Improved adhesion between base material and elastic layer

Abstract

An embodiment relates to improving adhesion between a base substrate and an elastic material layer. Plasma enhanced chemical vapor deposition (PECVD) is performed to deposit a silicide layer on the base substrate. An elastic material layer is formed on the surface of the silicide layer. An object formed by the method can include a base substrate, a silicide layer on the base substrate, and an elastic material layer on the surface of the silicide layer. By having the silicide layer with a certain surface roughness and thickness, the adhesion between the base substrate and the elastic material layer can be significantly improved.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Utility Patent Application No. 17 / 718,674, filed April 12, 2022, which is incorporated by reference in its entirety.

[0002] The present disclosure relates to a silicon compound layer that improves adhesion between a base substrate and an elastic material layer. [Background technology]

[0003] The object having a base substrate bonded to an elastic material layer has high utility and is widely used in various applications. The base substrate can be made of glass, metal, plastic, etc. In particular, the object having a base substrate bonded to a silicone rubber layer as an elastic material can be used in, for example, household products, automobile parts, and electronic parts, baby bottles, goggles, and bathroom products that require heat resistance and / or transparency and chemical safety. Summary of the Invention [Problem to be solved by the invention]

[0004] Typically, the elastic material is bonded to the base substrate by enhancing the adhesive properties of the silicone rubber layer, applying a primer to the surface of the base substrate, and attaching the cured silicone rubber and the base substrate with an adhesive. However, enhancing the adhesive properties of the silicone rubber layer is often achieved by adding highly reactive materials (e.g., carbon functional silanes) that cause poor heat resistance and distortion of the object. Moreover, the reactive materials can also adhere to the mold itself during injection molding, making it difficult to control the quality of the molding process.

[0005] In addition, applying a primer to the surface of the base substrate requires a complicated process of applying, drying, and baking the primer, which may cause defects due to uneven application of the primer. Although there are other methods for improving the adhesive properties of the base substrate (e.g., ultraviolet irradiation, plasma treatment, and corona treatment), these other methods often do not sufficiently improve the adhesive properties to the base material and require hazardous working environments and expensive equipment. Moreover, bonding the silicone rubber layer to the base material with an adhesive can also be difficult, since the adhesive usually has poor heat resistance or durability and can be damaged in the manufacturing process. [Means for solving the problem]

[0006] The present embodiment relates to an article of manufacture comprising a base substrate, a silicon compound layer on the base substrate, and a resilient material layer on the surface of the silicon compound layer, the silicon compound layer having a surface roughness in Ra units of 50 nm to 600 nm.

[0007] In one or more embodiments, the thickness of the silicide layer is less than 1000 nm but greater than 50 nm.

[0008] In one or more embodiments, the silicide layer is SiO x C y H z It is a layer.

[0009] In one or more embodiments, SiO x C y H z The layer contains 28-30 wt% silicon, 60-65 wt% oxygen, 0-1 wt% carbon and 6-9 wt% hydrogen.

[0010] In one or more embodiments, the base substrate comprises at least one of a thermoplastic polymer, a thermoset polymer, a silicone rubber, a metal, and a glass.

[0011] In one or more embodiments, the thermoplastic polymer is at least one of polypropylene (PP), polyestersulfone (PES), polyphenylsulfone (PPSU), polyamide (PA), tritan, polycarbonate (PC), and nylon.

[0012] In one or more embodiments, the elastic material layer is a material selected from the group consisting of liquid silicone rubber (LSR), heat cured rubber (HCR) silicone, and combinations thereof.

[0013] In one or more embodiments, the base substrate is PPSU and the elastic material layer is silicone rubber.

[0014] In one or more embodiments, the silicide layer is deposited on the base substrate using plasma enhanced chemical vapor deposition (PECVD).

[0015] In one or more embodiments, PECVD is performed by reacting the precursor hexamethyldisiloxane (HMDSO) with the reactive gas oxygen (O2) under plasma.

[0016] Embodiments also relate to a method of manufacturing an article of manufacture. Plasma enhanced chemical vapor deposition (PECVD) is performed to deposit a silicide layer on a base substrate of the article of manufacture. A layer of elastic material is formed on a surface of the silicide layer.

[0017] In one or more embodiments, the thickness of the silicide layer is less than 1000 nm but greater than 50 nm.

