CN111847492B - Preparation method of nano ettringite particles and modified nano ettringite particles and application of nano ettringite particles and modified nano ettringite particles in polyurethane film - Google Patents
Preparation method of nano ettringite particles and modified nano ettringite particles and application of nano ettringite particles and modified nano ettringite particles in polyurethane film Download PDFInfo
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Abstract
The invention discloses a preparation method of nano ettringite particles and modified nano ettringite particles and application thereof in polyurethane films, wherein Ca is contained 2+ 、Al 3+ 、SO 4 2‑ Dissolving the raw materials in deionized water, adding a surfactant, adjusting the pH of the system to 10.6-12.9 by using sodium hydroxide, stirring and reacting at 20-50 ℃ for 3-12 h, and supplementing a sodium hydroxide solution in the reaction process; after the reaction is finished, filtering, washing and drying to prepare the nano ettringite particles; according to the invention, common calcium source, aluminum source and sulfate are used as raw materials, nano ettringite particles are obtained under the regulation and control of a surfactant and alkali liquor, and are applied to the preparation of a polyurethane film after being modified by a silane coupling agent.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a preparation method of nano ettringite particles and modified nano ettringite particles and application of the nano ettringite particles and the modified nano ettringite particles in a polyurethane film.
Background
With the development of science and technology, the application of polymer films in national economy is more and more extensive, and the requirements on the use performance of film materials are higher and higher. The polyurethane film has the performances of high tension, water resistance, air permeability, obdurability, aging resistance, excellent biological and blood compatibility and chemical resistance, and is rapidly developed due to the easy use, the diversified functions and the like of the product, widely applied to a plurality of fields of medical treatment and health, high-grade textile fabrics, industry and the like, and is popular and favored by users.
Compared with other materials, the polyurethane has the characteristics of wear resistance, oil resistance, chemical corrosion resistance, ray radiation resistance and the like due to a plurality of functional groups and complex structures on the soft segment chain, but has the defects of low strength, poor water resistance, poor heat resistance and the like, and further application of the polyurethane is limited. Many researchers modify the organic silicon, acrylic resin, epoxy resin, natural products, and blending with plastics, filling short fibers, etc., but these modification methods all have the disadvantages of high cost or poor effect.
Ettringite is the sulfate attack of cement, ca in the hydration hardening process 2+ 、Al 3+ And SO 4 2- The insoluble needle crystal formed by combination loses crystal water between 90 ℃ and 400 ℃ and is in an amorphous state, the original crystal structure can be quickly recovered after water absorption, and the insoluble needle crystal is frequently used as a concrete expanding agent, and besides, other applications of ettringite are rarely disclosed in the prior art.
Disclosure of Invention
In order to solve the above technical problems, the present invention provides a method for preparing nano ettringite particles, which comprises using Ca 2+ 、Al 3+ 、SO 4 2- The raw materials are prepared into nano ettringite particles under the regulation and control of a surfactant and alkali liquor, and the average particle size of the nano ettringite particles is 20nm.
Another object of the present invention is to provide a method for preparing modified nano-ettringite particles, wherein the nano-ettringite particles are prepared by modifying with silane coupling agent, and the nano-ettringite particles modified with silane coupling agent can be uniformly dispersed in a polyurethane matrix, so as to reduce the stress concentration problem caused by agglomeration, increase the doping amount of nano-ettringite particles, and thereby improve the strength of a polyurethane film.
The invention also aims to provide application of the modified nano ettringite particles in preparation of polyurethane films.
The last object of the present invention is to provide a polyurethane film prepared by using the modified nano-ettringite particles as an additive, wherein the modified nano-ettringite particles are added into the raw materials for preparing the polyurethane film, so that the tensile strength, the elongation at break and the LOI value of the polyurethane film can be improved, and the water absorption of the polyurethane film can be reduced.
The technical scheme adopted by the invention is as follows:
a preparation method of nano ettringite particles comprises the following steps: will contain Ca 2+ 、Al 3+ 、SO 4 2- Dissolving the raw materials in deionized water, adding a surfactant, adjusting the pH of the system to 10.6-12.9 by using sodium hydroxide, stirring and reacting at 20-50 ℃ for 3-12 h, and supplementing a sodium hydroxide solution in the reaction process; after the reaction is finished, filtering, washing and drying are carried out, and the nano ettringite particles can be prepared.
