CN110040762B - Method for regulating and controlling growth of zinc oxide nanorod array based on two-dimensional colloid single-layer film - Google Patents
Method for regulating and controlling growth of zinc oxide nanorod array based on two-dimensional colloid single-layer film Download PDFInfo
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Abstract
The invention discloses a method for regulating and controlling growth of a zinc oxide nanorod array based on a two-dimensional colloid single-layer film. The method is simple and quick, the zinc oxide nanorod arrays with different heights can be obtained in different hydrothermal growth times, the zinc oxide nanorod arrays with different heights have different hydrophilicity and hydrophobicity, the regulation and control of the zinc oxide nanorod arrays at lower temperature and in shorter reaction time are realized, and the constructed zinc oxide nanorod arrays have excellent stability and have potential application values in the aspects of surface enhanced Raman, biomedical, nanophotonics, electrocatalysis and new energy application.
Description
Technical Field
The invention belongs to the technical field of construction of a semiconductor nanorod array structure, and particularly relates to a method for regulating and controlling growth of a zinc oxide nanorod array structure by using a two-dimensional colloid single-layer film as a template.
Background
Zinc oxide (ZnO) is an important semiconductor material, has a wide bandgap (3.37eV) and a high exciton binding energy (60meV), and has good piezoelectric properties, electrical conductivity, transparency, photoelectronic properties, etc., thereby having a wide application prospect in the fields of catalysis, solar cells, piezoelectric devices, biomedical sensing, micro/nano electronics, etc. The nano-structure ZnO has the performances of various shapes, high chemical stability, adjustable photoelectric property, good biocompatibility and the like, and can be used as an excellent substrate material for Surface Enhanced Raman Scattering (SERS). The ZnO nanorod with the array structure has the advantages of high surface-to-volume ratio, easiness in shape control, high growth speed, low cost and the like, and therefore becomes a preferred SERS active substrate material with high activity, high stability and reusability.
In general, researchers have prepared zinc oxide nanorod array structures by various synthesis techniques, including Chemical Vapor Deposition (CVD), electrodeposition, pulsed laser deposition, hydrothermal growth in a liquid medium, and the like. The CVD method for preparing the zinc oxide nano rod is to take a zinc simple substance or zinc oxide as a raw material to be in a gaseous reaction in a tube furnace, and prepare the zinc oxide nano rod through chemical processes such as evaporation or oxidation reduction, decomposition, chemical combination and the like. The CVD method generally needs to be performed at a high temperature of 500 ℃ or higher, and factors such as reaction temperature, type of reaction gas, partial pressure, flow rate, and kind of catalyst need to be controlled to some extent, which makes it difficult to realize large-scale production. The electrodeposition technology is that the substrate to be grown is used as a working electrode in an electrochemical cell, a graphite plate is used as a counter electrode, an electrolyte is an aqueous solution containing zinc salt (such as zinc nitrate and the like) and potassium chloride, and the deposition is carried out under the conditions of certain current and temperature, and the growth of a zinc oxide nanorod can be regulated and controlled by the electrodeposition technology through the current time and the electrolyte concentration. The electrochemical deposition method has the defect that the ZnO nano material cannot be obtained on the insulating substrate. The pulse laser deposition method is a method for evaporating raw materials by utilizing high energy of pulse laser to deposit the raw materials into nano materials, and can prepare a nano wire array with good orientation and controllable diameter and aspect ratio of at least 50. The hydrothermal growth method is a method for preparing metal oxide in an aqueous solution by taking water as a solvent and adding a reaction system to generate a high-temperature high-pressure environment in a sealed pressure container to accelerate an ionic reaction and promote a hydrolysis reaction.
