CN104559095B - It is used to prepare the resin combination of micro- porous membrane and micro- porous membrane - Google Patents
It is used to prepare the resin combination of micro- porous membrane and micro- porous membrane Download PDFInfo
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- CN104559095B CN104559095B CN201310517462.6A CN201310517462A CN104559095B CN 104559095 B CN104559095 B CN 104559095B CN 201310517462 A CN201310517462 A CN 201310517462A CN 104559095 B CN104559095 B CN 104559095B
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Abstract
The present invention relates to a kind of resin combination for being used to prepare micro- porous membrane and the micro- porous membrane being prepared, said composition to contain the component of following parts by weight：Polylactic resin A：20 80 parts by weight；The resin Composition B incompatible with polylactic acid：5 50 parts by weight；Filler C：5 50 parts by weight；Completely in B phases or filler C of the part in B phases percentage C%>（0.9×B%+10%）, wherein B% is B percentage by volumes shared in resin combination, and the moisture-vapor transmission for micro- porous membrane which prepares is higher than the moisture permeability for the film that filler is evenly distributed.The resin combination of the present invention for being used to prepare micro- porous membrane, can be used for preparing micro- porous membrane, can be used for the fields such as amenities, construction material.
Description
Technical field
The invention belongs to polymeric material field, is related to a kind of resin combination for being used to prepare micro- porous membrane, and
Thus micro- porous membrane that prepared by resin combination.
Background technology
The so-called micro- porous membrane of Waterproof Breathable, after referring to that polymer is mixed with filler, the methods of by curtain coating or blowing
Original film is made, then through one-way or bi-directional stretching, makes interfacial separation occurs between filler and polymer or polymer and polymer,
Produce film Voiding.It is disposable that the micro- porous membrane of Waterproof Breathable is chiefly used in nursing materials, physiological hygiene articles for use, paper diaper etc.
On articles for use.The polymer is usually polyolefin, especially polyethylene or polypropylene.Polyolefin polymers non-degradable,
And using oil as raw material, so such film has a certain impact environment.As patent document CN1204167C is revealed
Gas film, includes polypropylene copolymer and filler.
Strengthen with the environmentally protective theory of the public, the plastic film based on biodegradable and biological material is increasingly
Praised highly.Polylactic acid is a kind of Biodegradable polyester, and micro- porous membrane containing the polymer has been mentioned, and can be protected in health
It is applied in the fields such as reason, medical treatment.But since its performance and the gap of conventional polyolefins material, its moisture permeability generally compare
It is low.
The method that CN 201310185870.6 uses particle-filled-stretching, there is provided one kind biodegradation containing polylactic acid etc. gathers
Micro- porous membrane of compound, the area of surface holes of the diameter in 0.2~7 μ m accounts for the 0.5%-15% of total surface area, water-fast
Degree is more than 800mm, and moisture permeability is more than 1000g/ (m2Day), firm softness is less than 40mm.Moisture permeable waterproof film can be used as to be used to defend
Raw nursing field.
The content of the invention
The defects of polylactic acid is due in its processing performance, it usually needs compounding use is carried out with other resins, due to phase point
From presence, other resins in dispersed phase cannot be sufficiently tensile, this part resin can have vapor certain resistance
Every effect, cause its manufactured film moisture permeability relatively low.
For drawbacks described above of the prior art, the present invention provides a kind of resin combination for being used to prepare micro- porous membrane
Thing, it contains polylactic resin, the one or more of resins and filler incompatible with polylactic acid, and by the way that filler is selected
Selecting property is dispersed in the incompatible resin phase of the same polylactic acid, or is dispersed in interface of the polylactic acid with incompatible resin
On, make that there is very high penetrability by micro- porous membrane prepared by said composition, moisture-inhibiting reaches 1500g/（m2·d）More than.
Specifically, the present invention provides a kind of resin combination for being used to prepare micro- porous membrane, contains following parts by weight
Several components：Polylactic resin A：20-80 parts by weight；The resin Composition B incompatible with polylactic acid：5-50 parts by weight；Filler C：
5-50 parts by weight；Wherein, the filler C in B phases accounts for the percentage C% of filler C completely in B phases or partly>（0.9×B%+
10%）, wherein B% is B percentage by volumes shared in resin combination.
