therefore, chemical cleaning is normally performed in this pH range. Nonetheless, these active species also deteriorate the physicochemical properties of the selective layer of membrane. The service life of a membrane is subject to the total hours of chemical cleaning with
NaClO. Studies on polymeric membranes have shown that the long-term effects of
NaClO cleaning on the membrane properties are detrimental. Cleaning a membrane with an aggressive oxidizing chemical, e.g. sodium hypochlorite, will adversely affect the surface morphology, mechanical properties, pore size, and pore size distribution of the membranes’ selective layer. Consequentially, the permeability and selectivity of the membrane is compromised.
An object of the present invention is to provide a method for manufacturing chemically robust and durable SiC UF membranes.
Another object of the present invention is to provide SiC UF membranes wherein NaCIO ageing will have no substantial effect on the performance of such a
SiC UF membrane.
Another object of the present invention is to manufacture a SiC UF membrane provided with a highly adhesive, continuous, and robust SiC film, which is stable in
NaClO for at least 100hrs.
The present invention relates to a method for manufacturing a silicon carbide ceramic membrane via a chemical vapour deposition process, the method comprising the following steps: a) providing a source gas for forming a SiC film, b) providing a support substrate, c) positioning the support substrate in a chemical vapour deposition reactor, d) contacting the source gas with the support substrate in the chemical vapour deposition reactor under process conditions for the deposition of a SiC film onto the support substrate, wherein the process conditions comprise a temperature of at least 800 °C and at most 1200 °C and a pressure of at most 200 Pa.
The present inventors found that one or more of the aforementioned objects can be achieved by using such specific process conditions in the chemical vapour deposition process. The present inventors found that the temperature, pressure, and deposition time are related. The present inventors used the higher temperature because of the better stability of the membrane, but at higher temperatures the deposition rate is also higher leading to short deposition times, i.e. deposition times of a few minutes. In order to reduce the deposition rate at high temperatures the present inventors reduced the concentration of the gases by reducing the pressure to a value below 200 Pa.
In an example the process conditions comprise a temperature of at least 850 °C and at most 1100 °C. In an example the process conditions comprise a pressure of at least 5 Pa and at most 100 Pa.
In an example the source gas of a) comprises a mixture of a Si source gas and
C source gas, such as dichlorosilane and acetylene, respectively.
In an example the source gas of a) comprises a gas containing both Si and C, such as dichlorodimethylsilane.
In an example the deposition time during step d) ranges between 5 and 120 minutes.
In an example the support substrate of b) is a ceramic membrane having a specific pore size in a range of at least 2 and at most 200 nm, for example chosen from the group of alumina, titania, mullite, and zirconia.
In an example an inert gas is supplied during step d) to the chemical vapour deposition reactor, the inert gas being chosen from hydrogen and nitrogen, or a combination thereof.
The present invention also relates to a silicon carbide ceramic membrane obtained according to the present method, the membrane having a SiC film on a support substrate, wherein the thickness of the SiC film is at least 1 nm and at most 50 nm, preferably at least 4 nm and at most 30 nm.
In an example of silicon carbide ceramic membrane the membrane is an ultrafiltration membrane for which the mean diameter of the pores is between 2 and 150 nm.
The present invention also relates to a method for the production of drinking water and/or the treatment of wastewater water comprising at least a membrane obtained according to a method as discussed above or a membrane as discussed above.
The invention is further described by reference to the following examples, which are provided for illustration only. The invention is not limited to the examples but rather includes all variations that are evident from the teachings provided herein.
Figure 1 shows pure water permeability of pristine membranes, SiC coated and 5 NaClO aged SiC coated membranes.
Figure 2 shows pore size (nm) of pristine, SiC coated and NaClO aged SiC coated membranes.
Commercial tubular alumina membranes obtained from CoorsTek, The
Netherlands, were used as substrate for LP-CVD. The membranes consisting of a 40nm alumina selective layer on a 600nm macroporous alumina support had an inner diameter of 7mm, outer diameter of 10mm, and were 10cm in length. Membranes with water permeability of ca. 350 L.m-2.h-1.bar-1 were selected for the chemical vapour deposition process of SiC.