Besides the method, the porous alumina, the silicon nanowire, the graphene, the colloidal crystal and the like are used as templates, and the zinc oxide nanorod can be accurately controlled and synthesized by utilizing the pore channel structure, the regular morphology and the like of the templates. For example, Hou et al (The Journal of Physical Chemistry B,2004,108(32):11976-11980.) prepared a zinc oxide nanorod array structure with a diameter of 130nm and 260nm and a length of 7.6-14 μm by an evaporation method using a porous alumina array structure at 700-900 ℃. Kang et al (Sensors and activators B: Chemical,2018,273:48-55.) reported that dendritic zinc oxide nanorod array structures were grown on Si nanowire array structures by hydrothermal methods to form zinc oxide nanorod array structures with aspect ratios perpendicular to the Si nanowires of about 20, but the Si nanowire array substrates were constructed by etching with hydrofluoric acid and other solutions, which is dangerous. He et al (Journal of The Electrochemical Society,2017,164(13) D895-D900.) reported that a hexagonal-packed polystyrene two-dimensional array structure was used as a template, and a zinc oxide nanorod structure was grown by electrodeposition, and zinc oxide nanorod array structures of different lengths were obtained by controlling The concentration of an electrolyte solution during The reaction, The diameter of The zinc oxide nanorod was about 150nm and The length was about 1 μm, but an experimental apparatus with higher requirements for electrodeposition technology could not be made large-scale production. Zhang group (Dalton trans, 2015,44, 3447-3453) utilizes a patterned sapphire substrate with a hemisphere array to construct a highly ordered zinc oxide nanorod array structure on the surface of the substrate by a conventional hydrothermal growth method, wherein the length of the nanorod is about 1 μm and the diameter of the nanorod is about 60nm, the distance between patterned sapphire hemispheres can regulate the growth of the nanorod array structure, but the construction of the sapphire hemisphere substrate needs a large cost. Du et al (Applied Physics, A2019,125: 138.) prepared three-dimensional hierarchical zinc oxide hydrophobic nano-structure by using Polydimethylsiloxane (PDMS) flexible substrate, adjusted hydrothermal reaction conditions to obtain flexible active substrate with different surface morphology structures, the nano-rod structure all had better uniformity and length, but the irregular structure of PMDS flexible substrate surface could not be used as the best template for array structure growth.
Disclosure of Invention
The invention aims to provide a method for preparing a zinc oxide nanorod array with adjustable height and hydrophilicity and hydrophobicity by using a two-dimensional colloid single-layer film as a template through a hydrothermal method.
Aiming at the purposes, the technical scheme adopted by the invention comprises the following steps:
1. preparation of two-dimensional colloidal monolayer films
Taking a mixed solution of water and ethanol in a volume ratio of 1: 1-10: 1 as a solvent, and preparing 1-10% suspension of core-shell type poly (styrene-N-isopropylacrylamide) @ polyacrylic acid in percentage by mass; inserting a glass sheet into 0.01-0.08 mmol/L sodium dodecyl sulfate aqueous solution at an angle of 30-60 degrees with respect to the liquid surface, and then dripping the obtained suspension onto the glass sheet to disperse the suspension onto a gas-liquid interface along the glass sheet to form a close-packed two-dimensional colloid single-layer film; and finally, transferring the two-dimensional colloid single-layer film formed on the interface to the surface of a hydrophilic substrate, and airing under natural conditions.
2. Construction of zinc oxide nanorod array
Soaking the hydrophilic base material with the two-dimensional colloid single-layer film arranged on the surface, which is obtained in the step 1, in 5-20 mmol/L zinc acetate dihydrate ethanol solution for 3-6 h, taking out, drying at 70-90 ℃, and horizontally placing in a hydrothermal reaction kettle with the surface with the film facing upwards; adding hexamethylene tetramine into 10-50 mmol/L zinc nitrate hexahydrate aqueous solution, stirring to dissolve, then adding polyethyleneimine, adjusting the pH to 9-12 with ammonia water, then pouring into the hydrothermal reaction kettle, and carrying out hydrothermal growth for 10-180 min at 85-95 ℃ under a sealed condition to obtain the zinc oxide nanorod array.
In the step 1, preferably, a mixed solution of water and ethanol in a volume ratio of 1: 1-5: 1 is used as a solvent, and the core-shell type poly (styrene-N-isopropylacrylamide) @ polyacrylic acid is prepared into a suspension with a mass percentage of 3% -6%.
In the step 1, preferably, the glass sheet is inserted into 0.03-0.05 mmol/L sodium dodecyl sulfate aqueous solution at an angle of 30-60 degrees with respect to the liquid surface, and then the obtained suspension is dripped onto the glass sheet to be dispersed on a gas-liquid interface along the glass sheet to form a close-packed two-dimensional colloid single-layer film.