The resin combination of micro- porous membrane, the preferably component containing following parts by weight are used to prepare in the present invention：
Polylactic resin A：40-75 parts by weight；The resin Composition B incompatible with polylactic acid：10-40 parts by weight；Filler C：10-45 weight
Part.Excessive filler be easy to cause film strength decline, and very few filler can cause film void content low, influence moisture permeability.
The polylactic resin（A）Be polylactic acid or lactic acid and hydroxycarboxylic acid copolymer in one or more.It is excellent
The molecular structure of the polylactic acid of choosing is made of the 80-100mol% and respective enantiomer 0-20mol% of L lactic acid or D lactic acid
Molecular structure.The hydroxycarboxylic acid, can include hydroxyacetic acid, hydroxybutyric acid, hydroxypentanoic acid, hydroxycaproic acid or hydroxyl
Enanthic acid etc., preferably hydroxyacetic acid, hydroxypentanoic acid or hydroxycaproic acid.In addition, the copolymer of the lactic acid and hydroxycarboxylic acid is by L breasts
The 85-100mol% and hydroxycarboxylic acid unit 0-15mol% of acid or D lactic acid are formed.Above-mentioned polylactic resin can from L lactic acid or
The material of structure needed for selection is as raw material among one or both of D lactic acid and hydroxycarboxylic acid, and by dehydrating polycondensation and
Obtain.Preferably, can the lactide from the cyclic dimer as lactic acid, the second of the cyclic dimer as hydroxyacetic acid
The material of structure needed for selection, is obtained by ring-opening polymerisation in lactide and caprolactone etc..There is the ring-type two of L lactic acid in lactide
Polymers, that is, L lactides, cyclic dimer, that is, D lactides of D lactic acid, D lactic acid and L lactic acid are carried out in obtained from cyclic dimer
The racemic mixture of meso-lactide and D lactides and L lactides, that is, DL lactides.It can be used in the present invention any
A kind of lactide.But, the preferred D lactides of main material or L lactides.
On polylactic resin（A）Molecular weight, there is no particular limitation, but from improving molding processibility and mechanical property
Angle on consider, preferable weight-average molecular weight 50,000~500,000, further preferred 80,000-30 ten thousand.
The polylactic resin A is crystalline polylactic acid, amorphism polylactic acid or crystalline polylactic acid and amorphism
The composition of polylactic acid.Preferably amorphism polylactic acid or the composition of amorphism polylactic acid and crystalline polylactic acid.More preferably
For amorphism polylactic acid and the composition of crystalline polylactic acid, wherein amorphism polylactic acid weight content is further preferably higher than
50%。
It is preferably also to contain plasticizer D in the polylactic resin A.
Since polylactic acid is rigidly big, there is difficult processing, plasticizer is added in its process, it can be improved
Pliability simultaneously improves its processing performance.
The plasticizer D is preferably polyethylene glycol, polypropylene glycol, lactic acid oligomer, lactide oligomer, epoxy second
Alkane/epoxy propane copolymer, citrate triethyl, tributyl citrate, acetyl triethyl citrate, three fourth of acetyl tributyl citrate
Ester, Coronex, polycaprolactone and the copolymer of polylactic acid, the copolymer of poly-succinic fourth diester and polylactic acid, poly- alkyl
One or several kinds in the copolymer or castor oil of glycol and lactic acid and the copolymer of lactic acid.
The incompatible resin Composition B of the same polylactic acid, is to have thermoplastic fluoropolymer resin, there is provided film is with suitable
When flexibility.
From the viewpoint of the further flexibility and processing performance for improving film, the incompatible tree of the same polylactic acid
Polyolefins that fat component B is preferably glass transition temperature less than 40 DEG C, polyurethanes, vinyl acetate esters, polyamide-based, poly- first
Aldehydes, polynitriles class, aliphatic polyester series, aromatic polyester class, aliphatic-aromatic copolyester class, fatty poly-ester carbonate class,
Or the one or more in aromatic copolycarbonate class.
The polyolefins is：One or more in polyethylene, polypropylene or polybutene.
The polyurethanes is：Thermoplastic polyurethane.
The vinyl acetate esters are：One kind or several in polyvinyl acetate and ethylene-vinyl acetate copolymer
Kind.
