CN110343292A - A kind of cellulose nano-fibrous/halloysite nanotubes enhancing starch film and preparation method thereof - Google Patents
A kind of cellulose nano-fibrous/halloysite nanotubes enhancing starch film and preparation method thereof Download PDFInfo
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- CN110343292A CN110343292A CN201810285804.9A CN201810285804A CN110343292A CN 110343292 A CN110343292 A CN 110343292A CN 201810285804 A CN201810285804 A CN 201810285804A CN 110343292 A CN110343292 A CN 110343292A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/045—Reinforcing macromolecular compounds with loose or coherent fibrous material with vegetable or animal fibrous material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Abstract
The invention discloses a kind of cellulose nano-fibrous/halloysite nanotubes enhancing starch films and preparation method thereof, it comprises the following components in parts by weight: 1~6 part of starch, 0.5~3 part of polyvinyl alcohol, 0.3~1.8 part of plasticizer, cellulose nano-fibrous 0.01~0.06 part, 0.01~0.06 part of halloysite nanotubes, 89.08~98.91 parts of water.Preparation method (1) solution preparation specific as follows: cellulose nano-fibrous 0.01~0.06 part, 0.01~0.06 part of halloysite nanotubes, 99.88~99.98 parts of water are dispersed into suspension through ultrasonic wave；Prepare the polyvinyl alcohol water solution that mass concentration is 5%；After 1~6 part of starch, 0.03~1.8 part of plasticizer, 92.2~98.7 parts of water mixing, stir and be gelatinized under 90 DEG C of water bath conditions to obtain the final product；(2) it is prepared at film liquid: above-mentioned suspension, polyvinyl alcohol water solution, gelatinized corn starch is mixed evenly up at film liquid；(3) film preparation: it will be poured at film liquid and be cast drying and forming-film on film forming device.Operation of the present invention is easy, and the starch film-strength of production is high, elasticity is good, the gas barrier properties that block water are excellent.
Description
Technical field
The invention belongs to food processing technology fields, and in particular to a kind of cellulose nano-fibrous/halloysite nanotubes increasing
Strong starch film and preparation method thereof.
Background technique
Nowadays, plastic package material because of its good physical mechanics, block water gas barrier properties and economic and practical, make it
It is widely used in food packaging.However, the biodegradable difference of plastics also results in " white pollution " problem got worse, greatly
Ground destroys ecological environment.In addition, process in plastics is at high cost, pollution is burned greatly, become international environment difficulties.
Since the 1970s, more and more scientists are transferred to starch, protein and cellulose for sight is studied
Deng on the natural macromolecular material with good biodegradability properties, the features such as source is wide, yield is more, degradable, has it
It has boundless potential on food packaging applications.Wherein, starch is because of feature low in cost, degradable membrane material prepared therefrom
Have become one of the natural biodegradable material with preferable development prospect.However, the physical mechanics of pure starch membrane material
Performance, wet-hot aging performance, heat sealability etc. are poor also to be caused in its practical application by larger limitation.
Galapectite is a kind of kaolinic aquation deformation being made of silica.Since it has natural bio-compatible
Property, at low cost, the advantages that particle volume is small, large specific surface area, surface can be high, it is introduced into the right way can in starch film
Improve its performance.
Cellulose nano-fibrous (CNF) is a kind of reproducible natural biodegradable polymer material, due to its special crystalline substance
Body structure and nanoscale diameter, CNF have good mechanical property, are usually used in enhancing other matrixes as packing material, separately
Outside, huge specific surface area and macromolecular effect, moreover it is possible to adsorb other particles and help to disperse, prevent particle agglomeration from settling.
Currently, Chinese patent application " a kind of environment-friendly degradable type halloysite nanotubes-polyethylene coating materials and preparation method thereof "
(application number 201610579169.6) discloses a kind of environment-friendly degradable type halloysite nanotubes-polyethylene coating materials, by following weight
The raw material composition of part: 60-70 parts of linear low density polyethylene, 8-15 parts of wax cornstarch, 8-15 parts of plant fiber powder, silicon
3-6 parts of alkane coupling agent, 25-35 parts of degradation-type calcium carbonate master batch, 10-18 parts of vinyl-terminated silicone oil, containing hydrogen silicone oil 0.3-0.8
Part, appropriate sulfuric acid solution, appropriate platinum catalyst, 10-15 parts of halloysite nanotubes, 8-12 parts of white carbon black, appropriate dehydrated alcohol.This
The polyethylene coating materials of invention can be decomposed under field conditions (factors) water and carbon dioxide in 6-8 months, biology after use
Degradation speed is fast, without generating white pollution, meets the requirement of environmental protection；In addition white carbon black and modified galapectite is mutual
Effect can form special double filler networks so that compound coating materials tensile strength, in terms of be significantly improved.
