CN108641049A - A kind of preparation method of the aqueous super hydrophobic material of fluorine-free monomer - Google Patents
A kind of preparation method of the aqueous super hydrophobic material of fluorine-free monomer Download PDFInfo
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- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
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Abstract
The present invention is a kind of preparation method of the aqueous super hydrophobic material of fluorine-free monomer.This approach includes the following steps：1) surface of silica is modified；2) to the Surface grafting reaction of modified silica：Water, the silica of modification, sodium bicarbonate (NaHCO are added in the reactor3), emulsifier; ultrasonic disperse 30min; monomer dropping is entered into reaction system under protection of argon gas; initiator solution is added dropwise in reaction system by emulsification 30min after system temperature is risen to 80 DEG C; mechanical agitation; reaction 16~for 24 hours after, stop reaction, obtain the aqueous super hydrophobic material of different grafting amounts.The present invention can be coated on a variety of common used material surfaces, and preparation method is succinct, and the super hydrophobic surface obtained has excellent stability, therefore aqueous super hydrophobic material prepared by the present invention has a good application prospect in many fields.
Description
Technical field
Technical scheme of the present invention is related to organic and inorganic and polymeric material field, and in particular to a kind of fluorine-free monomer
The preparation method of aqueous super hydrophobic material.
Background technology
Early in 20th century, people find that the coarse structure of lotus leaf surface micro-meter scale is it with hydrophobicity and automatically cleaning
The key of function.2002 Nian Jiang thunders seminar [L.Jiang, et al.Adv.Mater., 2002,14,1857.] find in lotus leaf
There is also nanostructures in the mastoid process of surface micrometer structure, it is believed that micrometer structure is with the hierarchical structure that nanostructure is combined
Cause the basic reason of surface strong-hydrophobicity.Water skipper has been opened in the report that the seminar is published on Nature in 2004 can be
The secret [L.Jiang, et al.Nature, 2004,432,36.] flown on the water surface.When material surface is big to the contact angle of water
When 150 °, roll angle are less than 10 °, we claim this material to have super-hydrophobicity.It is this super-hydrophobic with special wettability
Coating it is anti-icing cover, anticorrosion [Q.Liu, et al.J.Electro.chem.Soc., 2016,163:213.], automatically cleaning and oil
Water separation [Y.Chen, et al.Appl.Surf.Sci., 2015,335:107.] etc. have important application.Therefore, closely
The preparation of super hydrophobic material has been to be concerned by more and more people over year.
Has the surface generally tool of super-hydrophobic effect there are two condition：One be surface have certain roughness, i.e., it is micro-
Micro-nano structure；The other is modifying low-surface energy substance on a rough surface.Common method has：Etching method, sol-gal process, mould
Plate method etc..For example, Huang et al. etches aluminum alloy surface using NaOH solution, flakey micro nano structure is constructed, by right
After surface modification low-surface energy substance, to the contact angle of water reached 156 ° [Y.Huang, et al.Appl.Surf.Soc.,
2015,356:1012.]；The method of Lee et al. collosol and gels forms the SiO with nanometer protrusion on silico-aluminum surface2It is thin
Low surface mass modification SiO is used in combination in film2Obtain super hydrophobic surface [J.W.Lee, et al.Mater.Lett., 2016,168:
83.]；Zhang et al. does template with cigarette ash and prepares ultra-hydrophobic paper [J.H.Zhang, the et al.RSC that contact angle is up to 160 °
Adv.,2016,6:12862.].Can scale, low cost prepare, it is easy to use, while there is the super-hydrophobic painting of crocking resistance
Layer is the Main way of current super hydrophobic material development.
Polymer/inorganic composite material with unique performance replaces traditional material extensively due to it in every field.
Wherein, silica/polymer composites are prepared and are applied to the hot spot that super-hydrophobic field has become research.But mesh
The super hydrophobic material of preceding preparation mainly dissolves low-surface-energy material using organic solvent such as methanol, ethyl alcohol or ethyl acetate
(LSEM), once amplification production organic solvent can cause huge environmental problem；And presently used low-surface-energy material master
If fluorine-containing monomer, of high cost.Secondly, in current techniques between the particle of these materials be only physical action, particle it
Between binding force it is poor, therefore nano particle is easy to fall off, and leads to the poor adhesive force of material.Presently mainly pass through addition
Adhesive increases micro- interparticle cohesion to reach, but this method comes with some shortcomings, and addition is very little, is not enough between increase particle
Binding force；Addition is excessive, can cause to be separated, also can covering material surface micro-nano structure, super-hydrophobic effect is not achieved.