It is described polyamide-based to be：It is made by interior acid amide ring-opening polymerisation, or obtained by diamine and binary acid polycondensation etc.
Polymer.
The polyformaldehyde class is：The homopolymer obtained by oxymethylene polymerization.
The polynitriles class is：Polyacrylonitrile, or the polymer of other nitriles.
The fatty acid polyglycol esters are by aliphatic dicarboxylic acid（Including its derivative）And aliphatic diol（Spread out including it
Biology）, hydroxycarboxylic acid（Including its derivative）Or the one or more of of lactone carry out polycondensations or ring-opening polymerisation forms.
The aromatic polyester is by aromatic dicarboxylic acid（Including its derivative）With aromatic series (or aliphatic) glycol
（Including its derivative）, hydroxycarboxylic acid（Including its derivative）Or lactone it is one or more of carry out polycondensations or ring-opening polymerisation and
Into.
The aliphatic-aromatic copolyester class be added in the monomer for state in composition aliphatic polyester it is a kind of or several
The aromatic series aliphatic dicarboxylic acid of kind（Including its derivative）Monomer, carries out what polycondensation formed.
The fatty poly-ester carbonate class is to include the resin of-O-R-O-CO- construction units.Wherein, R represents carbon
The alkylidene with substituent of atomicity 2~20 or carbon number 6~20 can be with the cycloalkylidene of substituent
It is one or more of.
The aromatic copolycarbonate class is to include the resin of-O-R-O-CO- construction units.Wherein R represents to contain benzene
One or more in the aromatic substituents with substituent of ring or condensed ring.
The incompatible resin Composition B of the same polylactic acid is more preferably polyethylene, polypropylene, polybutene, polychlorostyrene
It is ethene, polyacrylonitrile, polyurethane, polymethyl methacrylate, makrolon, polybutylene terephthalate (PBT), poly- to benzene two
Formic acid glycol ester, polystyrene, polyvinyl acetate, ethylene-vinyl acetate copolymer, poly butyric ester, poly- hydroxyl
Butyric acid valerate, poly butyric capronate, poly butylene succinate, poly-succinic tetramethylene adipate, polycaprolactone,
Poly terephthalic acid tetramethylene adipate, poly terephthalic acid adipic acid propylene glycol ester, poly terephthalic acid succinic acid fourth two
One or more in alcohol ester, poly- ethylene carbonate, polypropylene carbonate or polymerized thylene carbonate cyclohexyl.
The filler C refers to inorganic filler or/and organic filler.
Inorganic filler, can specifically include glass fibre, asbestos fibre, carbon fiber, graphite fibre, metallic fiber,
Potassium titanate crystal whisker, aluminium borate whisker, magnesium system whisker, silicon systems whisker, wollastonite, sepiolite, asbestos, slag fibre, eakleite,
Ellestadite, gypsum fiber, silicon dioxide fibre, silica/alumina fiber, Zirconium oxide fibre, boron nitride fiber, nitridation
It is one or more or glass flake in the threadiness inorganic filler such as silica fibre or boron fibre, non-bloating tendency mica, bloating tendency
Mica, graphite, metal foil, ceramic beads, talcum, clay, mica, sericite, zeolite, bentonite, vermiculite, montmorillonite, white clouds
Stone, kaolin, micro mist silicic acid, feldspar powder, potassium titanate, fine hollow glass ball, calcium carbonate, magnesium carbonate, calcium sulfate, titanium dioxide
The sheets such as titanium, silica, gypsum, novaculite, dawsonite or carclazyte or one kind or several in granular inorganic filler
Kind.
Organic filler, can specifically include the vegetative fibers such as starch, cellulose, sisal fiber or bamboo fibre, sheep
One or more in the organic synthetic fibers such as the animal fibers such as wool fibre, aramid fibre or aromatic polyester fibres.
Filler C be more preferably zeolite powder, talcum powder, mica powder, titanium dioxide, silica, calcium carbonate, calcium sulfate,
One kind or several in montmorillonite, ceramic microsphere, starch, cellulose, vegetative fiber, animal fiber or organic synthetic fibers
Kind.
Above-mentioned filler（C）Any form of surface treatment can be carried out, to strengthen it with the interfacial adhesion between resin.