Chinese patent application " a kind of degradable plastic film composite material of nano-cellulose enhancing and its preparation side
Method " (application number 201611180564.3) disclose a kind of enhancing of nano-cellulose degradable plastic film composite material and
Its preparation process, which is characterized in that with starch, polyvinyl alcohol, urea, glycerine, L-PROLINE, sodium hydroxide, nano TiO 2,
Manganese stearate, kaolin, pulullan polysaccharide, nano-cellulose, chitosan, sodium carboxymethylcellulose, attapulgite, graphite oxide
Alkene, polyethyleneimine, vinyl acetate etc. are raw material.Present invention Sodium proline modified Nano TiO2, is prepared for composite catalyst,
Using kaolin as bioactivator, using manganese stearate as degradation of promoter, it is prepared for biodegradable laminated film.Add carboxylic first
Base sodium cellulosate and attapulgite, chitosan blend prepare composite material.With vinyl acetate modified starch, by graft copolymerization system
For biodegradable composite；There are electrostatical binding power between graphene oxide and polyethyleneimine, THIN COMPOSITE is improved
The barrier property of film reduces oxygen permeability.
Summary of the invention
It is an object of that present invention to provide a kind of cellulose nano-fibrous/halloysite nanotubes enhancing starch film and its preparation sides
Method, preparation method of the invention, which can be simple and efficient, produces cellulose nano-fibrous/halloysite nanotubes enhancing starch film, improves
The compatibility and dispersibility of cellulose nano-fibrous/halloysite nanotubes enhancing starch film, obtained a kind of tensile strength it is high,
The Eco-friendly material that elasticity modulus is good, the gas barrier properties that block water are excellent.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of cellulose nano-fibrous/halloysite nanotubes enhancing starch film, comprises the following components in parts by weight: starch 1
~6 parts, 0.05~3 part of polyvinyl alcohol, 0.03~1.8 part of plasticizer, cellulose nano-fibrous 0.01~0.06 part, galapectite is received
0.01~0.06 part of mitron.
The starch is tapioca, potato starch, sweet potato starch, rice starch, wheaten starch, cornstarch, height
Fine strain of millet starch, pea starch, green starch, Chinese yam starch, banana starch, sago starch or Lotus Root Starch.
Internal diameter, overall diameter and the length of the halloysite nanotubes be respectively 1~30nm, 30~50nm and 100~
2000nm。
The plasticizer is xylitol, sorbierite, mannitol, propylene glycol, glycerol, fructose, sucrose, phthalic acid diethyl
Ester or glyceryl triacetate.
A kind of preparation method of cellulose nano-fibrous/halloysite nanotubes enhancing starch film, specific features and step are such as
Shown in lower:
(1) prepared by solution: cellulose nano-fibrous 0.01~0.06 part, 0.01~0.06 part of halloysite nanotubes, water
99.88~99.98 parts, suspension is dispersed into through ultrasonic wave；0.05~3 part of polyvinyl alcohol is added in Xiang Shuizhong, 99 DEG C of water-bath, stirs
8 hours, prepare the polyvinyl alcohol water solution that mass concentration is 5%；1~6 part of starch, 0.03~1.8 part of plasticizer and water 92.2
~98.7 parts, stirring is gelatinized up to gelatinized corn starch under water bath condition after mixing；
(2) it prepares: the resulting suspension of step (1), polyvinyl alcohol water solution and gelatinized corn starch being mixed equal at film liquid
It is even up at film liquid；
(3) film preparation: step (2) is resulting to pour into dry casting film-forming on film forming device at film liquid.
Ultrasonic power is 200~1800W in the step (1), and jitter time is 10~40min.
Stirring in water bath is gelatinized in the step (1) 80~95 DEG C of bath temperature, 10~50min of time, mixing speed are
60~360r/min.
The mixing speed of the step (2) is 500~3000r/min, and mixing time is 10~40min.
