CN115193667A - Anti-scaling copper shell and preparation method thereof - Google Patents
Anti-scaling copper shell and preparation method thereof Download PDFInfo
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- CN115193667A CN115193667A CN202210542366.6A CN202210542366A CN115193667A CN 115193667 A CN115193667 A CN 115193667A CN 202210542366 A CN202210542366 A CN 202210542366A CN 115193667 A CN115193667 A CN 115193667A
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- 239000010949 copper Substances 0.000 title claims abstract description 91
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 78
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002033 PVDF binder Substances 0.000 claims abstract description 74
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 73
- 238000005468 ion implantation Methods 0.000 claims abstract description 35
- 238000000576 coating method Methods 0.000 claims abstract description 31
- 239000011248 coating agent Substances 0.000 claims abstract description 26
- 150000002500 ions Chemical class 0.000 claims abstract description 25
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000000956 alloy Substances 0.000 claims abstract description 10
- 229910000990 Ni alloy Inorganic materials 0.000 claims abstract description 9
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 10
- 239000012188 paraffin wax Substances 0.000 claims description 10
- 238000005498 polishing Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000002513 implantation Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 2
- 230000008021 deposition Effects 0.000 abstract description 5
- 239000007769 metal material Substances 0.000 abstract description 2
- 238000002347 injection Methods 0.000 abstract 1
- 239000007924 injection Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 21
- 238000012360 testing method Methods 0.000 description 19
- 238000012546 transfer Methods 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 244000137852 Petrea volubilis Species 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910003460 diamond Inorganic materials 0.000 description 4
- 239000010432 diamond Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 description 3
- 239000012264 purified product Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 1
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 description 1
- 235000014824 magnesium bicarbonate Nutrition 0.000 description 1
- 239000002370 magnesium bicarbonate Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
- B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/002—Pretreatement
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/48—Ion implantation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2506/00—Halogenated polymers
- B05D2506/10—Fluorinated polymers
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Abstract
The invention relates to the technical field of metal materials, in particular to an anti-scaling copper shell and a preparation method thereof. The anti-scaling copper shell is made of a Cu/Ni/Ti alloy material, the anti-scaling copper shell is subjected to ion injection treatment, and the surface of the anti-scaling copper shell contains a modified PVDF coating; wherein the modified PVDF coating is prepared by the reaction of PVDF and dodecafluoroheptyl methacrylate (DFMA); in the Cu/Ni/Ti alloy material, the mass ratio of Cu to Ni to Ti is (40-60) to (20-30) to (10-20); the ion for the ion implantation treatment is one or more selected from Cr, F, C and N ions. The anti-scaling copper shell prepared by the invention has extremely low surface energy, inhibits the deposition of scale, plays a good anti-scaling role and has good application prospect.
Description
Technical Field
The invention relates to the technical field of metal materials, in particular to an anti-scaling copper shell and a preparation method thereof.
Background
The paraffin wax thermometer is a temperature sensing element, the main parts of which comprise a copper shell, a stainless steel push rod and a paraffin wax mixture, when the temperature of the external environment changes, the external heat is transferred to the paraffin wax mixture in the sealing through the copper shell, and the paraffin wax mixture expands or contracts due to the temperature rise or the temperature reduction so as to enable the push rod to displace. The paraffin wax thermometer bulb can quickly and automatically generate a mechanical action function after sensing the temperature change; the temperature sensor has the advantages of wide temperature sensing range, accurate sensing, simple structure and stable performance, and is widely applied to automatic control parts of building heating, heating and ventilation air conditioners, domestic hot water, automobile industry and the like.
However, it is difficult to avoid scaling on the surface of the copper shell during the use of the paraffin wax bulb. Fouling is a very common phenomenon which occurs in nature, in everyday life and in various industrial processes, in particular in various heat transfer processes, and the danger of fouling on heat transfer surfaces is mainly manifested as a severe reduction in the heat transfer capacity of the actual operation. Fouling of the heat transfer surfaces will create fouling resistance, resulting in a decrease in the overall heat transfer coefficient and a decrease in thermal efficiency during heat transfer. Therefore, under the same conditions, the heat transfer area actually required must be greatly increased to achieve the desired heat transfer effect, which is almost impossible to achieve in paraffin wax bulb applications.