The filler（C）In, still further preferably calcium carbonate, zeolite powder, talcum powder, mica powder, titanium dioxide, titanium dioxide
One or more in silicon, calcium sulfate or montmorillonite.Most preferably calcium carbonate.
The filler（C）Though average grain diameter it is nonessential, be preferred with 0.01~10 μm.
The resin combination is used to prepare micro- porous membrane, in order to further improve the flexibility of micro- porous membrane,
Bulking agent also containing parts by weight 0.1-5 parts by weight（E）.Bulking agent（E）It is with two or more in molecular structure
Can be with the one or more in the compound of carboxyl or the response type functional group of hydroxyl reaction, the response type functional group is ring
Oxygen functional group, isocyanate functional group, carbodiimides functional group, anhydride functional group, silane functional, oxazoline functional group or
One or more in phosphite ester functional group.Carboxyl or hydroxyl reaction by these response type functional groups with polylactic acid, can
To carry out increase-volume to polylactic acid.
Specifically, bulking agent（E）Can be toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, to two methylene of benzene
Group diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl methyl hydride diisocyanate, lysine three
Isocyanates, γ-glycidyl ether oxygen propyl trimethoxy silicane, polymerization charing diimine, ethylene-acrylate-maleic acid
One or more in acid anhydride terpolymer or acrylic polymer with epoxy-functional.
In addition, the resin combination for being used to prepare micro- porous membrane of the present invention, needs according to practical application, in addition can be
Suitable heat stabilizer, end-capping reagent, anti ultraviolet agent, fire retardant, nucleator, lubricant, antistatic additive or colouring agent etc. is added to help
One or more in agent.
Do not required particularly for the species of each auxiliary agent, various known commodity can be used.It polymerize from biodegradation
Consider on the adaptable angle of thing, the preferred hindered phenol series compound of heat stabilizer, phosphite ester based compound or thioether system chemical combination
One or more in thing；End-capping reagent preferred isocyanate based compound, carbodiimides based compound or oxazoline based compound
In one or more；The preferred benzophenone based compound of anti ultraviolet agent, benzotriazole based compound, aromatic series benzoic ether system
Compound, oxanilide based compound, cyanoacrylate based compound or the one or more being obstructed in amine compound；
Fire retardant preferably comprises the antimonials such as the halogen based compound of bromine or chlorine, antimony trioxide, inorganic hydrate or phosphorus compound etc.
In one or more；Nucleator preferred aliphat acid amides based compound, aliphatic ester compound or one kind in talcum powder or
It is several；One or more in the preferably low white oil of lubricant, paraffin or aliphatic amide based compound.
The all or part of distributions in B phases of filler C can cause the increase of B phase apparent sizes, and so-called apparent size refers to use
The methods of section, obtains the section of resin combination, after the profile that B is ticked with pen, utilizes image processing software Image J 1.46
The sectional area of all B phases is calculated, recycles the average value for the corresponding diameter of a circle that the sectional area calculates as B phases
Apparent size.The apparent size of the phase of the incompatible resin Composition B component of the same polylactic acid is optimized for 0.5 μm -50 μm, more
1 μm -20 μm of its diameter is optimized for, is further optimized for 2 μm -15 μm of diameter.The apparent size increase of B phases is conducive to obtained thin
The raising of film moisture permeability, but the increase of the apparent size of B phases can reduce the physical property of film.
The present invention also provides a kind of by the micro- porous thin of the resin combination for the being used to prepare micro- porous membrane preparation
Film.
The micro- porous membrane being prepared by the present invention, its moisture permeability is in 1500-4000g/（m2·d）.
The present invention is not particularly limited for the preparation method of film, can use film-forming method of the prior art.Example
Such as：After each component is mixed by melt blending, former film is made through being blow molded or being cast, then be made through uniaxial or biaxial stretching.
The resin combination of the present invention for being used to prepare micro- porous membrane, can be used for preparing micro- porous membrane, can
For fields such as amenities, construction materials.Due to the inclined distributed mutually of particle filled composite, make it in drawing process, two-phase tree
Fat can preferably be separated, and can also preferably produce hole in the resin phase incompatible with polylactic acid, be made by it
Micro- porous membrane have the characteristics that moisture permeability is high.
Embodiment
The present invention is described in more detail by following embodiments, but the embodiment does not form the limit to the present invention
System.