Commercially available 12.5 wt.% NaCIO was purchased from Sigma-Aldrich
Chemicals (The Netherlands). 5 wt.% NaCIO was prepared by diluting the 12.5 wt.% stock solution, and the pH was maintained at 12. Sodium alginate obtained from
Sigma-Aldrich Chemicals (The Netherlands) was used to study the fouling behaviour of membranes. Deionized water used to prepare all the solutions.
Hot-wall Low-Pressure Chemical Vapor Deposition (LP-CVD) furnace (Tempress Systems BV, The Netherlands) was used for the deposition of SiC.
Precursors used were Dichlorosilane (SiH2Cl2) and 5% acetylene (C2Hz) in hydrogen (Hz) balance for silicon (Si) and carbon (C) source, respectively. Ultrapure nitrogen from liquid Ns source was employed as purging gas in the system. During SiC deposition, the membranes were placed longitudinally to the flow of precursor gases.
Deposition conditions were adapted to obtain a thin amorphous SiC layer on membrane surface. SiC deposition was performed at two different temperatures and pressures. The SiC growth rate at both conditions were measured on silicon wafers with ellipsometry. Low-temperature SiC deposition was carried out at a temperature of 750°C, pressure of 600mTorr (80 Pa), and deposition time of 60mins. Hereafter, the membranes modified under the aforementioned conditions will be referred to as SiC- 7, where the suffix 7 represents the deposition temperature of 750°C. High- temperature SiC deposition was carried out at a temperature of 860°C, pressure of
100mTorr (13 Pa), and deposition time of 30mins. Hereafter, these membranes will be referred to as SiC-8, where the suffix 8 represents the deposition temperature of 860°C. Temperature, pressure, and deposition time were adjusted in both cases in such a way to obtain a SiC layer of same thickness. Si wafers were used to measure the thickness of deposited SiC layer. The purpose of selecting two different deposition conditions was to make a chemical stability comparison of SiC-7 and SiC-8 membranes in a cleaning medium i.e. sodium hypochlorite (NaClO).
Before the ageing experiments, SiC-7 and SiC-8 membranes were soaked in ultrapure water for 24hrs, and afterward their water permeability was measured. For membrane ageing procedure, dried membrane samples were soaked in 5 wt.% NaCIO solution in an air-tight container at ambient temperature (25+3C) in dark for 200hrs.
This corresponds to an exposure dose of 10000 g.hr/L. The ageing solutions were replaced every 24hrs to avoid the variation of concentration and pH with time.
Hereafter, the aged SiC-7, and SiC-8 membrane will be referred to as SiC-7-2A and
SiC-8-2A, where the suffix 2A represents 200hrs of ageing in 5 wt.% NaCIO. After 200hrs, SiC-7-2A and SiC-8-2A were removed from the 5 wt.% NaCIO solution, rinsed with ultrapure water, and soaked in ultrapure water overnight to remove residual
NaClO species before characterization and performance analysis.
The morphology of pristine alumina, SiC-7/SiC-8, and SiC-7-2A/SiC-8-2A membranes was observed by scanning electron microscopy (SEM, FEI Nova
NanoSEM 450, USA). Energy dispersive x-ray (EDX) analyzer coupled with SEM was used to determine the Si atomic%. Sample preparation for SEM involved breaking the membranes with a hammer to obtain a flat specimen which was afterward sputter coated with gold to increase sample conductivity to achieve clear images.
The surface chemical composition of the SiC-7/SiC-8 and SiC-7-2A/SiC-8-2A membranes was evaluated by x-ray photoelectron spectroscopy (XPS). XPS spectra were obtained using a ThermoFisher K-alpha XPS system. Further processing of the
XPS spectra was done using CasaXPS software.
The average pore size calculated using Young-Laplace equation, of the membranes was measured by capillary flow porometry (Porolux 500, IBFT GmbH,
Germany). FC43 (Benelux Scientific B.V., the Netherlands) was used as wetting agent for porometry measurements, and flow and feed pressure were recorded in time.