[0018] In one or more embodiments, the surface roughness of the silicide layer is between 50 nm and 600 nm in Ra units.

[0019] In one or more embodiments, the silicide layer is SiO x C y H z It is a layer.

[0020] In one or more embodiments, SiO x C y H z The layer contains 28-30 wt% silicon, 60-65 wt% oxygen, 0-1 wt% carbon and 6-9 wt% hydrogen.

[0021] In one or more embodiments, the base substrate comprises at least one of a thermoplastic polymer, a thermoset polymer, a silicone rubber, a metal, and a glass.

[0022] In one or more embodiments, the thermoplastic polymer is at least one of polypropylene (PP), polyestersulfone (PES), polyphenylsulfone (PPSU), polyamide (PA), Tritan, polycarbonate (PC), and nylon.

[0023] In one or more embodiments, the elastic material layer is a material selected from the group consisting of liquid silicone rubber (LSR), heat cured rubber (HCR) silicone, and combinations thereof.

[0024] In one or more embodiments, the base substrate is PPSU and the elastic material layer is silicone rubber.

[0025] In one or more embodiments, performing PECVD includes reacting the precursor hexamethyldisiloxane (HMDSO) with the reactive gas oxygen (O2) under plasma.

[0026] In one or more embodiments, forming the elastic material layer includes injecting a liquid elastic material into a mold containing a base substrate onto which the elastic material layer will be deposited. [Brief description of the drawings]

[0027] [Figure 1] 1 is a flow chart illustrating a method of bonding a layer of elastic material to a base substrate according to one embodiment. [Diagram 2]1 shows the structure of a base substrate, a silicon compound layer, and an elastic material layer according to one embodiment. [Diagram 3] 2 is a schematic diagram showing a cross-sectional view taken across the surface of a polymeric material substrate without a silicon compound layer deposited thereon, according to a comparative example; [Figure 4A] 1A-1D are cross-sectional views taken across a surface of a polymeric material substrate having a silicon compound layer, each having a thickness below a threshold level and a roughness below a threshold level, according to some embodiments. [Figure 4B] 1A-1D are cross-sectional views taken across a surface of a polymeric material substrate having a silicon compound layer, each having a thickness below a threshold level and a roughness below a threshold level, according to some embodiments. [Figure 4C] 1A-1D are cross-sectional views taken across a surface of a polymeric material substrate having a silicon compound layer, each having a thickness below a threshold level and a roughness below a threshold level, according to some embodiments. [Figure 5A] 1A-1D are cross-sectional views taken across a surface of a polymeric material substrate having silicon compound layers, each having a thickness below a threshold and a roughness within a threshold range, according to some embodiments. [Figure 5B] 1A-1D are cross-sectional views taken across a surface of a polymeric material substrate having silicon compound layers, each having a thickness below a threshold and a roughness within a threshold range, according to some embodiments. [Figure 5C] 1A-1D are cross-sectional views taken across a surface of a polymeric material substrate having silicon compound layers, each having a thickness below a threshold and a roughness within a threshold range, according to some embodiments. [Figure 6] FIG. 2 is a cross-sectional view taken across a surface of a polymeric material substrate having a silicon compound layer of thickness above a threshold and roughness within a threshold range, according to one embodiment. [Figure 7] FIG. 2 is a cross-sectional view taken across a surface of a polymeric material substrate having a silicon compound layer of thickness below a threshold and roughness above a threshold range according to one embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0028] Hereinafter, the embodiments will be described with reference to the accompanying drawings. However, the principles disclosed herein may be embodied in many different forms and should not be construed as being limited to the embodiments described herein. In this description, details of well-known features and techniques may be omitted to avoid unnecessarily obscuring the features of the embodiments. In the drawings, similar reference numerals in the drawings refer to similar elements. The shape, size, area, etc. of the figures may be exaggerated for clarity.

[0029] The embodiments relate to an article of manufacture having a base substrate bonded to an elastic material layer and a method of manufacturing such an article. A silicon compound layer with a predefined degree of surface roughness is deposited on the base substrate, and an elastic material layer is disposed on the silicon compound layer to enhance adhesion between the base substrate and the elastic material layer. A silicon compound layer with an average thickness of less than 1000 nm and a surface roughness of 50 nm to 600 nm in Ra units can be deposited using a plasma enhanced chemical vapor deposition (PECVD) method. Such articles of manufacture can be used as high heat resistant parts (e.g., automotive parts and electronic parts) or transparent and chemically safe parts (e.g., baby bottles, goggles and bath products).