Invention content
The present invention for endurance quality present in current techniques poor, adhesive and nano particle be difficult to appropriate allotment, at
The deficiencies of this height and pollution environment, provide a kind of preparation method of the aqueous super hydrophobic material of fluorine-free monomer.The present invention is with fluorine-containing
Emulsifier and not fluorochemical monomer carry out emulsion polymerization.The fluorine-containing emulsifier that the present invention uses can be coated on material surface and form low table
Face energy, generates super-hydrophobic effect, avoids and utilize high cost caused by fluorochemical monomer, it is often more important that will produce in the process
Homopolymer microballoon and SiO2@polymer form hierarchical structure, preferably construct super hydrophobic surface.
The technical scheme is that：
A kind of preparation method of the aqueous super hydrophobic material of fluorine-free monomer, includes the following steps：
1) surface of silica (grain size is 10~100nm) is modified, and can take following methods：
By silica dispersion in ethanol, after ultrasonic disperse 30min, add it in reactor, add ammonium hydroxide,
Silane coupling agent and water, at room temperature mechanic whirl-nett reaction 48h product is washed repeatedly with ethyl alcohol after reaction, centrifugation is heavy
It forms sediment, after vacuum drying, obtains the silica that surface carries double bond；
Wherein, quality of material ratio is silica：Ethyl alcohol：Ammonium hydroxide：Water：Silane coupling agent=1-100：1-1000：1-
100：1-100：1-100；The mass fraction of ammonium hydroxide is 25~28%；
The silane coupling agent is γ-methacryloxypropyl trimethoxy silane, vinyl trimethoxy silicon
Alkane, (b- methoxy ethoxies) silane of vinyl three or vinyltriethoxysilane；
2) to the Surface grafting reaction of modified silica, following methods can be taken：
Water, the silica of modification, sodium bicarbonate (NaHCO are added in the reactor3), emulsifier, ultrasonic disperse
30min under protection of argon gas enters monomer dropping into reaction system, emulsifies 30min, will after system temperature is risen to 80 DEG C
Initiator solution is added dropwise in reaction system, mechanical agitation, reaction 16~for 24 hours after, stop reaction, obtain the water of different grafting amounts
Property super hydrophobic material.
Its material proportion is that quality compares improved silica：Water：Monomer：Emulsifier：Initiator solution=0.1-10：1-
100：1-10：0.01-1：1-10；Sodium bicarbonate (the NaHCO of 0.10~0.24g is added in the water of 100mL3)；Initiator solution
A concentration of 10mL water in dissolved with 0.01~0.30g. initiator；
Wherein, emulsifier is perfluoro butyl sulfonic acid fluoride, perfluoroalkyl ethers acrylate, perfluoro octyl sulfonic acid potassium or perfluor alkane
Initiator is potassium peroxydisulfate, ammonium persulfate, isopropyl benzene hydroperoxide or isopropyl benzene hydroperoxide；Monomer is styrene, methyl-prop
One or more of e pioic acid methyl ester, ethyl methacrylate, butyl methacrylate and glyceral methacrylate.
The application of the aqueous super hydrophobic material of the fluorine-free monomer, includes the following steps：
The aqueous super hydrophobic material is configured to the dispersion liquid of required concentration, by dispersion liquid spraying and basis material table
On face, is dried at a temperature of placing it in 135~145 DEG C, that is, constitute super-hydrophobic coat；
The upper quality of material ratio is aqueous super hydrophobic material：Water=1：10-1000；Every square metre of matrix surface spraying
25~35g dispersion liquids.
The basis material is timber, metal, cement, fabric, plastics or glass.
The present invention substantive distinguishing features be：
The super hydrophobic material currently prepared mainly increases the binding force between particle, adhesive using addition adhesive
Additive amount be difficult to control, addition is very few, is not achieved effect, and addition is excessive, will produce phase separation, influences material hydrophobic effect.
