TW201204665A - Method of forming gradient hydrophobic surface - Google Patents

Abstract

This invention provides a method of forming a gradient hydrophobic surface, comprising: preparing an object with a plane; gradually dipping an area for hydrophobic treatment on the plane of the object into a modification solution or removing the same therefrom, wherein when any area is dipped in the modification solution, the area already dipped in the modification solution remains in the modification solution, and when the area is gradually removed from the modification solution, the area not yet left from the modification solution is provided with longer contact time with the modification solution; and obtaining the object from the modification solution. As such, by simply controlling the time during which any area of the plane is dipped into or removed from the modification solution, without having to control drip amount or spending high costs to maintain an environment for silane vapor generation, this invention can improve the drawbacks of existing methods of forming a gradient hydrophobic surface.

Description

201204665 VI. Description of the Invention: [Technical Field] The present invention relates to a method for forming a hydrophobic surface, and more particularly to a method for forming a gradient hydrophobic surface. [Prior Art] The gradient of the hydrophobic surface on the object allows the droplet to be driven thereon by a hydrophobic gradient. For example, in an earlier study, the researchers explored the thermal gradient of the Marangoni effect to create a movement of water droplets. In terms of the method of forming a gradient hydrophobic surface, Chaudhury and Whitesides (Μ. Κ. Chaudhury and GM Whitesides, Science, 1992, 256, 1539-1541) was first proposed in 1992 as a gas phase decane diffusion method such as a substrate or A gradient hydrophobic surface is formed on an object such as a test piece, and the specific method is to first maintain the plane of the substrate in a horizontal state, and then use the decane vapor volatilized by the oil droplets of the decane and the eucalyptus oil, and volatilize with the decane vapor. The distance is close, and a concentration gradient is generated in the plane of the aforementioned level, which is directly bonded to the substrate to generate a gradient of decane molecules, thereby achieving the purpose of forming a gradient hydrophobic surface on the substrate. In addition, Yu et al. (X. Yu, ZQ Wang, YG Jiang, X. Zhang, 2006, 22, 4483-4486) published a method for forming a graded hydrophobic surface on an object such as a substrate, which is placed vertically in a container. The gold substrate is gradually added to the container to gradually drop the alkyl mercaptan hydrophobic modification solution (HS(CH2)nCH3), and the modified solution in the container is gradually flooded to the substrate to perform gradient on the gold substrate. Hydrophobic modification, and then a hydroxyl group-containing alkyl mercaptan (HS(CH2)l()CH2〇H) affinity aqueous solution, bonded to the unreacted gold substrate 琍S] 3 201204665 points, reached on the gold substrate The effect of forming a gradient on the gradient of the hydrophobic surface is as described in the literature (PS Tsai, Yu. M. Yang, YL Lee, 2006, 22, 5660-5665). '100 pL of decane is dissolved in 25 mL of four-gas carbon. The modified solution contains 4000 ppmv, and after 30 minutes of reaction time, the test piece can be hydrophobically modified. The static contact angle of the droplets on the test piece is about 100°. However, the aforementioned methods of forming a gradient hydrophobic surface each have their own shortcomings to be improved.

The method of Chaudhury and Whitesides requires the use of volatile oxalate vapors and requires an environment and equipment that allows decane vapors to function effectively, thus requiring equipment costs in the south. In addition, Chaudhury and