Embodiment and the test method used in comparative example are as follows：
Thickness：Measured using 7050 type thickness gauge of instrument company of Sanyo, take the average value of 9 data.
Weight average molecular weight：Measured using gel permeation chromatography, using chloroform as mobile phase, measure 3 times, be averaged.
Filler location of C defines：Resin combination section is observed with TEM, general polylactic acid A and with polylactic acid not phase
The resin B and filler C of appearance, under the tem observation are presented different contrasts, the position of C are distinguished with this.For with polylactic acid contrast
Close resin can utilize the methods of known dyeing and improve its contrast.
The calculating of B%：B% is B percentage by volumes shared in resin combination, first with the density p of resin combinationct
Calculate mctThe volume of the composition of parts by weight, recycles the density p of BBCalculate mctThe corresponding volume of resin combination of part,
The ratio of the volume of B and the volume of resin combination is B%, and calculation formula is as follows：
The percentage C% of all or part of C in B phases：Resin combination section is seen with TEM as stated above
Examine, the photo 5 of 1000 times of random shooting diverse location enlargement ratio is opened, after the profile that B and filler C are ticked with pen, at image
Reason software I mageJ 1.46r calculate respectively filler C area S and in whole or in part B phases C area SC, Sc divided by S
Obtain C%.
The apparent diameter of B：With the section of acquirement resin combination the methods of section, after the profile that B is ticked with pen, figure is utilized
As processing software I mage J 1.46 calculate the sectional area of all B phases, the corresponding circle for recycling the sectional area to calculate
Diameter apparent size of the average value as B phases.
Rate of perviousness：Based on JIS Z0208:1976,25 DEG C of temperature, humidity 90%.Measure 3 times, is averaged.
Fastness to water：Based on JIS L1092:2009, A methods.Measure 3 times, is averaged.
Embodiment and the raw material used in comparative example are as follows：
＜ polylactic resin ＞（A）
A-1：Polylactic acid, 4032D, Natureworks companies of the U.S..
A-2：Polylactic acid, 4060D, Natureworks companies of the U.S..
Resin ＞ incompatible with polylactic acid ＜（B）
B-1：Poly butylene succinate, Bionolle 1020, Japanese Showa high score subsidiary.
B-2：Poly butyric-hydroxyl valerate, ENMAT Y1000P, Ningbo Tianan Biological Material Co., Ltd..
B-3：Poly terephthalic acid tetramethylene adipate, Ecoflex 7011, BASF Corp. of Germany.
B-4：Polypropylene carbonate, BioCO2 100, Inner Mongol Meng Xi new and high technologies group company.
＜ fillers ＞（C）
C-1：Calcium carbonate, 3.6-5.0 μm of particle diameter, common fine powder Co., Ltd. of Japan three.
C-2：Talcum powder, 3.5-5.5 μm of particle diameter, Haicheng Xinda Mining Co., Ltd..
C-3：5A zeolite powders, Shanghai zeolite molecular sieve company.
＜ plasticizer ＞（D）
D-1：Tributyl 2-acetylcitrate, Jiangsu Leimeng Chemical Industry Science and Technology Co., Ltd.
D-2：Polypropylene glycol, number-average molecular weight 2000, Jiangsu Hai'an Petrochemical Plant.
D-3：Polylactide-polyethylene glycol-polylactic acid triblock copolymer, according to the embodiment 1 of CN200810018621.7
Manufactured.
＜ bulking agents ＞（E）
E-1：Ethylene/methyl acrylate/glycidyl methacrylate copolymer, LotaderAX8900, France
Arkema companies.
E-2：Multi-epoxy functional group cinnamic acrylic ester oligomer, JoncyrlADR 4368, BASF Corp. of Germany.
E-3：Methyl diphenylene diisocyanate, BASF Corp. of Germany.
Embodiment 1-9：
The proportioning listed by table 1, is granulated with double screw extruder, 160-220 DEG C of extrusion temperature.Then, list is passed through
Screw extruder is blow molded, and prepares the former film that thickness is 80 μm.180-200 DEG C of blow temperatures.And then at 85 DEG C, to former film into
The biaxial tension that 3.5 × 3.5 times of row, then, carries out the test of various performances, the results are shown in Table 1 to the film of gained.