In the step 1, the hydrophilic substrate is any one of a silicon wafer, a quartz wafer, ITO conductive glass and FTO conductive glass which are treated by a mixed solution of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 7: 3.
In the step 2, preferably, the hydrophilic substrate on which the two-dimensional colloid single-layer film is arranged on the surface is soaked in 10-15 mmol/L zinc acetate dihydrate ethanol solution for 5 hours, then taken out, and dried at 90 ℃.
In the step 2, preferably, the cyclic hexamethylene tetramine is added into a 20-30 mmol/L zinc nitrate hexahydrate aqueous solution, the polyethylene imine is added after stirring and dissolving, the pH value is adjusted to 10-11 by ammonia water, wherein the molar ratio of the zinc nitrate hexahydrate to the cyclic hexamethylene tetramine to the polyethylene imine is 1: 1-1.2: 0.1-0.2, and the number average molecular weight of the polyethylene imine is 10000-30000.
In the step 2, the hydrothermal growth is preferably carried out for 30-120 min at 90 ℃ under a closed condition.
The invention takes a two-dimensional colloid monolayer film constructed by polymer microgel as a template, and prepares the zinc oxide nanorod array by a hydrothermal method, thereby realizing the regulation and control of the zinc oxide nanorod array at lower temperature and in shorter reaction time. By regulating and controlling the reaction time, the zinc oxide nanorod array with the height of 200-1000 nm can be obtained, and the array is gradually changed from hydrophilicity to hydrophobicity along with the increase of the height of the nanorod. The size of the high molecular microgel building units determines the density of the zinc oxide nano-rods, and the building units with different grain diameters can obtain zinc oxide nano-rod arrays with different morphological structures.
The method is simple and rapid, and the constructed zinc oxide nanorod array has excellent stability and has potential application value in the aspects of surface enhanced Raman, biomedicine, nanophotonics, electrocatalysis and new energy application.
Drawings
Fig. 1 is a scanning electron micrograph of the two-dimensional colloidal monolayer film obtained in example 1.
Fig. 2 is a scanning electron micrograph of a cross section of the two-dimensional colloidal monolayer film obtained in example 1.
Fig. 3 is an XRD pattern of the zinc oxide nanorod array grown for 30min in example 1.
Fig. 4 is a scanning electron microscope photograph of the zinc oxide nanorod array grown for 30min in example 1.
FIG. 5 is a cross-sectional scanning electron microscope and a contact angle photograph of the zinc oxide nanorod array grown for 30min in example 1.
Fig. 6 is a scanning electron microscope photograph of the zinc oxide nanorod array grown for 60min in example 2.
FIG. 7 is a sectional scanning electron microscope and a contact angle photograph of the zinc oxide nanorod array grown for 60min in example 2.
Fig. 8 is a scanning electron microscope photograph of the zinc oxide nanorod array grown for 120min in example 3.
FIG. 9 is a cross-sectional scanning electron microscope and a contact angle photograph of the zinc oxide nanorod array grown for 120min in example 3.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
The core-shell poly (styrene-N-isopropylacrylamide) @ polyacrylic acid (P (St-co-NIPAM) @ PAA) used in the examples was synthesized according to the method described in the literature "Colloid and Polymer Science,2015,293(8): 2405-: 0.20g N-isopropylacrylamide (NIPAM) and 1.80g styrene (St) were dissolved inHeating 90mL of deionized water in a water bath under the protection of nitrogen atmosphere and mechanical stirring (constant rotation speed of 400 r/min), and heating 10mL of deionized water with the concentration of 5.92 multiplied by 10 when the temperature of the system is raised to 70 DEG C-2Adding a mol/L potassium persulfate aqueous solution into a reaction system, and carrying out polymerization reaction for 8h to obtain a P (St-co-NIPAM) microsphere dispersion liquid; 1.0g of Acrylic Acid (AA) monomer and 0.1g of 0.1g N, N' -Methylenebisacrylamide (MBA) were dissolved in 10mL of distilled water, and then added to the dispersion of P (St-co-NIPAM) microspheres and 3mL of a 9.86X 10 concentration solution were added-2Heating the potassium persulfate water solution of mol/L in a constant-temperature water bath at 70 ℃ for 4h under the protection of nitrogen atmosphere and under mechanical stirring (constant rotating speed of 400 r/min), cooling to room temperature, alternately washing the product with water and absolute ethyl alcohol, centrifuging (rotating speed of 9000r/min), and freeze-drying to obtain P (St-co-NIPAM) @ PAA with uniform size and about 300nm of particle size.