In the step (3) at film liquid, control weight is 1g/cm2。
The film forming device of the step (3) is the batch cultur ware or other film forming vessel for being conducive to take off film of surface hydrophobicity.
Drying and forming-film in the step (3), condition are 20~50 DEG C of temperature, and humidity 20~50%, the time is for 24 hours.
The present invention has the advantages that cellulose nano-fibrous and starch chain can twine since galapectite nanometer is tubular structure
Around the tubular structure, good fine and close network structure is formed, its mechanical property is significantly increased.In addition, cellulose nano-fibrous
Tubular structure bonding can be intertwined by hydrogen bond action, improve the bond strength between tubular structure.The collaboration of the two
Effect significantly improves the stability of mechanical property and matrix structure.
Present invention process process is simple, low in cost, and the starch film tensile strength of production is high, elasticity modulus is good, transparency
Well, the gas barrier properties that block water are excellent, the characteristic for having ecology friendly.
Detailed description of the invention
Fig. 1 is the fine and close physical crosslinking that cellulose nano-fibrous/halloysite nanotubes of the invention enhance that starch film is formed
Network diagram.
Wherein, 1: halloysite nanotubes, 2: polyvinyl alcohol, 3: hydrogen bond, 4: it is cellulose nano-fibrous, 5: starch chain.
Specific embodiment
By following specific embodiments and reference examples, the present invention is further described.
Embodiment 1
(1) prepared by solution: pressing cellulose nano-fibrous 0.05 part, 0.05 part of halloysite nanotubes, 99.90 parts of water, ultrasound
Wavelength-division dissipates the water slurry for preparing cellulose nano-fibrous and halloysite nanotubes, ultrasonic power 400W, jitter time 30min；
2.5 parts of polyvinyl alcohol, 47.5 parts of water, stir 8 hours by 90 DEG C of water-bath, prepare the polyvinyl alcohol water solution that mass concentration is 5%；
5 parts of tapioca, 1.5 parts of plasticizer, 93.5 parts of water, after being configured to mixed liquor, 90 DEG C of stirring in water bath gelatinizations, time 45min is stirred
Mixing speed is 200r/min to get gelatinized corn starch；
(2) it is prepared at film liquid: suspension obtained by step (1), polyvinyl alcohol water solution, gelatinized corn starch is mixed evenly,
Mixing speed is 1500r/min, and the time is 30min to get at film liquid；
(3) film preparation: 1g/cm will be pressed at film liquid obtained by step (2)2Curtain coating in batch cultur ware is poured onto be dried to
Film, membrance casting condition are 40 DEG C of temperature, and relative humidity 40%, the time is for 24 hours.
The performance quality index of starch film obtained by this example is shown in Table 1.
Embodiment 2
(1) prepared by solution: pressing cellulose nano-fibrous 0.10 part, 0.10 part of halloysite nanotubes, 99.80 parts of water, ultrasound
Wavelength-division dissipates the water slurry for preparing cellulose nano-fibrous and halloysite nanotubes, ultrasonic power 400W, jitter time 30min；
2.5 parts of polyvinyl alcohol, 47.5 parts of water, stir 8 hours by 90 DEG C of water-bath, prepare the polyvinyl alcohol water solution that mass concentration is 5%；
5 parts of tapioca, 1.5 parts of plasticizer, 93.5 parts of water, after being configured to mixed liquor, 90 DEG C of stirring in water bath gelatinizations, time 45min is stirred
Mixing speed is 200r/min to get gelatinized corn starch；
(2) it is prepared at film liquid: suspension obtained by step (1), polyvinyl alcohol water solution, gelatinized corn starch is mixed evenly,
Mixing speed is 1500r/min, and the time is 30min to get at film liquid；
(3) film preparation: 1g/cm will be pressed at film liquid obtained by step (2)2Curtain coating in batch cultur ware is poured onto be dried to
Film, membrance casting condition are 40 DEG C of temperature, and relative humidity 40%, the time is for 24 hours.
The performance quality index of starch film obtained by this example is shown in Table 1.