Furthermore it is presently mainly to go to prepare super hydrophobic material using the fluorochemical monomer of low-surface-energy, fluorochemical monomer dosage is more, expensive,
And utilization organic solvent such as methanol, ethyl alcohol or ethyl acetate the dissolving low-surface-energy material (LSEM) of material, once amplification life
Production organic solvent can cause huge environmental problem.The present invention using fluorine-containing emulsifier and not fluorochemical monomer to silicon dioxide microparticle
Surface grafting is carried out, polymer long-chain in grafting, using hydrophobic polymer more than glass transition temperature, polymer chain starts
Movement, can mutually tangle between chain and chain, combine even closer between the microballoon and microballoon of material, therefore nano particle is not easy to take off
It falls, increases the wearability of material, avoid the deficiency brought using adhesive.Furthermore use emulsion polymerization, use water as divide
Powder avoids using organic solvent, and Environmental Safety, process is simple.And fluorine-containing emulsifier is seldom relative to fluorochemical monomer dosage, and it can
To save prodigious cost.
Beneficial effects of the present invention are：
(1) present invention can be coated on a variety of common used material surfaces, and preparation method for coating is succinct, and the super hydrophobic surface obtained
It has excellent stability, therefore aqueous super hydrophobic material prepared by the present invention has a good application prospect in many fields.
(2) strong applicability of aqueous super hydrophobic material of the invention, timber, metal, building inside and outside wall, fabric, plastics, glass
Glass surface can apply, and have superpower water proof anti-soil effect.
(3) present invention fluorine-containing emulsifier and the method that fluorochemical monomer does not use emulsion polymerization prepare aqueous super-hydrophobic material
Material, avoids of high cost caused by being typically prepared fluorochemical monomer used in super hydrophobic material, is greatly reduced cost, process letter
It is single.
(4) in use, dendritic morphology has contributed much the stability tool of coating to the present invention, and microsphere surface has
The polymer chain of many length, when material is more than glass transition temperature, polymer chain is kept in motion, and chain is mutual with chain
It tangles, so that microballoon is combined with microballoon even closer, to increase the adhesive force of super hydrophobic material, avoid addition adhesive not
The problem that homogeneous band comes.The static contact angle of gained coating of the invention is more than 150 °, and roll angle is less than 5 °, reaches super-hydrophobic effect
Fruit.
(5) present invention meets now generally acknowledged Cassie-Baxter models, the preparation of aqueous super hydrophobic material in the present invention
It is easy to operate, of low cost, expensive device and harsh process conditions are not necessarily to, complex operations are not necessarily to, are not necessarily to complex device, and have
Ultra-hydrophobicity that is excellent, stablizing, and obtained super hydrophobic material adhesive force is good, before there is good industrial development application
Scape.
Description of the drawings:
Fig. 1：The preparation flow figure of aqueous super hydrophobic material；
Fig. 2：The electromicroscopic photograph of silica in embodiment 1, wherein upper right corner illustration are that the static contact angle of the coating is surveyed
Try photo；
Fig. 3：The electromicroscopic photograph of modified silica in embodiment 1, wherein upper right corner illustration are that the static state of the coating connects
Feeler tests photo, and maximum static contact angle reaches 66.8 °；
Fig. 4：Grafting amount is the electromicroscopic photograph of silica after grafting in embodiment 1, and wherein upper right corner illustration is the coating
Static contact angle test photo, maximum static contact angle reaches 164.2 °；
Fig. 5：Electromicroscopic photograph of the material after 140 ° of heat treatment in embodiment 1, wherein upper right corner illustration are the coating
Static contact angle test photo, maximum static contact angle reaches 158.3 °；
Specific implementation mode
The present invention is described further with reference to embodiment and attached drawing；
Silica (grain size is 10~100nm) of the present invention is known products, and those of ordinary skill in the art can
To be prepared by commercially available or known method.
Preparation flow of the present invention is as shown in Fig. 1, first with silane coupling agent to silica (grain size is 10~100nm)
Surface is modified, and forms the silica that surface carries double bond, and the method for then utilizing emulsion polymerization is dredged on surface grafting
The polymer long-chain of water has prepared dendritic aqueous super hydrophobic material.