The main cause of fouling is the adhesion of various deposits to the heat transfer surfaces in the water system. According to the different scale forming mechanism, the scale can be divided into several categories, such as crystal scale, particle scale, chemical reaction scale, corrosion scale and biological scale. However, in actual use, it is difficult to encounter a single type of dirt, and often several types of dirt are mixed together and interact, so that the problem is difficult to study and solve. The most prominent of these deposits is crystalline scale. The crystallization scale is a growth of insoluble salt or oxide crystals attached to the heat transfer surface. The generation of the crystals is mostly caused by crystallization due to the influence of temperature increase on the decrease in solubility of inorganic salts such as calcium carbonate, calcium sulfate, and calcium phosphate in water. The formation area is mainly the heat transfer surface with higher temperature. The scale is hard and compact, has strong adhesive force and large thermal resistance, and seriously influences the heat transfer efficiency and the reaction speed (also called sensitivity) of the paraffin wax thermal bulb, so that the method has great practical significance for researching how to prevent the scale from forming on the surface of the thermal bulb, particularly the surface of a copper shell.
In summary, there is a need to develop a novel copper shell with strong anti-scaling performance to solve the problems existing in the prior art and meet the requirements of actual production.
Disclosure of Invention
Based on this, there is a need to provide a new anti-scaling copper shell to overcome the deficiencies of the prior art.
One object of the invention is to provide an anti-scaling copper shell, wherein the anti-scaling copper shell is made of a Cu/Ni/Ti alloy material, the anti-scaling copper shell is subjected to ion implantation treatment, and the surface of the anti-scaling copper shell contains a modified PVDF (polyvinylidene fluoride) coating;
wherein the modified PVDF coating is prepared by the reaction of PVDF and dodecafluoroheptyl methacrylate (DFMA).
Furthermore, in the Cu/Ni/Ti alloy material, the mass ratio of Cu, ni and Ti is (40-60): (20-30): (10-20).
Further, the ion implantation treatment is performed by using one or more ions selected from Cr, F, C and N ions.
In the process of forming the dirt, on one hand, the dirt can be deposited on a heat transfer surface to increase the thermal resistance, but on the other hand, the dirt substance is washed by fluid and falls off to reduce the thermal resistance of the dirt. The fouling resistance response over time is a superposition of the results of these 2 phenomena. The rate of deposition of scale depends on the form of fouling, such as precipitation, crystallization, formation of organics, and the like. The rate of scale removal is related to the hardness, viscosity, flow velocity in the tube, shear force and system structure of the scale, and also to the surface energy of the heat transfer surface. Studies have shown that the formation of scale is mainly determined by the surface energy of the fouling and the heat transfer surface, the greater the surface energy of the material and its surface, the greater the adhesion between the fouling and the metal surface, and the more easily the fouling is formed on the metal surface. The smaller the surface energy is, the better the smoothness and uniformity of the solid surface is, and the solid surface has uniform and compact lattice arrangement and few defects such as dislocation, vacancy and the like, and bacteria attachment or organic and inorganic matter deposition causes great obstacles. Thus, the greater the surface energy, the greater the mass of scale deposited per unit of heat transfer surface, i.e., the more scale is likely to form on the metal surface.
The material modifying method of ion implantation is to irradiate high speed and high energy ion beam onto the surface of solid material in vacuum and to form one unique matter layer after the two materials produce serial physical and chemical actions. The ion implantation on the metal surface can produce alloys with different properties within 1-3 μm of the surface. The surface energy of the metal is reduced because both the bond energy and the free electron concentration of the metal surface are reduced and the entropy of the metal surface is increased.
Another object of the present invention is to provide a method for preparing the anti-scaling copper shell, which comprises the following steps:
(1) Ion implantation process
Polishing and polishing the copper shell, and after ultrasonic cleaning, putting the copper shell into an ion implanter for ion implantation treatment to obtain an ion implantation modified copper shell;
(2) Preparation of modified PVDF coatings
S1, adding PVDF into a KOH solution, heating for reaction, washing, filtering and drying to obtain alkali-treated PVDF;
s2, adding the PVDF subjected to alkali treatment and an initiator into a dodecafluoroheptyl methacrylate solution, stirring and heating to react under the nitrogen atmosphere, washing, filtering, distilling and purifying, and drying in vacuum to obtain modified PVDF;
s3, adding the modified PVDF into an organic solvent, heating and stirring to obtain a modified PVDF coating solution;
(3) And (3) putting the ion-implanted modified copper shell into the modified PVDF coating solution, soaking and drying to obtain the anti-scaling copper shell.