In the reaction process, sodium hydroxide solution is supplemented every 1 hour to adjust the pH of the solution to be 10.6-12.9, and the complete structural formula of the ettringite crystal is { Ca } 6 [Al(OH) 6 ] 2 ·24H 2 O}(SO 4 ) 3 ·2H 2 O, first, the aluminum ions combine with hydroxide ions to form aluminum octahedra { Al (OH) 6 } 3- Then aluminum octahedron combines with calcium ion to form basic unit column structure { Ca 3 Al(OH) 6 ·12H 2 O} 3+ And finally { (SO) with inter-pillar trench 4 2- ) 3 ·2H 2 O is combined to form an ettringite complete structure. The generation of aluminum octahedron is the slowest step in the whole reaction, and the continuous supplement of sodium hydroxide can improve the generation rate of aluminum octahedron in the later stage of the reaction, improve the process of the whole reaction system and improve the conversion rate of raw materials.
Further, adjusting the pH of the system to 10.5 with sodium hydroxide; the stirring reaction condition is preferably stirring reaction at 25 ℃ for 6-8 h.
Further, the Ca 2+ 、Al 3+ 、SO 4 2- The ratio of the amounts of the Ca 2+ The concentration in deionized water was 0.12mol/L. The pH range of the reaction system and the concentration of each raw material in the solution are the key for controlling the formation rate of the ettringite, and the higher the pH value of the reaction system and the ion concentration of the solution, the faster the formation and growth rate of the ettringite is, and the more difficult the morphology is to control.
Further, the surfactant contains Ca in mass 2+ 、Al 3+ And SO 4 2- 0.1 to 10% by mass of the total amount of the raw materials (A), preferably5 to 8 percent.
Further, the Ca is contained 2+ The raw material of (2) is selected from any one or more of calcium hydroxide, calcium oxide, calcium chloride and calcium nitrate.
Further, the Al content is 3+ The raw material is selected from any one or more of sodium metaaluminate, aluminum nitrate, aluminum chloride and aluminum sulfate.
Further, the SO-containing 4 2- The raw material is selected from any one or more of sodium sulfate, potassium sulfate, calcium sulfate and aluminum sulfate.
Further, the surfactant is selected from any one or more of sodium hexametaphosphate, sodium potassium tartrate and boric acid. Na generated by sodium hexametaphosphate with positive charge on the surface of ettringite crystal 4 P 6 O 18 2- Ca capable of being selectively adsorbed on surface of ettringite crystal 2+ Completely wrap the surface of the ettringite crystal, reduce the surface energy of the ettringite crystal and further inhibit the continuous growth of the ettringite crystal. The potassium sodium tartrate and the boric acid can also wrap the ettringite crystal, thereby inhibiting the ettringite crystal from continuing to grow. The addition of the above surfactants can thus be controlled to obtain the desired particle size of the product of the invention.
The invention also provides a preparation method of the modified nano ettringite particles, and the modified nano ettringite particles are prepared by modifying the nano ettringite particles by a silane coupling agent.
Further, the silane coupling agent is present in an amount of 3 to 10% by mass, preferably 5% by mass, based on the nano-sized ettringite particles.
Further, the preparation method of the modified nanometer ettringite particle specifically comprises the following steps: ultrasonically dispersing the nanometer ettringite particles in ethanol, adding deionized water and a silane coupling agent, stirring at 55-65 ℃ for 6-8 h, and then filtering, washing and drying to obtain the modified nanometer ettringite particles.
Further, the mass ratio of the nano ettringite particles, the deionized water and the silane coupling agent is 1:0.25:0.05.
further, the concentration of the nano ettringite particles to ethanol is 0.02 to 0.05g/mL, preferably 0.03g/mL.
Further, the volume ratio of ethanol to deionized water is 9.
Further, the ethanol is absolute ethanol; the silane coupling agent is KH-550, molecules of the silane coupling agent are provided with amino and hydroxyl after hydrolysis in water, so that the silane coupling agent can be simultaneously combined with waterborne polyurethane and nano-ettringite particles, chain extension reaction can be carried out on the waterborne polyurethane and the amino in the polyurethane emulsification process, and the silane coupling agent KH-550 is used as an intermediate to connect polyurethane and the nano-ettringite particles in a hydrolysis condensation mode, so that the acting force of the ettringite nano-particles and the polyurethane is improved.