Example 1
1. Preparation of two-dimensional colloidal monolayer films
Taking a mixed solution of water and ethanol in a volume ratio of 1:1 as a solvent, and preparing a suspension with the mass percentage of 4% by using P (St-co-NIPAM) @ PAA; and (3) inserting the glass sheet into 500mL of 0.04mmol/L sodium dodecyl sulfate aqueous solution at an angle of 45 degrees with the liquid surface, and then dropwise adding the obtained suspension onto the glass sheet to disperse the suspension onto a gas-liquid interface along the glass sheet to form a close-packed two-dimensional colloid single-layer film. And finally, transferring the two-dimensional colloid single-layer film formed on the interface to the surface of a silicon wafer (1cm multiplied by 1cm) treated by the mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 7:3, and airing under natural conditions. A Hitachi SU8220 type cold field scanning electron microscope is adopted to observe the morphology structure of a sample, and as can be seen from figures 1-2, P (St-co-NIPAM) @ PAA is arranged on the surface of a silicon wafer in a single-layer hexagonal close packing manner.
2. Construction of zinc oxide nanorod array
Soaking the silicon wafer with the two-dimensional colloid single-layer film arranged on the surface in 10mL of 10mmol/L zinc acetate dihydrate ethanol solution for 5h, taking out, drying at 90 ℃, and horizontally placing in a 50mL hydrothermal reaction kettle with the film side facing upwards; adding 0.298g (25mmol) of zinc nitrate hexahydrate and 0.14g (25mmol) of hexamethylene tetramine into 40mL of water, stirring to dissolve, then adding 0.135g (3mmol) of polyethyleneimine with the number-average molecular weight of 10000, adjusting the pH value to 10.5 by using ammonia water, then pouring into a hydrothermal reaction kettle, and carrying out hydrothermal growth for 30min at 90 ℃ under a closed condition to obtain a zinc oxide nanorod array (P (St-co-NIPAM) @ PAA/ZnONRs).
A Bruker D8Discover X-ray diffractometer is adopted to measure the crystal structure of a sample, a Hitachi SU8220 cold field scanning electron microscope is adopted to observe the appearance structure of the sample, and a video optical contact angle measuring instrument of OCA 20 model of Germany Dataphysics company is adopted, and the results are shown in figures 3-5. As can be seen from FIG. 3, the lattice diffraction of the zinc oxide nanorods appears in the sample, which proves that the zinc oxide nanorods have been successfully prepared. As can be seen from fig. 4 and 5, the growth height of the zinc oxide nanorods was about 203.8nm, and the surface contact angle was 44.3 °.
Example 2
In step 2 of this example, hydrothermal growth was carried out at 90 ℃ for 60min under a closed condition, and the other steps were the same as in example 1, to obtain a zinc oxide nanorod array. As can be seen from fig. 6 and 7, the growth height of the zinc oxide nanorods was 543.7nm, and the contact angle was 85.6 °.
Example 3
In step 2 of this example, hydrothermal growth was performed at 90 ℃ for 120min under a closed condition, and the other steps were the same as in example 1, to obtain a zinc oxide nanorod array. As can be seen from fig. 8 and 9, the growth height of the zinc oxide nanorods was 1013.2nm, and the contact angle was 123.7 °.
Example 4
1. Preparation of two-dimensional colloidal monolayer films
Taking a mixed solution of water and ethanol in a volume ratio of 5:1 as a solvent, and preparing a suspension with the mass percentage of 6% by using P (St-co-NIPAM) @ PAA; the glass sheet is inserted into 500mL of 0.05mmol/L sodium dodecyl sulfate aqueous solution at an angle of 60 degrees with the liquid surface, and then the obtained suspension is dripped onto the glass sheet to be dispersed on a gas-liquid interface along the glass sheet to form a close-packed two-dimensional colloid single-layer film. And finally, transferring the two-dimensional colloid single-layer film formed on the interface to the surface of a silicon chip (1cm multiplied by 1cm) treated by the piranha acid, and airing under natural conditions.