The Whitesides method is extremely difficult to control the gradient spacing and is a major drawback. If the method of Yu et al. is used, the liquid foam will be activated from the liquid surface when the modified solution is dropped. The spraying of the liquid droplets onto the substrate will affect the surface gradient of the substrate and cause the surface gradient of the substrate to be different. On the other hand, the gradient density and precision formed by the dropping method of Yu et al. on the substrate are inevitably related to the size of the droplets dropped. When the droplets dropped are larger, the height of the liquid surface rises more every time; when the droplets dropped are smaller, the liquid level of the human body rises to a smaller extent. Therefore, when the hydrophobic gradient is formed by the method of Yu et al., if the fine density and accuracy of the gradient are sacrificed without migrating the larger droplets, a technical means capable of generating smaller droplets is required. Therefore, in order to accurately drip the solution to form a gradient hydrophobic surface, it is necessary to precisely control the amount of solution dripping, so that the method of Yu et al. is not [S] 4 201204665, it is only difficult to avoid the problem of liquid droplet splashing, and more Careful and large-scale manual work or high-cost precision mechanical equipment, and high labor costs or equipment costs will make its manufacturing costs impossible to reduce. SUMMARY OF THE INVENTION In view of the above disadvantages of the method of forming a gradient hydrophobic surface, it is an object of the present invention to provide a simple and low cost method for forming a gradient hydrophobic surface. In order to achieve the foregoing object, the technical means adopted by the present invention is that the gradient forming hydrophobic surface forming method comprises: having an object having a plane having an exposed hydroxyl group, and defining a plurality of regions on the plane; The stepwise unidirectional movement of the object relative to the -modification solution causes the plurality of regions on the plane of the object to continuously increase and decrease the contact time with the modifying solution. wherein the modifying solution comprises a solvent selected from the group consisting of chloroform, methanol and toluene. And the organic solvent in a group and the stone dissolved in the organic solvent; ^ the modified solution obtains the foregoing object, wherein each region on the plane of the object is sequentially increased in contact with the modified solution or Decreasing and weakening or weakening, so that the plane of the aforementioned object forms a gradient hydrophobic surface. The gradient of the hydrophobic surface formed by the month of the month adopts the above-mentioned + step, so it is only necessary to control the time of each area of the plane to be immersed in the reforming solution without controlling the solution to drip into the stalker~ without spending a high cost to maintain矽 矽 发生 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Low 201204665 [Embodiment] The present invention provides a method of forming a gradient hydrophobic surface, comprising the following first step to third step. The first step is to have a planar object having an exposed hydroxyl group and defining a plurality of regions on the plane for hydrophobic treatment. Preferably, the object is a substrate made of a glass material such as titanium dioxide (TiTi or barium titanate). However, the object forming the gradient hydrophobic surface by the present invention is not limited to the substrate, and is not limited thereto. The sheet can be implemented in accordance with the requirements for objects of different shapes and shapes without escaping the invention. Further, the technique of making the aforementioned plane have an exposed hydroxyl group belongs to a known technique. Specific common technical means for having an exposed hydroxyl group include cleaning the plane, and performing acid treatment on the plane, and preparing an acidic cleaning solution by using distilled water, a glass sub-cleaning liquid, an equal proportion of sterol and concentrated hydrochloric acid. Further, it is combined with ultrasonic vibration for cleaning and acid treatment. Other feasible means of well-known technology are not described here. • The second step is to gradually move the aforementioned object relative to a modified solution in a unidirectional manner. The plurality of regions are continuously increased or decreased in contact with the aforementioned modified solution, and the modified solution comprises a selected from the group consisting of four gasified carbons. An organic solvent of a group of gas imitation, methanol and toluene and a decane dissolved in the organic solvent. Preferably, the decane concentration of the aforementioned modifying solution is 10-4000 ppmv. The aforementioned so-called modification of the aforementioned object relative to a modification The stepwise unidirectional movement of the solution may be such that the object moves unidirectionally toward the modified solution, so that the plurality of regions are immersed one by one into the modified solution; or may be a plurality of regions of the shilling pre-Si 6 201204665 All are immersed in the front eo ^ L ± 』 extend the modified solution, and then move the object toward the direction away from the modified solution, so that the above multiple areas leave the modified solution one by one. The self-modifying solution obtains the foregoing object, and the regions on the plane of the object for hydrophobic treatment are sequentially connected to (4) (4) hydrophobicity, and the plane of the object is formed as a gradient hydrophobic surface. 4〇〇ppmv, The contact time can be made, that is, the modified solution, when the decane concentration of the modified solution is the longest contact in the region of the touch-modified solution