The invention also provides application of the modified nano ettringite particles in preparation of polyurethane films.
The addition amount of the modified nanometer ettringite particles in the preparation of the polyurethane film accounts for 2-10% of the mass of the polyurethane raw material.
The invention also provides a polyurethane film prepared by using the modified nano ettringite particles as an additive.
Further, the preparation method of the polyurethane film comprises the following steps: and ultrasonically and uniformly mixing a water-soluble polyurethane solution and the modified nano ettringite particles to obtain a mixed solution, standing to eliminate bubbles, casting the mixed solution into a template to form a film, drying at room temperature, and heating and drying to obtain the polyurethane film.
Further, the mass percentage of the modified nano ettringite particles relative to the water-soluble polyurethane solution is 2-4%.
The ultrasonic time is 1.5-3 h.
The standing time is 1-1.5 h.
The drying time at room temperature is 20-28 h.
The condition of heating and drying is drying in an oven at 65-75 ℃ for 2.5-3.5 h.
The invention uses the commonly used Ca-containing 2+ 、Al 3+ 、SO 4 2- Of (2)The modified waterborne polyurethane film composite material is prepared by adding the nano-ettringite particles into waterborne polyurethane, and due to the high-modulus performance of the ettringite nano-particles, the mechanical property and the flame retardance of the waterborne polyurethane film can be improved after the nano-ettringite particles are added, so that the application range of the waterborne polyurethane film is enlarged. Meanwhile, the nano ettringite particles have the advantages of easily obtained preparation raw materials, low cost and easy popularization and use.
Compared with the prior art, the invention has the following advantages:
(1) The raw materials for preparing the nano ettringite particles disclosed by the invention are common and easy to obtain, the cost of the raw materials is low, and the preparation process is simple;
(2) The ettringite structure is 3 CaO. Al 2 O 3 ·3CaSO 4 ·32H 2 And O contains 32 crystal water, and the nano ettringite particles prepared by the method are modified by a silane coupling agent and then are used in the preparation of the polyurethane film, so that the crystal water can be released under the heating condition, the ignition point of the polyurethane film is reduced, and the flame retardance is improved.
(3) When the modified nanometer ettringite particles obtained by modification of the silane coupling agent are applied to preparation of a polyurethane film, the ettringite nanoparticles are uniformly dispersed in a water-based polyurethane matrix, and polyurethane molecules are wound on the polyurethane matrix to form physical cross-linking points, so that movement of polyurethane molecular chains is hindered, and the mechanical property of the polyurethane film is enhanced.
(4) The nanometer ettringite particles are subjected to surface modification by the silane coupling agent, the binding force of the nanometer ettringite particles and the waterborne polyurethane is improved, the nanometer ettringite particles can be uniformly dispersed in a polyurethane matrix, the problem of stress concentration caused by agglomeration can be avoided, the mixing amount of the nanometer ettringite particles is increased, and the strength of the polyurethane film is improved.
(5) The invention innovatively prepares the nanometer ettringite particles and innovatively applies the modified nanometer ettringite particles to the preparation of the polyurethane film so as to improve the mechanical property and the flame retardant property of the film.
Drawings
FIG. 1 is a flow chart of the preparation of polyurethane film using modified nano ettringite particles of the present invention;
FIG. 2 is an SEM image of nano-ettringite particles prepared in example 1;
FIG. 3 is an XRD pattern of nano-ettringite particles prepared in example 1;
FIG. 4 is an SEM image of the tensile section of the polyurethane film composite when the amount of the modified nano ettringite particles added is 0% in the practical example;
FIG. 5 is an SEM image of the tensile section of the polyurethane film composite material when the modified nano ettringite particles are added in an amount of 3% in the application example.
Detailed Description
The invention is described in detail below with reference to the following examples and the accompanying drawings.