2. Construction of zinc oxide nanorod array
Soaking the silicon wafer with the two-dimensional colloid single-layer film arranged on the surface in 10mL of 15mmol/L zinc acetate dihydrate ethanol solution for 5h, taking out, drying at 90 ℃, and horizontally placing in a 50mL hydrothermal reaction kettle with the film side facing upwards; adding 0.238g (20mmol) of zinc nitrate hexahydrate and 0.112g (20mmol) of hexamethylene tetramine into 40mL of water, stirring to dissolve, then adding 0.108g (2.4mmol) of polyethyleneimine with the number-average molecular weight of 10000, adjusting the pH to 9 with ammonia water, then pouring into a hydrothermal reaction kettle, and carrying out hydrothermal growth for 60min at 90 ℃ under a sealed condition to obtain the zinc oxide nanorod array.
Example 5
1. Preparation of two-dimensional colloidal monolayer films
Taking a mixed solution of water and ethanol in a volume ratio of 3:1 as a solvent, and preparing a suspension with the mass percentage of 3% by using P (St-co-NIPAM) @ PAA; the glass sheet is inserted into 500mL0.03mmol/L sodium dodecyl sulfate aqueous solution at an angle of 30 degrees with the liquid surface, and the obtained suspension is dripped onto the glass sheet to be dispersed on a gas-liquid interface along the glass sheet to form a close-packed two-dimensional colloid single-layer film. And finally, transferring the two-dimensional colloid single-layer film formed on the interface to the surface of a silicon chip (1cm multiplied by 1cm) treated by the piranha acid, and airing under natural conditions.
2. Construction of zinc oxide nanorod array
Soaking the silicon wafer with the two-dimensional colloid single-layer film arranged on the surface in 10mL of 10mmol/L zinc acetate dihydrate ethanol solution for 5h, taking out, drying at 90 ℃, and horizontally placing in a 50mL hydrothermal reaction kettle with the film side facing upwards; 0.358g (30mmol) of zinc nitrate hexahydrate and 0.168g (30mmol) of hexamethylene tetramine are added into 40mL of water, stirred and dissolved, then 0.162g (3.6mmol) of polyethyleneimine with the number-average molecular weight of 10000 is added, ammonia water is used for adjusting the pH value to 11, then the mixture is poured into a hydrothermal reaction kettle, and hydrothermal growth is carried out for 120min at 90 ℃ under a sealed condition, so that the zinc oxide nanorod array is obtained.
Claims (9)
1. A method for regulating and controlling the growth of a zinc oxide nanorod array based on a two-dimensional colloid monolayer film is characterized by comprising the following steps:
(1) preparation of two-dimensional colloidal monolayer films
The volume ratio of water to ethanol is 1: 1-10: 1The mixed solution is used as a solvent, and the core-shell type poly (styrene-N-Isopropyl acrylamide) @ polyacrylic acid is prepared into suspension with the mass percentage of 1 percent to 10 percent; inserting a glass sheet into 0.01-0.08 mmol/L sodium dodecyl sulfate aqueous solution at an angle of 30-60 degrees with respect to the liquid surface, and then dripping the obtained suspension onto the glass sheet to disperse the suspension onto a gas-liquid interface along the glass sheet to form a close-packed two-dimensional colloid single-layer film; finally, transferring the two-dimensional colloid single-layer film formed on the interface to the surface of a hydrophilic substrate, and airing under natural conditions;
the above core-shell type poly (styrene-N-The synthesis method of isopropyl acrylamide) @ polyacrylic acid comprises the following steps: 0.20gN-Dissolving isopropyl acrylamide and 1.80g styrene in 90mL deionized water, heating in water bath under nitrogen atmosphere and mechanical stirring at constant speed of 400r/min, heating to 70 deg.C, and adding 10mL of 5.92 × 10-2Adding a mol/L potassium persulfate aqueous solution into the reaction system, and carrying out polymerization reaction for 8h to obtain poly (styrene-N-Isopropyl acrylamide) microsphere dispersion; 1.0g of an acrylic monomer and 0.1g ofN,N' -Methylenebisacrylamide was dissolved in 10mL of distilled water and then added to poly (styrene-N-Isopropylacrylamide) and 3mL of a 9.86X 10 concentration solution was added to the microsphere dispersion-2Heating the mol/L potassium persulfate aqueous solution in a constant-temperature water bath at 70 ℃ for 4h under the protection of nitrogen atmosphere and the mechanical stirring at a constant rotating speed of 400r/min, cooling to room temperature, alternately washing the product with water and absolute ethyl alcohol, centrifuging at a rotating speed of 9000r/min, and freeze-drying to obtain the core-shell type poly (styrene-N-Isopropylacrylamide) @ polyacrylic acid;