Further, in the step (1), the implantation energy of the ion implantation treatment is 50 to 100 kev.
Further, in the step (1), the implantation concentration of the ion implantation treatment is (2 × 10) 15 )-(2×10 17 ) ions/cm 2 。
Further, in the step (1), the ion implantation treatment reduces the surface energy of the copper shell.
Further, in the step S1, the heating reaction temperature is 60-70 ℃, and the reaction time is 10-20 min.
Further, in the step S2, the molar ratio of the PVDF and the dodecafluoroheptyl methacrylate after the alkali treatment is 1 (1-3).
Further, in the step S2, the heating reaction temperature is 70-80 ℃, and the reaction time is 8-16 h.
Further, in the step S3, the heating and stirring temperature is 80-90 ℃, and the stirring time is 10-20 h.
The invention also aims to provide the application of the anti-scaling copper shell in the paraffin wax thermal bulb.
The invention has the following beneficial effects:
1. the modified PVDF coating is PVDF grafted DFMA, the PVDF has excellent characteristics of strong hydrophobicity, corrosion resistance, high mechanical strength and the like, and after the DFMA is grafted, the hydrophobic angle of the modified PVDF is further increased, so that liquid in the environment is difficult to adhere to the surface of the coating, and the possibility of depositing inorganic salts such as calcium carbonate on the surface of a copper shell is reduced; meanwhile, the modified PVDF obviously reduces the surface energy by introducing a large number of fluorine-containing groups, forms a synergistic effect with the copper shell after ion implantation treatment, has extremely low surface energy on the surface of the material, greatly reduces the nucleation rate and the adhesive strength of inorganic salt crystals, further inhibits the deposition of dirt and plays a good anti-scaling role.
2. The modified PVDF coating has the advantages of small thickness, small using amount, low cost, no influence on the heat transfer efficiency of the copper shell and good application prospect.
Drawings
FIG. 1 is a graph showing the results of performance tests conducted on the anti-scaling copper shells prepared in example 1 and comparative examples 1-2 in the test examples of the present invention;
wherein,
FIG. 1 (a) 1 is a topographical view of a sample of comparative example 1 prior to testing;
FIG. 1 (a) 2 is a topographical view of a sample of example 1 prior to testing;
FIG. 1 (a) 3 is a topographical view of a sample of comparative example 2 prior to testing;
FIGS. 1 (b) 1 and 1 (c) 1 are topographical maps of comparative example 1 samples after testing;
FIGS. 1 (b) 2 and 1 (c) 2 are topographical maps of the samples of example 1 after testing;
FIGS. 1 (b) 3 and 1 (c) 3 are the morphology of the sample of comparative example 2 after the test.
Detailed Description
In order to more clearly illustrate the technical solution of the present invention, the following examples are listed. The starting materials, reactions and work-up procedures which are given in the examples are, unless otherwise stated, those which are customary on the market and are known to the person skilled in the art.
The words "preferred", "preferably", "more preferred", and the like, in the present invention, refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
It should be understood that other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention.
The meaning of "up and down" in the present invention means that when the reader faces the drawings, the upper side of the reader is the upper side, and the lower side of the reader is the lower side, and is not a specific limitation to the mechanism of the apparatus of the present invention.
When a component, element, or layer is referred to as being "on," "bonded to," "connected to," or "coupled to" another element or layer, it may be directly on, bonded to, connected to, or coupled to the other element, or layer, or intervening elements or layers may be present. In contrast, when an element is referred to as being "directly on," "directly coupled to," "directly connected to" or "directly coupled to" another element or layer, there may be no intervening elements or layers present. Other words used to describe the relationship between elements should be interpreted in a similar manner (e.g., "between.. Versus" directly between.. Versus, "" adjacent to "directly adjacent to," etc.). As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The copper shell in the embodiment of the invention is ordered from a local manufacturer.