Example 1
A preparation method of nano ettringite particles comprises the following steps:
0.12mol of Ca 2+ 、0.04mol Al 3+ 、0.06mol SO 4 2- Dissolving in 1000mL of deionized water, adding sodium hexametaphosphate accounting for 5 percent of the total mass of the three, adding 0.1mol/L of sodium hydroxide solution to adjust the pH of the solution to 10.5, stirring and reacting at 25 ℃ for 6h, supplementing the sodium hydroxide solution every 1h to adjust the pH of the solution to 10.5, filtering and washing the obtained suspension solution to be neutral, and vacuum-drying the solid at 50 ℃ for 24h to obtain the nano ettringite particles. Wherein Ca 2+ The source of (b) can be calcium hydroxide, calcium oxide, calcium chloride or calcium nitrate; al (aluminum) 3+ The source of the sodium aluminate can be sodium metaaluminate, aluminum nitrate, aluminum chloride or aluminum sulfate; SO (SO) 4 2- The source of (b) may be sodium sulfate, potassium sulfate, calcium sulfate or aluminum sulfate.
The SEM image of the nano ettringite particles prepared by the embodiment is shown in FIG. 2, and the average particle size of the nano ettringite particles is 20nm; the XRD pattern is shown in figure 3, and it can be seen that the nano ettringite particles are successfully prepared in the embodiment.
Example 2
A preparation method of nano ettringite particles comprises the following steps:
0.12mol of Ca 2+ 、0.04mol Al 3+ 、0.06mol SO 4 2- Dissolving in 1000mL of deionized water, adding boric acid accounting for 8% of the total mass of the three, adding 0.1mol/L of sodium hydroxide solution to adjust the pH of the solution to 10.5, stirring and reacting at 25 ℃ for 8h, supplementing the sodium hydroxide solution every 1h to adjust the pH of the solution to 10.5, filtering and washing the obtained suspension solution to be neutral, and vacuum-drying the solid at 50 ℃ for 24h to obtain the nano ettringite particles. Wherein Ca 2+ The source of (A) can be calcium hydroxide, calcium oxide, calcium chloride or calcium nitrate; al (Al) 3+ The source of the sodium aluminate can be sodium metaaluminate, aluminum nitrate, aluminum chloride or aluminum sulfate; SO (SO) 4 2- The source of (b) may be sodium sulfate, potassium sulfate, calcium sulfate or aluminum sulfate.
Example 3
A preparation method of nano ettringite particles comprises the following steps:
0.12mol of Ca 2+ 、0.04mol Al 3+ 、0.06mol SO 4 2- Dissolving in 1000mL of deionized water, adding sodium potassium tartrate accounting for 3% of the total mass of the three, adding 0.1mol/L of sodium hydroxide solution to adjust the pH of the solution to 10.5, stirring and reacting at 40 ℃ for 5 hours, supplementing the sodium hydroxide solution every 1 hour to adjust the pH of the solution to 10.5, filtering and washing the obtained suspension solution to be neutral, and vacuum-drying the solid at 50 ℃ for 24 hours to obtain the nano ettringite particles. Wherein Ca 2+ The source of (A) can be calcium hydroxide, calcium oxide, calcium chloride or calcium nitrate; al (aluminum) 3+ The source of the sodium aluminate can be sodium metaaluminate, aluminum nitrate, aluminum chloride or aluminum sulfate; SO (SO) 4 2- The source of (b) may be sodium sulfate, potassium sulfate, calcium sulfate or aluminum sulfate.
Comparative example 1
A preparation method of nano ettringite particles comprises the following steps:
0.12mol of Ca 2+ 、0.04mol Al 3+ 、0.06mol SO 4 2- Dissolving in 1000mL of deionized water, adding sodium hexametaphosphate accounting for 1 percent of the total mass of the three, adding 0.1mol/L of sodium hydroxide solution to adjust the pH of the solution to 10.5, stirring and reacting at 25 ℃ for 6h, supplementing the sodium hydroxide solution every 1h to adjust the pH of the solution to 10.5, filtering and washing the obtained suspension solution to be neutral, and vacuum-drying the solid at 50 ℃ for 24h to obtain the nano ettringite particles. Wherein Ca 2+ The source of (A) can be calcium hydroxide, calcium oxide, calcium chloride or calcium nitrate; al (aluminum) 3+ The source of the sodium aluminate can be sodium metaaluminate, aluminum nitrate, aluminum chloride or aluminum sulfate; SO (SO) 4 2- The source of (b) may be sodium sulfate, potassium sulfate, calcium sulfate or aluminum sulfate.