[0030] Method for bonding an elastic layer to a base substrate 1 is a flow chart illustrating a method of bonding an elastic material layer to a base substrate according to one embodiment. The following embodiment is described with reference to using a silicone rubber layer as the elastic material layer, but is not limited thereto, and various materials can be used as the elastic material layer.

[0031] First, at 102, a base substrate is prepared for the object. The base substrate may be formed from at least one of thermoplastic polymers, thermosetting polymers, silicone rubber, metals such as stainless steel, aluminum, gold, silver, copper, iron, inorganic materials such as aluminum oxide, titanium oxide, and glass. In particular, when the base substrate comprises a thermoplastic polymer, the base substrate may be formed from at least one of polypropylene (PP), polyestersulfone (PES), polyphenylsulfone (PPSU), polyamide (PA), tritan, polycarbonate (PC), and nylon. These thermoplastic polymers have high heat resistance and impact resistance. Therefore, a base substrate comprising a thermoplastic polymer may be advantageous for applications such as medical devices, baby products, kitchen products, etc., which require repeated disinfection by high temperature and water vapor.

[0032] A deposition method is then performed at 104 to deposit a silicide layer on the base substrate. The silicide layer is primarily silicon dioxide, SiO x C y H z In particular, it may be a layer of SiO x C y H z The layer has an average thickness of less than 1000 nm and a surface roughness in Ra units of 50 nm to 600 nm. Ra means the arithmetic mean of the absolute values ​​of the profile height deviations from the mean line of the surface of the layer. SiO x C y H z The surface roughness and thickness ranges were determined based on experiments described in detail below with reference to FIGS.

[0033] A silicon compound layer (e.g., SiO x C y H zThe surface roughness of the layer (layer) can be measured, for example, as described in Ichiko Misuzu et al., “Profile Surface Roughness Measurement Using Metrological Atomic Force Microscope and Uncertainty Evaluation,” 11 th This can be measured using atomic force microscopy (AFM) as described in Laser Metrology for Precision Measurement and Inspection in Industry 2014 (September 2-5, 2014). The surface roughness of the examples described below with reference to Figures 3-7 was measured using the same method.

[0034] A silicon compound layer (e.g., SiO x C y H z The thickness of the silicide layer can be determined by analyzing scanning electron microscope (SEM) images. First, the surface of the substrate, with or without silicide, is pretreated with a platinum coating to prevent any damage to the silicide layer. The pretreated surface is then treated with a focused ion beam (FIB). A cross-section of the FIB-treated surface is then taken with the SEM. The pixels of the taken image are then analyzed to determine the thickness at multiple points of the image. The average value of the thickness at multiple points is taken as the thickness of the silicide layer.

[0035] In one embodiment, the silicide layer having a surface roughness is achieved by performing plasma enhanced chemical vapor deposition (PECVD) to deposit the silicide layer. As an example, the PECVD process may be performed at relatively low temperature and pressure conditions to obtain the desired surface roughness of the silicide layer on the base substrate. The pressure of the PECVD process may be 1×10 -2The pressure may be 1 Torr or less, and the temperature of the base substrate during at least a portion or the entire PECVD process may be 50° C. to 200° C. A Si-containing precursor gas and a reactive gas may be used in the PECVD process. The Si-containing precursor is hexamethyldisiloxane (HMDSO) and the reactive gas is oxygen (O2).

[0036] The silicide layer formed by such a PECVD process is SiO x C y H z In one or more embodiments, the silicon, oxygen, carbon, and hydrogen ratios are in the ranges of 28-30 wt%, 60-65 wt%, 0-1 wt%, and 6-9 wt%, respectively. The composition of the silicide layer can be determined, for example, using Rutherford Backscattering Spectrometry (RBS) Elastic Recoil Detection (ERD) techniques, as is well known in the art.