Embodiment 3
(1) prepared by solution: pressing cellulose nano-fibrous 0.15 part, 0.15 part of halloysite nanotubes, 99.70 parts of water, ultrasound
Wavelength-division dissipates the water slurry for preparing cellulose nano-fibrous and halloysite nanotubes, ultrasonic power 400W, jitter time 30min；
2.5 parts of polyvinyl alcohol, 47.5 parts of water, stir 8 hours by 90 DEG C of water-bath, prepare the polyvinyl alcohol water solution that mass concentration is 5%；
5 parts of tapioca, 1.5 parts of plasticizer, 93.5 parts of water, after being configured to mixed liquor, 90 DEG C of stirring in water bath gelatinizations, time 45min is stirred
Mixing speed is 200r/min to get gelatinized corn starch；
(2) it is prepared at film liquid: suspension obtained by step (1), polyvinyl alcohol water solution, gelatinized corn starch is mixed evenly,
Mixing speed is 1500r/min, and the time is 30min to get at film liquid；
(3) film preparation: 1g/cm will be pressed at film liquid obtained by step (2)2Curtain coating in batch cultur ware is poured onto be dried to
Film, membrance casting condition are 40 DEG C of temperature, and relative humidity 40%, the time is for 24 hours.
The performance quality index of starch film obtained by this example is shown in Table 1.
Reference examples 1: starch film the preparation method is the same as that of Example 1 step (1)~(3), wherein being added without cellulose Nanowire
Peacekeeping halloysite nanotubes suspension, as blank control.
Reference examples 2: starch film the preparation method is the same as that of Example 1 step (1)~(3), wherein being added without cellulose Nanowire
Peacekeeping halloysite nanotubes suspension, only addition prepares angstrom Lip river by 99.95 parts of 0.05 part of halloysite nanotubes, water ultrasonic wave dispersions
The water slurry of stone nanotube, ultrasonic power 400W, jitter time 30min.
Reference examples 3: starch film the preparation method is the same as that of Example 1 step (1)~(3), wherein being added without cellulose Nanowire
Peacekeeping halloysite nanotubes suspension, only addition is prepared fine by 99.95 parts of cellulose nano-fibrous 0.05 part, water ultrasonic wave dispersions
Tie up the water slurry of plain nanofiber, ultrasonic power 400W, jitter time 30min.
The thickness measurement of film: referring to GB/T6672-2001 " plastic film and Foil thickness measurement-mechanical measurement method ", benefit
It takes 3 points of measurements at random on film with digital micrometer, is averaged, test condition is 22 DEG C, relative humidity 57%.
The tensile strength and elongation at break of the film of film measure: with reference to GB/T1040.03-2006 " plastic tensile performance
Measure third portion: the experimental condition of thin modeling and thin slice ", film is cut into the strip of 1cm × 8cm, is surveyed using omnipotent mechanics machine
Fixed, test condition is 22 DEG C, relative humidity 57%.
The water vapour permeability of the film of film measures: GB/T1037-1988 " plastic film and sheet material water vapor permeability test side
The cup type method of method ", it is measured using quasi- cup method, relative humidity is 80% inside and outside film.
1 embodiment 1-3 of table and reference examples starch film main performance index
As seen from the above table, after starch film is added in cellulose nano-fibrous and halloysite nanotubes, the thickness of starch film is slightly
Reduce.It is strong caused by halloysite nanotubes HNT is uniformly dispersed in starch film after pure starch film is added in halloysite nanotubes
Degree and elongation at break increased.After cellulose nano-fibrous CNF is added, intensity and elongation at break are improved, vapor
Transmitance decline, this is because long Filamentous cellulose nano-fibrous CNF and starch film form cross-linked network, so that starch film point
Dissipate more uniform, structure is more stable, so that film-strength increases.Further, since halloysite nanotubes are tubular structures, it is very thin
Cellulose nano-fibrous CNF and starch chain can wind the tubular structure, and form mutual hydrogen bond action, significantly increase
Tensile strength.
Claims (11)
1. a kind of cellulose nano-fibrous/halloysite nanotubes enhance starch film, it is characterised in that: the group including following parts by weight
Point: 1~6 part of starch, 0.05~3 part of polyvinyl alcohol, 0.03~1.8 part of plasticizer, cellulose nano-fibrous 0.01~0.06 part,
0.01~0.06 part of halloysite nanotubes, 89.08~98.91 parts of water.
2. one kind according to claim 1 is cellulose nano-fibrous/halloysite nanotubes enhance starch film, feature exists
In: the starch is tapioca, potato starch, sweet potato starch, rice starch, wheaten starch, cornstarch, sorghum shallow lake
Powder, pea starch, green starch, Chinese yam starch, banana starch, sago starch or Lotus Root Starch.