Comparative example 2
A preparation method of nanometer ettringite particles comprises the following steps:
0.18mol of Ca 2+ 、0.06mol Al 3+ 、0.09mol SO 4 2- Dissolving in 1000mL of deionized water, adding boric acid accounting for 8% of the total mass of the three, adding 0.1mol/L of sodium hydroxide solution to adjust the pH of the solution to 10.5, stirring and reacting at 25 ℃ for 12h, supplementing the sodium hydroxide solution every 1h to adjust the pH of the solution to 10.5, filtering and washing the obtained suspension solution to be neutral, and vacuum-drying the solid at 50 ℃ for 24h to obtain the nano ettringite particles. Wherein Ca 2+ The source of (A) can be calcium hydroxide, calcium oxide, calcium chloride or calcium nitrate; al (Al) 3+ The source of the sodium aluminate can be sodium metaaluminate, aluminum nitrate, aluminum chloride or aluminum sulfate; SO (SO) 4 2- The source of (b) may be sodium sulfate, potassium sulfate, calcium sulfate or aluminum sulfate.
Comparative example 3
A preparation method of nano ettringite particles comprises the following steps:
0.24mol of Ca 2+ 、0.08mol Al 3+ 、0.12mol SO 4 2- Dissolving in 1000mL deionized water, adding potassium sodium tartrate accounting for 3% of the total mass of the three, adding 0.1mol/L sodium hydroxide solution to adjust the pH of the solution to 12.0, stirring and reacting at 40 ℃ for 5h, supplementing sodium hydroxide solution every 1h to adjust the pH of the solution to 12.0, filtering the obtained suspension solution, and washing until the obtained suspension solution is washedAnd (3) drying the neutral solid in vacuum at 50 ℃ for 24 hours to obtain the nanometer ettringite particles. Wherein Ca 2+ The source of (A) can be calcium hydroxide, calcium oxide, calcium chloride or calcium nitrate; al (Al) 3+ The source of the sodium aluminate can be sodium metaaluminate, aluminum nitrate, aluminum chloride or aluminum sulfate; SO (SO) 4 2- The source of (b) may be sodium sulfate, potassium sulfate, calcium sulfate or aluminum sulfate.
Example 4
A preparation method of modified nanometer ettringite particles comprises the following steps:
adding 5g of the nano ettringite particles prepared in the example 1 into 180ml of absolute ethyl alcohol, performing ultrasonic dispersion for 30min to uniformly disperse the nano ettringite particles into the absolute ethyl alcohol, adding 20ml of deionized water and KH-550 accounting for 5% of the mass of the nano ettringite particles into the absolute ethyl alcohol, stirring and reacting for 6h at 60 ℃, performing suction filtration on reaction liquid, repeatedly washing a filter cake by using the absolute ethyl alcohol, and drying for 12h at 40 ℃ to obtain the modified nano ettringite particles. Finally, the obtained modified nano ettringite particles are ground by a mortar, pass through a 250-mesh sieve and are stored in a sealed manner.
Comparative example 4
The other method is the same as the method of example 4 except that KH-550 is replaced with KH-570.
The application example is as follows: application of modified nano ettringite particles in preparation of polyurethane film
The modified nano ettringite particles prepared in example 4 are added as a raw material for preparing a polyurethane film, and the preparation method of the polyurethane film specifically comprises the following steps:
weighing 15g of 30% aqueous polyurethane solution with mass concentration, adding 0%,1%,2%,3%,4%,5% of the modified nano-ettringite particles prepared in example 4 into the aqueous polyurethane solution, mixing the two solutions, performing ultrasonic treatment for 2h to uniformly disperse the modified nano-ettringite particles into the 30% aqueous polyurethane solution, standing the mixed solution for 1h to remove bubbles in the solution, finally casting the mixed solution into a polyethylene template to form a film, drying the film at room temperature for 1d, putting the film into an oven at 70 ℃ for drying for 3h, taking the film out, preparing the polyurethane film, and testing the performance of the polyurethane film, wherein the test results are shown in table 1:
TABLE 1
From the table above, it can be seen that the tensile strength and elongation at break of the polyurethane film can be significantly improved by adding the modified nano ettringite particles, and the flame retardant property of the polyurethane film is improved. The effect is better when the doping amount is 2-4%, wherein the comprehensive performance is best when the doping amount is 3%, the tensile strength and the elongation at break reach the highest values, the water absorption rate is relatively lower, and the flame retardant property is relatively better; if the nano ettringite particles are added too much, the nano ettringite particles cannot be uniformly dispersed in the aqueous polyurethane matrix, and are easy to form agglomeration, so that the phenomenon of stress concentration is caused, and the mechanical property of the polyurethane film is deteriorated.