The PVDF in the embodiment of the invention is FR904 polyvinylidene fluoride produced by Shanghai Sanai Rich materials Co.
The ion implanter in the embodiment of the invention is a SYZ-100 ion implanter of the Beijing mechanical industrial automation research institute.
Example 1
The anti-scaling copper shell is made of a Cu/Ni/Ti alloy material, is subjected to ion implantation treatment, and has a modified PVDF coating on the surface;
wherein the modified PVDF coating is prepared by the reaction of PVDF and DFMA;
the mass ratio of Cu to Ni to Ti is 50;
the ions for the ion implantation treatment are Cr ions.
The preparation method of the anti-scaling copper shell comprises the following steps:
(1) Ion implantation process
Gradually grinding copper shell with 600#, 800#, 1000#, 2000# water sand paper, polishing with suspended 0.5 μm diamond spray polishing agent, ultrasonically cleaning with acetone and anhydrous ethanol for 15 min, and implanting Cr ions (beam intensity 10 mA, implantation energy 60 kev, implantation concentration 2 × 10) into the pretreated copper shell 16 ions/cm 2 ）；
(2) Preparation of modified PVDF coatings
S1, adding PVDF into a KOH water/absolute ethyl alcohol mixed solution (water: absolute ethyl alcohol =1: v/v) with the mass fraction of 10%, stirring for 10 min at 60 ℃, then washing with deionized water, filtering, and drying to obtain alkali-treated PVDF;
s2, adding the PVDF subjected to alkali treatment and an initiator azobisisobutyronitrile into a water/absolute ethyl alcohol mixed solution of DFMA (PVDF subjected to alkali treatment: DFMA =1:2, n/n), stirring for 30 min under a nitrogen atmosphere, reacting for 10 h at 70 ℃, washing with deionized water, filtering, collecting a filtered product, placing the filtered product into a Soxhlet extractor, distilling and purifying with deionized water, and drying the purified product for 24 h under vacuum at 60 ℃ to obtain modified PVDF;
s3, adding the modified PVDF into a DMF solvent, and stirring at 80 ℃ for 12 hours to obtain a transparent solution, namely the modified PVDF coating;
(3) And (3) putting the copper shell subjected to ion implantation treatment in the step (1) into the modified PVDF coating solution prepared in the step (2), soaking for 24 hours, and drying to obtain the anti-scaling copper shell.
Example 2
An anti-scaling copper shell is made of a Cu/Ni/Ti alloy material, the anti-scaling copper shell is subjected to ion implantation treatment, and the surface of the anti-scaling copper shell comprises a modified PVDF coating;
wherein the modified PVDF coating is prepared by the reaction of PVDF and DFMA;
the mass ratio of Cu to Ni to Ti is 55;
the ions for the ion implantation treatment are Cr ions.
The preparation method of the anti-scaling copper shell comprises the following steps:
(1) Ion implantation process
Gradually grinding copper shell with 600#, 800#, 1000#, 2000# water sand paper, polishing with suspended 0.5 μm diamond spray polishing agent, ultrasonically cleaning with acetone and anhydrous ethanol for 15 min, and implanting Cr ions (beam intensity of 10 mA, implantation time of 10 mA) into the pretreated copper shellEnergy 60 kev, infusion concentration 2X 10 15 ions/cm 2 ）；
(2) Preparation of modified PVDF coatings
S1, adding PVDF into a KOH water/absolute ethyl alcohol mixed solution (water: absolute ethyl alcohol =1: v/v) with the mass fraction of 10%, stirring for 10 min at 70 ℃, then washing with deionized water, filtering, and drying to obtain alkali-treated PVDF;
s2, adding the PVDF subjected to alkali treatment and an initiator azobisisobutyronitrile into a water/absolute ethyl alcohol mixed solution of DFMA (PVDF subjected to alkali treatment: DFMA = 1.5, n/n), stirring for 30 min under a nitrogen atmosphere, reacting for 9 h at 75 ℃, washing with deionized water, filtering, collecting a filtered product, placing the filtered product into a Soxhlet extractor, distilling and purifying with deionized water, and drying the purified product for 24 h under vacuum at 60 ℃ to obtain modified PVDF;
s3, adding the modified PVDF into a DMF solvent, and stirring for 14 hours at 85 ℃ to obtain a transparent solution, namely the modified PVDF coating;
(3) And (3) putting the copper shell subjected to ion implantation treatment in the step (1) into the modified PVDF coating solution prepared in the step (2), soaking for 24 hours, and drying to obtain the anti-scaling copper shell.