After the deposition of SiC at 750°C, a thick SiC layer has been observed on the surface of the membrane. Additionally, random deposits of SiC were also observed along the cross-section of the membrane. The deposition of SiC at 860°C resulted in formation of a thin SiC layer at the surface of the membrane, and deposits of SiC were also observed at the sub-surface (3-6um) of the membrane. However in the deeper parts of the selective layer complete shielding by SiC was not observed.
Pure water permeability (PWP) of the pristine, SiC deposited, and SiC membrane aged in NaClO for 200hrs was measured and the results are shown in Fig. 1. The PWP of the pristine alumina membranes was ca. 350 L.m-2.h-1.bar-1. After the deposition of SiC at 750°C, the PWP of the membrane dropped down to 200 L.m-2.h- 1.bar-1. Increasing the SiC deposition temperature to 860°C further reduced the PWP to 128. Pore size (nm) of the pristine, SiC deposited, and SiC membrane aged in
NaClO for 200hrs was measured and the results are shown in Fig. 2.
Ageing in 5 wt.% NaCIO for 200hrs had different effects on the PWP of both membranes. For SiC-7 membrane, NaClO resulted in substantial increase in PWP.
The PWP of SiC-7-2A membrane increased to ca. 339 L/(m2.h.bar). Furthermore, the
SiC-7-2A membrane changed its appearance from black to off-white after ageing (200hrs in 5 wt.% NaClO), thus implying that the SiC layer had been completely deteriorated. NaClO ageing had no effect on the PWP of the SiC-8 membrane. The
PWP of SiC-8-2A membrane after ageing (200hrs in 5 wt.% NaCIlO) showed no increase.
The present inventors found that the thick SiC layer on the surface and random deposits of SiC along the cross-section of SiC-7-2A were completely removed by exposure to NaClO. The removal of SiC layer led to increase of porosity and pore size of SiC-7-2A. For SiC-8-2A, NaClO exposure had no effect on the SiC layer. The present inventors found that the SiC layer present on the surface and along the cross- section was intact. In addition, a close analysis of the SiC-8-2A revealed that the alumina particles were still completely shielded by the SiC layer. These results demonstrate the stability of SiC layer deposited at high-temperature (860°C) towards harsh oxidizing treatment of NaClO. Without being bound to any scientific theory the present inventors assume that in comparison with low-temperature (750°C) SiC deposition, high-temperature (860°C) and low-pressure (100mTorr) deposition of SiC on alumina substrate leads to some shielding of alumina particles and thus better adhesion strength of the SiC layer to the alumina support. However, complete shielding of the selective layer by SiC was not observed.
The present inventors thus found that complexity of the SiC water filtration membrane preparation is minimized by employing the present method as discussed above, i.e. LP-CVD. The present invention also facilitates the preparation of the SiC membranes at 850-950 °C in about 30mins. Additionally, no post-treatment of the as- prepared SiC layer is required. As such, two precursors are required, and gas-phase reactions lead to formation of chemically robust SiC. Furthermore, the SiC water filtration membranes according to the present invention are stable in oxidizing chemicals (sodium hypochlorite) over long-term (200hrs). Repeated cleaning would facilitate the restoration of the membrane to its original properties, thus extending the service life of membrane. Because the SiC layer can be coated on an alumina support (sintered at 1000 °C), the pore size distribution of the alumina support will be leading to a narrow pore size distribution of the SiC coated membrane.
From the above one will deduce that the advantages of a CVD-coated alumina support versus full SiC membranes are the following. For a full SiC membrane the support should be sintered at 2000 °C whereas an alumina support can be sintered at about 1000 °C. The sintering process of the active membrane layer in a full SiC membrane is at about 2000 °C whereas the CVD process is carried out at a temperature of 850 to 1200 °C. It is difficult to obtain full SiC membranes with uniform pore sizes of less than 70 nm. Alumina membranes can be made with uniform pore sizes down to 20 nm so also CVD-coated SiC membranes can be produced with pore sizes smaller than 70 nm.