The total reaction time is 5-20 minutes. When the concentration of decane in the modified solution is 30 ppmv, the longest contact time in the area contacting the modified solution can be 1:1 minute. The following description of the specific embodiment of the present invention will be described. It should be noted that the embodiments are intended to illustrate the technical features of the present invention and are not intended to limit the scope of the present invention. [Embodiment 1] The present embodiment relates to the preparation of an object having a plane such that the plane has an exposed hydroxyl group to facilitate formation of a graded hydrophobic surface on the plane. . Referring to Figure 1, the object used in this example is a test piece. The test piece has a flat surface. Nine areas are planned in this plane. The uppermost area of the nine areas is used as the take-up area. The take-up zone does not participate in the formation of a gradient hydrophobic surface. The remaining 8 areas will be treated hydrophobically and identified as A to H areas from top to bottom. The test piece used in this embodiment has a predetermined thickness, and its specification is 5 〇 mm X mm. The upper take-up area includes an area from the upper end, that is, an area of 1 〇 mm X 24 mm. The f $] 7 201204665 40mm from the take-up area is drawn from the aforementioned A area to each of the 8 areas and has an area of 5 mm X 24 mm. In this embodiment, one of the aforementioned test pieces and the acid solution are treated by the following steps, so that the plane has an exposed hydroxyl group. Into the cleaning a, will clean the glass instrument special cleaning agent to: 3 〇 3 times steaming money to prepare for use. The above-mentioned cleaning surface instrument-specific clearing is generally known in the art to which the present invention pertains, and belongs to the route. General business

b. After taking a volume of methanol, an equal volume of concentrated hydrochloric acid is placed to prepare an acidic cleaning solution for use. c. First put the 3〇mL straight glass containing the glass test piece into the above prepared detergent, and then use the ultrasonic wave to shake the money for iq minutes, then rinse it with distilled water for 5~6 times. d. Take the glass test piece with the tweezers and place it in the above-mentioned cleaned glass cup and then fill the glass cleaner, and shake it with the ultrasonic oscillating machine for 2 minutes, directly pour off the cleaning agent (no more auxiliary, and can be recycled and cleaned) The agent is used to clean the glass for the next time) and then rinsed with distilled water for 5 to 6 times. e. Next, add the sterol concentrated hydrochloric acid acidic cleaning solution configured in step b, and shake for 20 minutes, then pour off the acid solution and rinse with distilled water for 5 to 6 times. If a large number of test pieces are processed in batches, and the test pieces subjected to the above cleaning and acid treatment are to be sealed for later use, after the above washing steps are completed, the distilled water is directly filled and sealed with a wax film. That is, the purpose of sealing the clean test piece is achieved. [Example 2] This example relates to the preparation of a modified solution. 8 201204665 This example uses the following steps to prepare a modified solution. a. Cleaning the vessel; specifically, taking a serum bottle that can be sealed by a screw cap. Use a cleaning agent to oscillate with a ultrasonic oscillating machine for 10 minutes. After the shaking, it is washed with distilled water and sent to an oven for drying. b. Take a 250mL beaker and a 100mL measuring cylinder and rinse with an organic solvent. Pour an appropriate amount of organic solvent into the beaker, and then pour 10〇mL into the above-mentioned washed serum bottle. Preferably, the organic solvent is gas, sterol or toluene.

〇, 40 decane was extracted with a micropipette, quickly placed in the organic solvent of the above serum bottle and capped, and uniformly mixed to complete the preparation of the modified solution of 4 矽 / / lOOmL organic solvent (400 ppmv). According to the above method, the modified solution of the desired concentration can be prepared by the amount of decane taken. That is, a modified solution having 30 ppm of decane can be obtained by using the above method, and a modified solution having 4 〇〇〇 ppmv of decane can be obtained by using 400 μm of decane according to the above method. [Embodiment 3] This embodiment exemplifies that the crucible region for the hydrophobic treatment on the plane of the test piece is immersed in the modified solution, and the crucible region to the G region for the hydrophobic treatment on the plane of the test piece is made one by one. The specific embodiment of the above modified solution is sequentially immersed. For the purpose of the present invention, the specific means for controlling the immersion of the test piece into the modified medium is not limited to the use of human control or mechanical control. The exemplified in this embodiment employs a programmable robotic arm. First, set the robot arm program to immerse the test piece in the modified solution for 5 minutes and then immerse it for 5 minutes. Then repeat the operation for two more times until the test piece is immersed for 8 times. Μ 201204665 That is, the test piece is finished and the test piece is moved to the above organic solvent for 6 times to wash the solution for 8 different reaction times. Since the argon-immersed solution is immersed in the modified solution, the H region, that is, the region where the modified solution is first immersed, is immersed in the immersion solution, and is modified/introduced/ The time of the liquid is the sum of the time accumulated in the area from the Α area to the Η area. Change the ten-time change. The immersion time of the area where the first change into the modified solution is the total reaction time.