Embodiment 1：
The preparation for the material that grafting amount is 80%
(1) modification of silica (grain size is 10~100nm)
2g silica is taken to be dispersed in the ethyl alcohol of 200ml, ultrasonic disperse 30min adds 10ml distilled waters, 2ml ammonia
γ-methacryloxypropyl trimethoxy silane of water (mass fraction is 25~28%) and 6g, speed of agitator control exist
300r/min stops reaction after reacting 48h at room temperature, product is washed 3 times, after vacuum drying with ethyl alcohol, obtains surface modification
Silica.
Attached drawing 2 is obtained with 450 electron scanning electron-microscope scanning silica of model FEI Nano SEM, and Fig. 3 is to change
The electron microscope of silica after property.Silica after it can be seen that before modified in attached drawing 2 and 3 does not obviously become both topographically
To change, there is hydrophobic silane coupling agent on modified silica, contact angular data variation is apparent, becomes 66.8 ° from 17.7 °,
Demonstrate modified successful generation.
(2) method for using emulsion polymerization carries out Surface grafting reaction to improved silica
The modified silica of dry 0.4g is dispersed in the distilled water of 100ml, 0.24g bicarbonates are sequentially added
Sodium (NaHCO3), 0.04g perfluoroalkyl ethers acrylate, ultrasonic disperse 30min is added in reactor, oil bath heating to 80
DEG C, it is passed through argon gas, mechanical agitation, and 2g methyl methacrylates are added in backward reaction system, 30min is emulsified, by 0.04g mistakes
Potassium sulfate is dissolved in 10mL water, is added drop-wise in the reactor of front after dissolving completely, and 1h is dripped off, speed of agitator 250r/min, and 80
DEG C isothermal reaction 16h, gained lotion is stood, and the aqueous super-hydrophobic material that grafting amount is 80% is obtained using TGA (thermogravimetric analysis)
Material；
Attached drawing 4 is the Electronic Speculum with the silica after the grafting of 450 electron scanning electron-microscope scannings of model FEI Nano SEM
Figure, contact angle are 164.2 °, and attached drawing 5 is electron microscope of the material after 140 DEG C of heat treatment, and contact angle is 158.2 °,
From, as can be seen that material is after 140 DEG C of heat treatment, pattern is unlike so loose before processing, between material more in attached Figure 4 and 5
Step up close.It is primarily due to hydrophobic polymer and is being heated to glass transition temperature or more, polymer chain setting in motion, chain and chain
Between can mutually tangle, between the microballoon and microballoon of material combine it is even closer.The material is added to the water and is configured to quality
For 2% dispersion liquid, 25g dispersion liquids are sprayed according to every square metre of matrix surface, by the material spraying in spring Asia woven fabric,
After being dried at 140 DEG C, wearability test is carried out to it with abrasion instrument, at pressure 250g, surveys its wear-resisting linearity curve, 600 circles
Contact angle keeps its super-hydrophobic effect still greater than 150 ° afterwards.
Embodiment 2：
The preparation for the material that grafting amount is 60%
(1) silica (grain size is 10~100nm) is modified with one step of case study on implementation (1)
(2) emulsion polymerization carries out Surface grafting reaction to improved silica
The improved silica of dry 0.8g is dispersed in the distilled water of 100ml, 0.24g sodium bicarbonates are sequentially added
(NaHCO3), 0.04g perfluoroalkyl ethers acrylate, ultrasonic disperse 30min is added in reactor, oil bath heating to 80 DEG C,
It is passed through argon gas, mechanical agitation, speed of agitator 250r/min, and 2g methyl methacrylates are added in backward reaction system, lotion
0.04g potassium peroxydisulfates are dissolved in 10ml water by 30min, are added drop-wise in reaction system after dissolving completely, 1h is dripped off, 80 DEG C of perseverances
Temperature reaction 16h, gained lotion is stood, and obtains the aqueous super hydrophobic material that grafting amount is 60%；The material is added to the water
It is configured to the dispersion liquid of mass ratio 2%, 25g dispersion liquids are sprayed according to every square metre of matrix surface, by the material spraying in spring Asia
In woven fabric, after being dried at 140 DEG C, wearability test is carried out to it with abrasion instrument, at pressure 250g, surveys its wearability song
Line, 800 circle after contact angle still greater than 150 °, keep its super-hydrophobic effect.