Claims (12)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL2034161A NL2034161B1 (en) | 2023-02-16 | 2023-02-16 | method for manufacturing a silicon carbide ceramic membrane |
| PCT/NL2024/050077 WO2024172653A1 (en) | 2023-02-16 | 2024-02-15 | Method for manufacturing a silicon carbide ceramic membrane |
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| Application Number | Priority Date | Filing Date | Title |
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| NL2034161A NL2034161B1 (en) | 2023-02-16 | 2023-02-16 | method for manufacturing a silicon carbide ceramic membrane |
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| NL2034161B1 true NL2034161B1 (en) | 2024-09-03 |
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| NL2034161A NL2034161B1 (en) | 2023-02-16 | 2023-02-16 | method for manufacturing a silicon carbide ceramic membrane |
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| NL (1) | NL2034161B1 (en) |
| WO (1) | WO2024172653A1 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0538143A1 (en) | 1991-10-18 | 1993-04-21 | Tech-Sep | Inorganic filtration membranes with essentially oxygen-free ceramic separating layer |
| US5789024A (en) * | 1996-05-15 | 1998-08-04 | New Jersey Institute Of Technology | Subnanoscale composite, N2-permselective membrane for the separation of volatile organic compounds |
-
2023
- 2023-02-16 NL NL2034161A patent/NL2034161B1/en active
-
2024
- 2024-02-15 WO PCT/NL2024/050077 patent/WO2024172653A1/en not_active Ceased
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0538143A1 (en) | 1991-10-18 | 1993-04-21 | Tech-Sep | Inorganic filtration membranes with essentially oxygen-free ceramic separating layer |
| US5789024A (en) * | 1996-05-15 | 1998-08-04 | New Jersey Institute Of Technology | Subnanoscale composite, N2-permselective membrane for the separation of volatile organic compounds |
Non-Patent Citations (6)
| Title |
|---|
| CHEN MINGLIANG ET AL: "Highly permeable silicon carbide-alumina ultrafiltration membranes for oil-in-water filtration produced with low-pressure chemical vapor deposition", SEPARATION AND PURIFICATION TECHNOLOGY, vol. 253, 1 December 2020 (2020-12-01), NL, pages 117496, XP093069505, ISSN: 1383-5866, DOI: 10.1016/j.seppur.2020.117496 * |
| CHEN MINGLIANG ET AL: "Oil-in-water emulsion separation: Fouling of alumina membranes with and without a silicon carbide deposition in constant flux filtration mode", WATER RESEARCH, ELSEVIER, AMSTERDAM, NL, vol. 216, 8 March 2022 (2022-03-08), XP087021103, ISSN: 0043-1354, [retrieved on 20220308], DOI: 10.1016/J.WATRES.2022.118267 * |
| NGUYEN TUAN-KHOA ET AL: "Superior Robust Ultrathin Single-Crystalline Silicon Carbide Membrane as a Versatile Platform for Biological Applications", APPLIED MATERIALS & INTERFACES, vol. 9, no. 48, 6 December 2017 (2017-12-06), US, pages 41641 - 41647, XP093069797, ISSN: 1944-8244, DOI: 10.1021/acsami.7b15381 * |
| NGUYEN TUAN-KHOA ET AL: "Superior Robust Ultrathin Single-Crystalline Silicon Carbide Membrane as a Versatile Platform for Biological Applications", APPLIED MATERIALS & INTERFACES, vol. 9, no. 48, 6 December 2017 (2017-12-06), US, pages 41641 - 41647, XP093069802, ISSN: 1944-8244, DOI: 10.1021/acsami.7b15381 * |
| PHAM H T M ET AL: "Very thin SiC membranes for micromachined vacuum sensors", 2008 IEEE SENSORS,LECCE, ITALY, IEEE, PISCATAWAY, NJ, USA, 26 October 2008 (2008-10-26), pages 1143 - 1146, XP031375281, ISBN: 978-1-4244-2580-8 * |
| WANG LI ET AL: "Growth mechanism for alternating supply epitaxy: the unique pathway to achieve uniform silicon carbide films on multiple large-diameter silicon substrates", RSC ADVANCES, vol. 6, no. 20, 1 January 2016 (2016-01-01), GB, pages 16662 - 16667, XP093069796, ISSN: 2046-2069, DOI: 10.1039/C5RA24797G * |
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| WO2024172653A1 (en) | 2024-08-22 |
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