(2) construction of zinc oxide nanorod array
Soaking the hydrophilic base material with the two-dimensional colloid single-layer film arranged on the surface, which is obtained in the step (1), in 5-20 mmol/L zinc acetate dihydrate ethanol solution for 3-6 h, taking out, drying at 70-90 ℃, and flatly placing in a hydrothermal reaction kettle with the surface with the film facing upwards; adding hexamethylene tetramine into 10-50 mmol/L zinc nitrate hexahydrate aqueous solution, stirring to dissolve, then adding polyethyleneimine, adjusting the pH to be 9-12 by ammonia water, then pouring into the hydrothermal reaction kettle, and carrying out hydrothermal growth for 10-180 min at 85-95 ℃ under a sealed condition to obtain the zinc oxide nanorod array.
2. The method for regulating and controlling the growth of the zinc oxide nanorod array based on the two-dimensional colloidal single-layer film according to claim 1, which is characterized in that: in the step (1), a mixed solution of water and ethanol in a volume ratio of 1: 1-5: 1 is used as a solvent to prepare the core-shell type poly (styrene-N-Isopropyl acrylamide) @ polyacrylic acid is prepared into suspension with the mass percentage of 3 percent to 6 percent.
3. The method for regulating and controlling the growth of the zinc oxide nanorod array based on the two-dimensional colloidal single-layer film according to claim 1, which is characterized in that: in the step (1), the glass sheet is inserted into 0.03-0.05 mmol/L sodium dodecyl sulfate aqueous solution at an angle of 30-60 degrees with respect to the liquid surface, and the obtained suspension is dripped onto the glass sheet to be dispersed on a gas-liquid interface along the glass sheet to form a close-packed two-dimensional colloid single-layer film.
4. The method for regulating and controlling the growth of the zinc oxide nanorod array based on the two-dimensional colloidal single-layer film according to claim 1, which is characterized in that: in the step (1), the hydrophilic substrate is any one of a silicon wafer, a quartz wafer, ITO conductive glass and FTO conductive glass which are treated by a mixed solution of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 7: 3.
5. The method for regulating and controlling the growth of the zinc oxide nanorod array based on the two-dimensional colloidal single-layer film according to claim 1, which is characterized in that: in the step (2), the hydrophilic base material with the two-dimensional colloid single-layer film arranged on the surface is soaked in 10-15 mmol/L zinc acetate dihydrate ethanol solution for 5 hours, then taken out and dried at 90 ℃.
6. The method for regulating and controlling the growth of the zinc oxide nanorod array based on the two-dimensional colloidal single-layer film according to claim 1, which is characterized in that: in the step (2), the hexamethylene tetramine is added into 20-30 mmol/L zinc nitrate hexahydrate aqueous solution, the mixture is stirred and dissolved, then the polyethyleneimine is added, and ammonia water is used for adjusting the pH to be 10-11.
7. The method for regulating and controlling the growth of the zinc oxide nanorod array based on the two-dimensional colloidal single-layer film according to claim 1, which is characterized in that: in the step (2), the molar ratio of the zinc nitrate hexahydrate to the hexamethylene tetramine and the polyethyleneimine is 1: 1-1.2: 0.1-0.2.
8. The method for regulating and controlling the growth of the zinc oxide nanorod array based on the two-dimensional colloidal single-layer film according to claim 7, characterized in that: in the step (2), the number average molecular weight of the polyethyleneimine is 10000-30000.
9. The method for regulating and controlling the growth of the zinc oxide nanorod array based on the two-dimensional colloidal single-layer film according to claim 1, which is characterized in that: in the step (2), carrying out hydrothermal growth for 30-120 min at 90 ℃ under a sealed condition.
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