By analogy, the time set by the G area is the sum of the time accumulated from the Α area to the g area, and the time set by the area is the sum of the time accumulated from the A area to the F area, and the remaining A area to the e area is also . Since the known technique has a robot arm control precision of at least 0.1 mm' and the test piece is immersed downward without splashing, it is possible to improve the problems of the prior art. [Embodiment 4] & The present embodiment does not measure the hydrophobicity, that is, the X of the droplet is measured on the test piece, and the droplet is dripped in the region of the test piece, and the static contact angle measuring instrument is used. Make measurements. The static contact angle measuring instrument used in the present embodiment and the subsequent embodiments is ΡΧ6(7), Franee. In the embodiment of the two bodies, water droplets of 2.0 μΐ^ are respectively collected in the area of the test piece, and the contact angle balance time is taken for 5 seconds, and then measured and photographed. [Example 5] △ This example exemplifies a total reaction time of 5, 10, 15, and 20 minutes. The sample solution used in the present embodiment is a solution of the modified solution in the form of an organic solvent, and has a concentration of 400. Phenol of ppmv. 10 201204665 As shown in Table 1 below, if the immersion time of the first immersion in the modified solution is 20 minutes, the immersed area with the shortest immersion time is only immersed in the modified solution for 50 seconds. The contact angle of the A region in which the aforementioned immersion time is only 150 seconds has reached 103 °. It can be seen from Table 1 that when the immersion time of the A region of the test piece is 112.5 seconds, 75 seconds, and 37.5 seconds by the modification solution of 400 ppmv, the contact angle of the A region is also as high as 89, respectively. °, 104°, and 93 ° [Table 1] Concentration 400 ppmv Time 5min lOmin 15min 20min Area Time Ave Time Ave Time Ave Time Ave A 37.5 93 75 104 112.5 89 150 103 B 75.0 97 150 105 225 86 300 103 C 112.5 95 225 100 337.5 85 450 101 D 150.0 92 300 103 450 93 600 89 E 187.5 94 375 106 562.5 93 750 92 F 225.0 94 450 104 675 79 900 101 G 262.5 89 525 104 787.5 80 1050 90 Η 300.0 82 600 101 900 85 1200 98 [Example 6] This example illustrates an embodiment in which the total reaction time is 1 minute and 8 minutes. The reforming solution used in this example was prepared by using terpene as an organic solvent and immersing in a concentration of 30 ppmv. As shown in Table 2 below, if the total reaction time is 8 minutes, and the time for immersing the modified solution in different regions is changed from 60 seconds to 480 seconds, the contact angles of the modified regions are distributed at 76 ° to 96 °; The total reaction time is 1 minute and the time for immersing the modified solution in different regions is from 7.5 seconds to 60 seconds. The contact angle of each region is distributed from 5 Γ to 84 °; if the total reaction time is 1 minute, the immersion in different regions is changed. The time of the solution is gradually changed from 7.5 seconds to 480 seconds, and the contact angle of each region is distributed between 51 ° and 96 °. [ s] 11 201204665

[Table 2] Concentration 30 ppmv Time 8min lmin ~~ Area Time Ave Time Ave A 60 76 7.5 51 B 120 82 15 56 C 180 85 22.5 — 1 One 66 D 240 95 r 3〇Γ 75 E 300 91 37.5 70 F 360 91 45 68 G 420 95 52.5 76 H 480 96 60 84 [Example 7] This example exemplifies a total reaction time of 1 〜 minutes to the reforming solution used in the examples: the embodiment. In this case, it is 3 〇 PPmV (4). For organic solvents, when immersed in concentrated Η &, Λ, 77 ', that is, the Η area is 〇 as the bell, the contact angle of each area of the test piece is dip ^ 59.3 〇. 64, 74.^ L" 88 · 0, 105.3° and 1〇4_0°. The data of these contact angles show that the hydrophilic glass that has not been modified is completely modified to have hydrophobicity. These generations: Τ η + the degree of contact angle change with hydrophobicity is shown in Figure 2, Di The method does form a gradient hydrophobic surface. Confirm this

i S] P2 36 60 68 75 80 30 ppmv lOmin P3 39 65 62 73 80

Ave 36i〇 59^3 64?7 743 80J Standard deviation 3.0 —6.0 3.1 1.2 06~~ 12 201204665 F 148.8 88 88 88 88.0 G 302.4 104 92 94 96.7 Η 609.6 102 107 卜 103 104.0

In addition to the embodiments exemplified in the above embodiments, those skilled in the art to which the present invention pertains may adapt to the needs, but still do not escape the scope of the invention, particularly related to, for example, a modified solution. The concentration of the organic solvent and decane, the time of immersion in the modified solution, and the like can be selected or adjusted while still being covered by the present invention.