FIGS. 4 and 5 are SEM images of the tensile section of the polyurethane film composite material when the amount of the modified nano ettringite particles added is 0% and 3%, respectively, and it can be seen that the tensile section of the polyurethane film is relatively flat without the addition of the nano ettringite particles; after 3% of nano ettringite particles are added, the tensile section of the polyurethane film is uneven, and the fracture difficulty is increased. It is demonstrated that the tensile strength of the polyurethane film is increased after the nano ettringite particles are added.
Comparative application
The nano ettringite particles prepared in each of the above comparative examples 1 to 3 were modified in the same manner as in example 4, and the modified nano ettringite particles were used to prepare a polyurethane film in the same manner as in application example 1, wherein the amount of the modified nano ettringite particles added was 3%, and the properties of the film were measured, and the results are shown in table 2.
TABLE 2
| Mixing amount/% | Water absorption/%) | Tensile strength/MPa | Elongation at break/% | LOI value | |
| Comparative example 1 | 3 | 12.31 | 36.71 | 340.2 | 25.6 |
| Comparative example 2 | 3 | 10.03 | 44.99 | 348.5 | 27.9 |
| Comparative example 3 | 3 | 11.58 | 40.65 | 341.7 | 27.1 |
| Comparative example 4 | 3 | 10.89 | 47.56 | 367.6 | 27.9 |
The above detailed description of the preparation method of nano ettringite particles and modified nano ettringite particles and their application in polyurethane films with reference to examples is illustrative and not restrictive, and several examples can be cited within the limits of the invention, so that changes and modifications without departing from the general concept of the invention shall fall within the protection scope of the invention.
Claims (7)
1. A preparation method of modified nano ettringite particles is characterized by comprising the following steps: will contain Ca 2+ 、Al 3+ 、SO 4 2- Dissolving the raw materials in deionized water, adding a surfactant, adjusting the pH of the system to 10.5-12.9 by using a sodium hydroxide solution, stirring and reacting at 20-50 ℃ for 3-12 h, and supplementing the sodium hydroxide solution in the reaction process to maintain the pH of the reaction system to 10.5-12.9; after the reaction is finished, filtering, washing and drying to obtain nano ettringite particles, and modifying the nano ettringite particles by a silane coupling agent to obtain the modified nano ettringite particles;
the Ca 2+ 、Al 3+ 、SO 4 2- The mass ratio of (a) to (b) is 6; the Ca 2+ The concentration of the solution in deionized water is 0.12mol/L;
the surfactant contains Ca 2+ 、Al 3+ And SO 4 2- 0.1 to 10 percent of the total mass of the raw materials;
the average particle size of the nano ettringite particles is 20nm;
the mass percentage of the silane coupling agent relative to the nano ettringite particles is 3 to 10 percent.
2. The method according to claim 1, wherein the Ca is contained 2+ The raw material is selected from one or more of calcium hydroxide, calcium oxide, calcium chloride and calcium nitrateSeed; said Al-containing 3+ The raw material is selected from any one or more of sodium metaaluminate, aluminum nitrate, aluminum chloride and aluminum sulfate.
3. The method of claim 1, wherein the SO-containing gas is produced by a process according to claim 1 4 2- The raw material is selected from any one or more of sodium sulfate, potassium sulfate, calcium sulfate and aluminum sulfate.
4. The method according to claim 1, wherein the surfactant is selected from any one or more of sodium hexametaphosphate, lithium carbonate and boric acid.
5. The modified nano ettringite particles prepared by the preparation method according to any one of claims 1 to 4.
6. The use of the modified nano ettringite particles of claim 5 in the preparation of polyurethane films.
7. A polyurethane film prepared by using the modified nano ettringite particles of claim 5 as an additive.
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| CN106365482A (en) * | 2016-08-30 | 2017-02-01 | 河南理工大学 | Superfine ettringite, preparation method and application of superfine ettringite to cement-based grouting material |
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