3. one kind according to claim 1 is cellulose nano-fibrous/halloysite nanotubes enhance starch film, feature exists
In: internal diameter, overall diameter and the length of the halloysite nanotubes are respectively 1~30nm, 30~50nm and 100~2000nm.
4. one kind according to claim 1 is cellulose nano-fibrous/halloysite nanotubes enhance starch film, feature exists
In: the plasticizer be xylitol, sorbierite, mannitol, propylene glycol, glycerol, fructose, sucrose, diethyl phthalate or
Glyceryl triacetate.
5. according to claim 1 one kind described in one of -4 it is cellulose nano-fibrous/halloysite nanotubes enhancing starch film system
Preparation Method, feature and step are:
(1) solution prepare: cellulose nano-fibrous 0.01~0.06 part, 0.01~0.06 part of halloysite nanotubes, water 99.88~
99.98 parts, suspension is dispersed into through ultrasonic wave；0.05~3 part of polyvinyl alcohol is added in Xiang Shuizhong, 99 DEG C of water-bath, stirs 8 hours,
Prepare the polyvinyl alcohol water solution that mass concentration is 5%；1~6 part of starch, 0.03~1.8 part of plasticizer and water 92.2~98.7
Part, stirring is gelatinized up to gelatinized corn starch under water bath condition after mixing；
(2) it is prepared at film liquid: the resulting suspension of step (1), polyvinyl alcohol water solution and gelatinized corn starch is mixed evenly i.e.
It obtains into film liquid；
(3) film preparation: step (2) is resulting to pour into dry casting film-forming on film forming device at film liquid.
6. one kind according to claim 5 is cellulose nano-fibrous/preparation method of halloysite nanotubes enhancing starch film,
It is characterized by: ultrasonic power is 200~1800W in the step (1), jitter time is 10~40min.
7. one kind according to claim 5 is cellulose nano-fibrous/preparation method of halloysite nanotubes enhancing starch film,
It is characterized by: 80~95 DEG C of bath temperature, 10~50min of time that stirring in water bath is gelatinized in the step (1), mixing speed
For 60~360r/min.
8. one kind according to claim 5 is cellulose nano-fibrous/preparation method of halloysite nanotubes enhancing starch film,
It is characterized by: the mixing speed of the step (2) is 500~3000r/min, mixing time is 10~40min.
9. one kind according to claim 5 is cellulose nano-fibrous/preparation method of halloysite nanotubes enhancing starch film,
It is characterized by: in the step (3) at film liquid, control weight is 1g/cm2。
10. one kind according to claim 5 is cellulose nano-fibrous/the preparation side of halloysite nanotubes enhancing starch film
Method, it is characterised in that: the film forming device of the step (3) is the batch cultur ware or other conducive to the film forming for taking off film of surface hydrophobicity
Vessel.
11. one kind according to claim 5 is cellulose nano-fibrous/the preparation side of halloysite nanotubes enhancing starch film
Method, it is characterised in that: drying and forming-film in the step (3), condition are 20~50 DEG C of temperature, and humidity 20~50%, the time is
24h。
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| CN110744658A (en) * | 2019-11-20 | 2020-02-04 | 湖南工业大学 | Starch-reinforced wood composite material and preparation method thereof |
| CN112175243A (en) * | 2020-09-21 | 2021-01-05 | 桂林理工大学 | High-performance cellulose acetate composite material and preparation method thereof |
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| CN113788989B (en) * | 2021-09-13 | 2023-05-30 | 桂林理工大学 | Starch-based nanocomposite with ultraviolet shielding function and preparation method thereof |
| CN113831563A (en) * | 2021-09-29 | 2021-12-24 | 广西大学 | Cassava residue nano cellulose-cassava starch film and preparation method thereof |
| CN115260601A (en) * | 2022-08-11 | 2022-11-01 | 桂林理工大学 | Tough starch/polyvinyl alcohol-based nano composite material with ammonia response and antibacterial functions as well as preparation method and application thereof |
| CN115260601B (en) * | 2022-08-11 | 2023-11-17 | 桂林理工大学 | Tough starch/polyvinyl alcohol-based nanocomposite with ammonia response and antibacterial functions, and preparation method and application thereof |
| CN115316549A (en) * | 2022-08-25 | 2022-11-11 | 李雄 | Feed additive for improving reproductive capacity of cocks and preparation method thereof |
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