[0037] Returning to Figure 1, at 106 an elastic material layer is formed on the surface of the silicon compound layer. In particular, the elastic material layer can be formed by applying an elastic material onto the surface of the silicon compound layer having a surface roughness within a threshold range. The effect is to improve adhesion between the base substrate and the resulting elastic material layer. The elastic material can be LSR, HCR, or a combination thereof.

[0038] In one embodiment, the elastic material is applied to a base substrate having a silicon compound layer by placing or clamping the object comprising the base substrate and the silicon compound layer into a mold of an injection molding machine and filling the mold of the injection machine with the elastic material to apply the elastic material to the surface of the silicon compound layer.

[0039] In one embodiment, a plasma treatment is performed on the surface of the base substrate prior to depositing the silicide layer, which reduces contaminants or other particles on the base substrate, resulting in improved adhesion between the base substrate and the silicide layer that is deposited thereon.

[0040] Furthermore, an ionization process may be performed on the surface of the silicide layer prior to forming the elastic material layer. Although the relatively high surface roughness of the silicide layer improves the physical and mechanical adhesion with the elastic material layer, performing an ionization process can further improve the adhesion by increasing the surface energy of the surface of the silicide layer.

[0041] composite structure 2 shows a composite structure 100 according to one embodiment, comprising a base substrate 110, a silicon compound layer 130, and an elastic material layer 120. The following composite structure 100 may form part or the entirety of an article and may be obtained by carrying out the steps detailed in connection with FIG.

[0042] Base substrate 110 forms the base material for composite structure 100 and may be formed from the materials and properties described in connection with step 102 of the method shown in Figure 1. Elastic material layer 120 provides texture and impact resistance to the object formed with composite structure 100 and may be formed from the materials and properties described in connection with forming elastic material layer 106 described above in connection with Figure 1.

[0043] The silicon compound layer 130 is formed between the base substrate 110 and the elastic material layer 120 and is formed from materials and properties described in connection with step 104 of the method illustrated in FIG. 1. In particular, the surface of the silicon compound layer 130 in contact with the elastic material layer 120 may have a surface roughness within a threshold range to improve bonding of the elastic material layer 120 to the base substrate 110. The silicon compound layer 130 may also have an average thickness less than a threshold value. In one example, the base substrate 110 may be formed of PPSU and the elastic material layer 120 may be formed of silicone rubber, while the silicon compound layer 130 may have a surface roughness within 50 nm to 600 nm and an average thickness less than 1000 nm but greater than 50 nm.

[0044] Experimental Results In the following examples, SiO x C y H z The silicone adhesion to a PPSU baby bottle container was tested using a layer. In the example, an ionization procedure was performed to activate the surface of the PPSU, and then SiO x C y H z To form the layer, a PECVD process was used that required HMDSO as the Si-containing precursor and O2 as the reactive gas. Then, SiO x C y H z After the PPSU substrate in the form of a baby bottle with layers is placed in the mold of an injection molding machine, the mold is filled with LSR silicone. The PPSU substrate with LSR silicone is then cooled to cure the silicone. x C y H z After attaching the silicone to the PPSU via the layer, the baby bottles were immersed in boiling water at 2 atmospheres of pressure for a predetermined amount of time to determine if the bond between the PPSU and silicone would be maintained. A separate adhesive was used to attach the silicone to the PPSU substrate, SiO x C y H z Nothing was placed between the layer and the silicone.

[0045] FIG. 3 is a graph showing a comparative example of SiO x C y H z 1 is a scanning electron microscope (SEM) image of a cross section taken across the surface of an uncoated PPSU substrate and a silicone. x C y H z The layer thickness was zero and the roughness of the PPSU substrate was less than 5 nm (Ra). x C y H z Without the layer, the silicone separated from the PPSU even before being immersed in boiling water.

[0046] 4A-4C show SiO 2 films with roughness below a threshold level according to some embodiments. x C y H z 1 is a SEM image of a cross-section taken across the surface of a PPSU substrate having a layer of SiO x C y H z The roughness of the layer was less than 50 nm (Ra). x C y H z The average layer thickness is 42.8 nm, and the SiO x C y H z FIG. 4B is a SEM image of a PPSU substrate with a layer roughness of 0.26 nm (Ra). x C y H z The layer thickness is 197 nm, and the SiO x C y H z 1 is a SEM image of a PPSU substrate with a layer roughness of 11.15 nm (Ra). x C y H z Three separate cycles of PECVD were performed to obtain a SiO x C y H z The layer thickness is 721 nm, and the SiO x C y H z4A-4C are SEM images of a PPSU substrate where the layer roughness was 25.64 nm (Ra). In the examples of FIGS. 4A-4C, the silicone initially adhered to the PPSU substrate, but then separated when the substrate and silicone were immersed in boiling water for 30 hours. Thus, these examples show that the SiO x C y H z If the layer roughness is lower than 50 nm (Ra), SiO x C y H z Even layer thicknesses below 1000 nm indicate that the silicone was not properly attached to the substrate.