Embodiment 3：
The preparation for the material that grafting amount is 40%
(1) silica (grain size is 10~100nm) is modified with one step of case study on implementation (1)
(2) emulsion polymerization carries out Surface grafting reaction to improved silica
The modified silica of dry 1.2g is dispersed in the distilled water of 100ml, 0.24g bicarbonates are sequentially added
Sodium (NaHCO3), 0.02g perfluoroalkyl ethers acrylate, ultrasonic disperse 30min is added in reactor, oil bath heating to 80
DEG C, it is passed through argon gas, mechanical agitation, and 2g methyl methacrylates are added in backward reaction system, lotion 30min, by 0.04g mistakes
Potassium sulfate is dissolved in 10mL water, is added drop-wise in the reactor of front after dissolving completely, and 1h is dripped off, speed of agitator 250r/min, and 80
DEG C isothermal reaction 16h, gained lotion is stood, and it is that the 40% aqueous super hydrophobic material material is added to the water to obtain grafting amount
It is configured to the dispersion liquid that quality is 2%, 25g dispersion liquids are sprayed according to every square metre of matrix surface, by the material spraying in spring Asia
In woven fabric, after being dried at 140 DEG C, wearability test is carried out to it with abrasion instrument, at pressure 250g, surveys its wearability song
Line, 700 circle after contact angle still greater than 150 °, keep its super-hydrophobic effect.
Embodiment 4：
The preparation for the material that grafting amount is 20%
(1) silica (grain size is 10~100nm) is modified with one step of case study on implementation (1)
(2) emulsion polymerization carries out Surface grafting reaction to improved silica
The improved silica of dry 1.6g is dispersed in the distilled water of 100ml, 0.24g sodium bicarbonates are sequentially added
(NaHCO3), 0.02g perfluoroalkyl ethers acrylate, ultrasonic disperse 30min is added in reactor, oil bath heating to 80 DEG C,
It is passed through argon gas, mechanical agitation, and 2g methyl methacrylates are added in backward reaction system, lotion 30min, by 0.04g over cures
Sour potassium is dissolved in 10mL water, is added drop-wise in the reactor of front after dissolving completely, and 1h is dripped off, speed of agitator 250r/min, 80 DEG C
Isothermal reaction 16h stands gained lotion, obtains the aqueous super hydrophobic material that grafting amount is 20%；The material is added to the water
It is configured to the dispersion liquid that quality is 2%, 25g dispersion liquids are sprayed according to every square metre of matrix surface, by the material spraying in spring Asia
In woven fabric, after being dried at 140 DEG C, wearability test is carried out to it with abrasion instrument, at pressure 250g, surveys its wearability song
Line, 600 circle after contact angle still greater than 150 °, keep its super-hydrophobic effect.
Embodiment 5：
The preparation for the material that grafting amount is 10%
(1) silica (grain size is 10~100nm) is modified with one step of case study on implementation (1)
(2) emulsion polymerization carries out Surface grafting reaction to improved silica
The modified silica of dry 1.8g is dispersed in the distilled water of 100ml, 0.24g bicarbonates are sequentially added
Sodium, (NaHCO3), 0.02g perfluoroalkyl ethers acrylate, ultrasonic disperse 30min is added in reactor, heating water bath to 80
DEG C, it is passed through argon gas, mechanical agitation, and 2g methyl methacrylates are added in backward reaction system, 30min is emulsified, by 0.04g mistakes
Potassium sulfate is dissolved in 10mL water, is added drop-wise in the reactor of front after dissolving completely, and 1h is dripped off, speed of agitator 250r/min, and 80
For 24 hours, gained lotion is stood for DEG C isothermal reaction, obtains the aqueous super hydrophobic material that grafting amount is 10%；The material is added to water
In be configured to the dispersion liquid that quality is 2%, 25g dispersion liquids are sprayed according to every square metre of matrix surface, by the material spraying in the spring
In sub- woven fabric, after being dried at 140 DEG C, wearability test is carried out to it with abrasion instrument, at pressure 250g, surveys its wearability song
Line, 500 circle after contact angle still greater than 150 °, keep its super-hydrophobic effect.