1 (unit of table：Parts by weight)
Table 1（It is continuous）(unit：Parts by weight)
Claims (10)
- A kind of 1. resin combination for being used to prepare micro- porous membrane, it is characterised in that：Component containing following parts by weight：It is poly- Lactic acid Resin A：20-80 parts by weight；The resin Composition B incompatible with polylactic acid：5-50 parts by weight；Filler C：5-50 parts by weight, Wherein filler C is at least one of calcium carbonate or talcum powder；Wherein, the filler C in B phases is accounted for completely in B phases or partly The percentage C% of filler C>(0.9 × B%+10%), wherein B% are B percentage by volumes shared in resin combination.
- 2. the resin combination according to claim 1 for being used to prepare micro- porous membrane, it is characterised in that：Contain following weight Measure the component of number：Polylactic resin A：40-75 parts by weight；The resin Composition B incompatible with polylactic acid：10-40 parts by weight；Fill out Expect C：10-45 parts by weight.
- 3. the resin combination according to claim 1 for being used to prepare micro- porous membrane, it is characterised in that：The poly- breast Acid resin A is amorphism polylactic acid or the composition of amorphism polylactic acid and crystalline polylactic acid.
- 4. the resin combination according to claim 3 for being used to prepare micro- porous membrane, it is characterised in that：The poly- breast Also contain plasticizer D in acid resin A.
- 5. the resin combination according to claim 4 for being used to prepare micro- porous membrane, it is characterised in that：The plasticising Agent D is selected from polyethylene glycol, polypropylene glycol, lactic acid oligomer, lactide oligomer, ethylene oxide/propylene oxide copolymer, lemon Acid esters triethyl, tributyl citrate, acetyl triethyl citrate, tributyl 2-acetylcitrate, sorbitol ester, polycaprolactone/ Copolymer of poly lactic acid, poly-succinic fourth diester/copolymer of poly lactic acid, poly- alkyl diol/lactic acid copolymer or castor oil/lactic acid One or several kinds in copolymer.
- 6. the resin combination according to claim 1 for being used to prepare micro- porous membrane, it is characterised in that：Described is same poly- The incompatible resin Composition B of lactic acid is selected from polyethylene, polypropylene, polybutene, polyvinyl chloride, polyacrylonitrile, polyurethane, poly- first Base methyl acrylate, makrolon, polybutylene terephthalate (PBT), polyethylene terephthalate, polystyrene, poly-vinegar Vinyl acetate, ethylene-vinyl acetate copolymer, poly butyric ester, polyhydroxybutyrate valerate, poly butyric caproic acid Ester, poly butylene succinate, poly-succinic tetramethylene adipate, polycaprolactone, poly terephthalic acid adipic acid butanediol Ester, poly terephthalic acid adipic acid propylene glycol ester, poly terephthalic acid succinic acid-butanediol ester, poly- ethylene carbonate, poly- trimethylene One or more in carbonic ester or polymerized thylene carbonate cyclohexyl.
- 7. the resin combination for being used to prepare micro- porous membrane according to any one of claim 1-6, it is characterised in that： With a diameter of 0.5 μm -50 μm of the phase of the incompatible resin Composition B component of polylactic acid.
- 8. a kind of resin combination for being used to prepare micro- porous membrane as any one of claim 1-6 prepares micro- more Hole film.
- A kind of 9. micro- porous membrane prepared by resin combination for being used to prepare micro- porous membrane as described in claim 7.
- 10. micro- porous membrane according to claim 9, it is characterised in that:Its moisture permeability is in 1500-4000g/ (m2·d)。
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| CN112745647A (en) * | 2020-12-30 | 2021-05-04 | 重庆和泰润佳股份有限公司 | Non-breathable biodegradable resin and preparation method thereof |
| CN115521593B (en) * | 2021-12-29 | 2024-04-12 | 嘉兴高正新材料科技股份有限公司 | High-toughness environment-friendly transparent composite film material and preparation method thereof |
| CN114685965B (en) * | 2022-04-29 | 2023-02-03 | 悟锐新材料科技(江苏)有限公司 | Fully-degradable hard polylactic acid composite material and preparation method thereof |
| CN115925443B (en) * | 2022-12-30 | 2023-07-04 | 中南大学 | Solid waste-based ceramic membrane support raw material with wide firing range and solid waste-based ceramic membrane support |
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