[0047] 5A-5C are schematic diagrams illustrating SiO 2 films with roughness within a range according to some embodiments. x C y H z 1 is a SEM image of a cross-section taken across the surface of a PPSU substrate having a layer of SiO x C y H z The roughness of the layer was 50 nm (Ra) or more, but less than 600 nm (Ra). x C y H z The average layer thickness is 127.3 nm, and the SiO x C y H z FIG. 5B is an SEM image of a PPSU substrate with a layer roughness of 56.85 nm (Ra). x C y H z The average layer thickness is 263.1 nm, and the SiO x C y H z FIG. 5C is an SEM image of a PPSU substrate with a layer roughness of 203.4 nm (Ra). x C y H z The average layer thickness is 400.7 nm, and the SiO x C y H z5A-5C are SEM images of a PPSU substrate where the layer roughness was 454 nm (Ra). In the examples of FIGS. 5A-5C, the silicone was attached to the PPSU substrate and remained attached to the substrate even after the substrate and silicone were immersed in boiling water for 50 hours. Thus, these examples show that the SiO x C y H z The roughness of the layer is in the threshold range of 50 nm (Ra) to 600 nm (Ra), and the SiO x C y H z An average layer thickness of less than 1000 nm indicates that the silicone was properly attached to the substrate.

[0048] FIG. 6 is a schematic diagram of a SiO x C y H z The roughness of the layer is within the threshold range, but the SiO x C y H z 1 is a SEM image of a cross section taken across the surface of a PPSU substrate where the average thickness of the layer exceeds a threshold level. x C y H z The average thickness of the layer is 1,207.9 nm, and the SiO x C y H z The roughness of the layer was 224.1 nm (Ra). In this example, the silicone was initially attached to a PPSU substrate, but separated from the substrate after immersion in boiling water for 30 hours. This example was performed using SiO x C y H z Layer thicknesses greater than 1000 nm indicate that the silicone does not attach properly to the substrate.

[0049] 7 is a cross-sectional view taken across the surface of a PPSU substrate having a silicide layer with a thickness below a threshold level and a roughness above a threshold range, according to one embodiment. x C y H z The layer thickness is 256.6 nm, and the SiO x Cy H z The roughness of the layer was 732 nm (Ra). In this example, the silicone was initially attached to a PPSU substrate but separated from the substrate after immersion in boiling water for 30 hours. x C y H z When the layer roughness exceeds 600 nm (Ra), SiO x C y H z It is shown that even layer thicknesses below 1000 nm do not allow the silicone to attach properly to the substrate.

[0050] Experiments were also conducted using materials other than PPSU as the base substrate. Specifically, a lap shear test was conducted according to ASTM D1002 using two specimens, each of which was coated with a silicon compound layer (e.g., a SiOxCyHz layer). Then, LSR was applied to the silicon compound layered surface of one specimen. Then, the other specimen was overlapped on the silicon compound layered surface facing the LSR coated surface. The specimens were pressed together until the LSR reached a predetermined thickness (e.g., 1 mm), and then baked to cure the LSR into silicone. The two specimens were then pulled in opposite directions to test the fracture shear strength at the overlapping portion of the specimens.

[0051] For various materials (e.g., polycarbonate, glass, polypropylene, and stainless steel) as specimen materials, the maximum shear force before failure was measured to test the applicability of the silicon compound to these materials. The SiOxCyHz layer was deposited under similar PECVD conditions as the examples in Figures 5A-5C, and is therefore assumed to have a thickness of less than 1000 nm and a roughness in the range of 50 nm (Ra) to 600 nm (Ra). The lap shear test was performed three times for each material with and without the SiOxCyHz layer, and the average maximum sheer force was compared. The results are as follows: [Table 1]

[0052] As shown in Table 1, there was a significant increase in the maximum shear force when the SiOxCyHz layer was deposited on the sample materials. In the case of stainless steel, the increased shear force due to the deposition of the SiOxCyHz layer was approximately 691 times. Although only PPSU, polycarbonate, glass, polypropylene and stainless steel were used as basis substrate materials, similar results are expected for other materials.