For example, even if the four gasified carbons need to be treated for their properties, they can still use the modified solution containing 4000 ppmv decane in carbon tetrachloride, and the immersion time of 30 minutes to form the gradient hydrophobicity. surface. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1. A test piece used in an embodiment of the present invention. Figure 2. Graph of contact angle variation.

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Claims (1)

201204665 VII. Patent application scope: 1. A method for forming a gradient hydrophobic surface, comprising: (1) preparing a material having a plane having an exposed nitrogen oxide group and defining a plurality of regions on the plane; (2) The stepwise unidirectional movement of the object relative to a modified solution causes the plurality of regions on the plane of the object to continuously increase or decrease the contact time with the modified solution, wherein the modified solution comprises a solvent selected from the group consisting of chloroform, methanol, and An organic solvent of a group consisting of toluene and a decane dissolved in the organic solvent; and (3) obtaining the object, wherein each region on the plane of the object is sequentially increased or decreased by contact with the modified solution. Strong or weak hydrophobic, so that the plane of the aforementioned object is formed as a gradient hydrophobic surface. 2. The method according to the above-mentioned claim, wherein the object is gradually moved unidirectionally relative to a modified solution, so that the contact time between the plurality of regions on the plane of the object and the modified solution is continuously increased or decreased. The steps include: a) gradually moving the object toward the reforming solution in a unidirectional manner so that a region on the plane of the object is immersed in the modifying solution; and b) immersing other regions on the plane of the object one by one in the foregoing When the solution is modified, and any region is immersed in the modified solution, the region immersed in the modified solution is continuously immersed in the modified solution; the self-modifying solution acquires the object, and the regions on the plane of the object are sequentially The length of the solution is changed to be strong and weak, so that the plane of the object is formed as a gradient hydrophobic surface. 3. If the method described in claim 1 is applied, the aforementioned method [s] 201204665 is gradually moved in one direction relative to the -modified solution, so that the contact time between the domain of the object and the modified solution is continuously increased or decreased. Step a) to make all the areas on the plane of the aforementioned object and - to return to the modified solution; b) to gradually move the aforementioned object away from the direction of the modified solution to make the area of the object in the plane one by one庠 said that Jin left the aforementioned modified solution When the liquid 'and any-region leaves the modified solution, the region that has not left the modified solution is continuously immersed in the modified solution; °° 'sequentially obtained by immersing in the planar shape of the modified object Each zone on the plane has a long and short solution and is strong and weak hydrophobic, thus becoming a gradient hydrophobic surface. 4. The method of claim 2, wherein the modified solution has a crushing concentration of 10-4000 ppmv. 5. The method of claim 3, wherein the decane concentration of the modified solution is 10-4000 ppmv 0 6. The method of the fourth modification of the patent application, the tempering solution of the modified solution The agronomy is 400 ppmv, and the immersion time of the first immersion in the modified solution area is 5-20 minutes. 7. The method according to item 4 of the patent application scope, wherein the grading time of the first immersion in the region of the modified solution is 1-3 ppm, and the immersion time of the first immersion in the region of the modified solution is 1:1 minute, According to the method of claim 5, the agronomic degree of the above-mentioned modified solution is 4 〇〇 ppmv, and the immersion time of the region of the first manning solution is 5-20 minutes. i 15 201204665 9. The method according to claim 5, wherein the modification is performed at 30 ppmv, and the immersion time of the first immersion in the region of the modified solution is 1 to 10 minutes. 10. The method according to any one of claims 1 to 9, wherein the object is made of a glass material, wherein the glass material is selected from the group consisting of titanium oxide and barium titanate. Eight, schema: (such as the next page) 16