Aqueous super hydrophobic material prepared by the present invention utilizes the hydrophobic polymer more than glass transition temperature, polymer
Chain setting in motion can mutually tangle between chain and chain, and even closer, therefore nano particle is combined between the microballoon and microballoon of material
It is not easily to fall off, the wearability of material is increased, the deficiency brought using adhesive is avoided；And the present invention uses emulsion polymerization
Method synthesis, avoid use organic solvent, environmental pollution is small, and preparation process is simple；Furthermore the present invention uses fluorine-containing emulsifier
Fluorochemical monomer does not carry out emulsion polymerization, avoids due to the use of fluorochemical monomer deficiency of high cost caused by expensive.It is (super thin
Water material is skin effect, and emulsifier can be coated on microsphere surface, the fluorine-containing emulsifier meeting that the present invention uses after emulsion polymerization
It is coated on material surface and forms low-surface-energy, generate super-hydrophobic effect, avoid using high cost caused by fluorochemical monomer, it is heavier
What is wanted is that will produce homopolymer microballoon and SiO in the process2@polymer form hierarchical structure, preferably construct super-hydrophobic
Surface.)
Unaccomplished matter of the present invention is known technology.
Claims (4)
1. a kind of preparation method of the aqueous super hydrophobic material of fluorine-free monomer, it is characterized in that this approach includes the following steps：
1）Silica（Grain size is 10 ~ 100nm）Surface be modified, following methods can be taken：
In ethanol by silica dispersion, it after ultrasonic disperse 30min, adds it in reactor, adds ammonium hydroxide, silane
Coupling agent and water, at room temperature mechanic whirl-nett reaction 48h product is washed repeatedly with ethyl alcohol, centrifugation, very after reaction
After sky is dry, the silica that surface carries double bond is obtained；
Wherein, quality of material ratio is silica：Ethyl alcohol：Ammonium hydroxide：Water：Silane coupling agent=1-100：1-1000：1-100：1-
100：1-100；
The silane coupling agent is γ-methacryloxypropyl trimethoxy silane, vinyltrimethoxysilane, second
(b- methoxy ethoxies) silane of alkenyl three or vinyltriethoxysilane；
2）To the Surface grafting reaction of modified silica, following methods can be taken：
Water, the silica of modification, sodium bicarbonate are added in the reactor（NaHCO3）, emulsifier, ultrasonic disperse 30min, in argon
Monomer dropping is entered into reaction system under gas shielded, 30min is emulsified, after system temperature is risen to 80 DEG C, by initiator solution
Be added dropwise in reaction system, mechanical agitation, reaction 16 ~ for 24 hours after, stop reaction, obtain the aqueous super-hydrophobic material of different grafting amounts
Material；
Its material proportion is that quality compares improved silica：Water：Monomer：Emulsifier：Initiator solution=0.1-10：1-100：1-
10：0.01-1：1-10；Sodium bicarbonate (the NaHCO of 0.10 ~ 0.24g is added in the water of 100 mL3)；The concentration of initiator solution
For the initiator dissolved with 0.03 ~ 0.10g. in the water of 10 mL；
Wherein, emulsifier is perfluoro butyl sulfonic acid fluoride, perfluoroalkyl ethers acrylate, perfluoro octyl sulfonic acid potassium or perfluor alkane；Draw
Hair agent is potassium peroxydisulfate, ammonium persulfate, isopropyl benzene hydroperoxide or isopropyl benzene hydroperoxide；Monomer is styrene, metering system
One or more of sour methyl esters, ethyl methacrylate, butyl methacrylate and glyceral methacrylate.
2. the preparation method of the aqueous super hydrophobic material of fluorine-free monomer as described in claim 1, it is characterized in that the ammonium hydroxide
Mass fraction is 25 ~ 28%.
3. the application of the aqueous super hydrophobic material of fluorine-free monomer as described in claim 1, it is characterized in that including the following steps：
The aqueous super hydrophobic material is configured to the dispersion liquid of required concentration, by dispersion liquid spraying and substrate material surface
On, it is dried at a temperature of placing it in 135 ~ 145 DEG C, that is, constitutes super-hydrophobic coat；
The upper quality of material ratio is aqueous super hydrophobic material：Water=1：10-1000；Every square metre of matrix surface spraying 25 ~
35g dispersion liquids.
4. the application of the aqueous super hydrophobic material of fluorine-free monomer as claimed in claim 3, it is characterized in that the basis material is
Timber, metal, cement, fabric, plastics or glass.
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