[0053] Although the present disclosure has been described above with reference to several embodiments, various modifications can be made within the scope of the disclosure. Accordingly, the above disclosure is intended to be illustrative and not limiting.

Claims

1. A base material; A silicon compound layer on the base substrate, the silicon compound layer having a surface roughness of 50 nm to 600 nm in Ra units; a layer of elastic material on a surface of the silicon compound layer; A manufactured product comprising:

2. 10. The article of manufacture of claim 1, wherein the silicide layer has a thickness less than 1000 nm but greater than 50 nm.

3. The silicon compound layer is SiO ｘ C ｙ H ｚ 3. The article of manufacture of claim 2 which is a layer.

4. The SiO ｘ C ｙ H ｚ 4. The article of manufacture of claim 3, wherein the layer comprises 28-30 wt% silicon, 60-65 wt% oxygen, 0-1 wt% carbon, and 6-9 wt% hydrogen.

5. 10. The article of manufacture of claim 1, wherein the base substrate comprises at least one of a thermoplastic polymer, a thermoset polymer, a silicone rubber, a metal, and a glass.

6. 6. The article of manufacture of claim 5, wherein the thermoplastic polymer is at least one of polypropylene (PP), polyestersulfone (PES), polyphenylsulfone (PPSU), polyamide (PA), Tritan, polycarbonate (PC), and nylon.

7. 10. The article of manufacture of claim 1, wherein said resilient material layer is a material selected from the group consisting of liquid silicone rubber (LSR), heat cured rubber (HCR) silicone, and combinations thereof.

8. 14. The article of manufacture of claim 13, wherein said base substrate is PPSU and said elastic material layer is silicone rubber.

9. 10. The article of manufacture of claim 1, wherein the silicide layer is deposited on the base substrate using plasma enhanced chemical vapor deposition (PECVD).

10. The PECVD process involves the deposition of a precursor, hexamethyldisiloxane (HMDSO), in a plasma with a reactive gas, oxygen (O ２ 10. The article of manufacture of claim 9, wherein the reaction is carried out by reacting

11. depositing a silicide layer on a base substrate of the article by plasma enhanced chemical vapor deposition (PECVD); forming an elastic material layer on a surface of the silicon compound layer; The method includes:

12. The method of claim 11 , wherein the thickness of the silicide layer is less than 1000 nm but greater than 50 nm.

13. The method of claim 12, wherein the surface roughness of the silicide layer is between 50 nm and 600 nm in Ra.

14. The silicon compound layer is SiO ｘ C ｙ H ｚ The method of claim 11 , wherein the layer is a layer.

15. The SiO ｘ C ｙ H ｚ The method of claim 14, wherein the layer comprises 28-30 wt% silicon, 60-65 wt% oxygen, 0-1 wt% carbon and 6-9 wt% hydrogen.

16. The method of claim 11 , wherein the base substrate comprises at least one of a thermoplastic polymer, a thermoset polymer, a silicone rubber, a metal, and a glass.

17. 17. The method of claim 16, wherein the thermoplastic polymer is at least one of polypropylene (PP), polyestersulfone (PES), polyphenylsulfone (PPSU), polyamide (PA), Tritan, polycarbonate (PC), and nylon.

18. The method of claim 1 , wherein the elastic material layer is a material selected from the group consisting of liquid silicone rubber (LSR), heat cured rubber (HCR) silicone, and combinations thereof.

19. The method of claim 11 , wherein the base substrate is PPSU and the elastic material layer is silicone rubber.

20. To perform PECVD, the precursor hexamethyldisiloxane (HMDSO) is mixed with the reactive gas oxygen (O ２ 12. The method of claim 11 , comprising reacting with .

21. The method of claim 11 , wherein forming the elastic layer comprises injecting a liquid elastic material into a mold containing the base substrate onto which the elastic layer is deposited.

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