Example 3
An anti-scaling copper shell is made of a Cu/Ni/Ti alloy material, the anti-scaling copper shell is subjected to ion implantation treatment, and the surface of the anti-scaling copper shell comprises a modified PVDF coating;
wherein the modified PVDF coating is prepared by the reaction of PVDF and DFMA;
the mass ratio of Cu to Ni to Ti is 60;
the ions subjected to the ion implantation treatment are Cr ions.
The preparation method of the anti-scaling copper shell comprises the following steps:
(1) Ion implantation process
Gradually grinding copper shell with 600#, 800#, 1000#, 2000# water sand paper, polishing with suspended 0.5 μm diamond spray polishing agent, ultrasonically cleaning with acetone and anhydrous ethanol for 15 min, and implanting ions into the pretreated copper shellIn the machine, cr ion implantation (beam intensity 10 mA, implantation energy 60 kev, implantation concentration 2X 10) 17 ions/cm 2 ）；
(2) Preparation of modified PVDF coatings
S1, adding PVDF into a KOH water/absolute ethyl alcohol mixed solution (water: absolute ethyl alcohol =1: v/v) with the mass fraction of 10%, stirring for 12 min at 65 ℃, then washing with deionized water, filtering, and drying to obtain alkali-treated PVDF;
s2, adding the PVDF subjected to alkali treatment and an initiator azobisisobutyronitrile into a water/absolute ethyl alcohol mixed solution of DFMA (PVDF subjected to alkali treatment: DFMA =1, 2.5, n/n), stirring for 30 min under a nitrogen atmosphere, reacting for 12 h at 75 ℃, washing with deionized water, filtering, collecting a filtered product, placing the filtered product into a Soxhlet extractor, distilling and purifying with deionized water, and drying the purified product for 24 h under vacuum at 60 ℃ to obtain modified PVDF;
s3, adding the modified PVDF into a DMF solvent, and stirring for 12 hours at 88 ℃ to obtain a transparent solution, namely the modified PVDF coating;
(3) And (3) putting the copper shell subjected to ion implantation treatment in the step (1) into the modified PVDF coating solution prepared in the step (2), soaking for 24 hours, and drying to obtain the anti-scaling copper shell.
Comparative example 1
An anti-scaling copper shell, the comparative example differing from example 1 in that: the comparative example comprises the following steps (1): the copper shell is gradually ground by using water sand paper of No. 600, no. 800, no. 1000 and No. 2000, then polished by using suspended diamond spray polishing agent with 0.5 mu m, and then ultrasonically cleaned by using acetone and absolute ethyl alcohol for 15 min, the copper shell is not subjected to ion implantation treatment, and other preparation methods are the same as those of the example 1.
Comparative example 2
An anti-scaling copper shell, the comparative example differing from example 1 in that: in step (2) of this comparative example, PVDF was directly dissolved in DMF to prepare a coating without modifying PVDF, and the other preparation methods were the same as in example 1.
Test example
The anti-scaling copper shells prepared in example 1 and comparative examples 1-2 were subjected to a performance test.
The test method comprises the following steps:
100 g of calcium bicarbonate and 100 g of magnesium bicarbonate are added into a thermostatic bath filled with 2500 mL of running water, after stirring and dissolving, the samples prepared in the example 1 and the comparative examples 1 and 2 are put into the solution, the thermostatic bath is set to be 90 ℃, after heating for 12 h, the power is cut off, the samples are placed for 12 h, the heating and power-off operations are circulated, and after 500 h is accumulated, the scaling condition on the surface of each sample is observed.
The test results are shown in table 1 and fig. 1.
TABLE 1 results of anti-fouling Properties test
| Sample (I) | Before testing | After testing |
| Example 1 | Glossy and non-fouling | Glossy, substantially dirt-free |
| Comparative example 1 | Glossy and non-fouling | Substantially matt, with dirt covering the surface |
| Comparative example 2 | Glossy and non-fouling | Dull, surface covered with dirt |
FIG. 1 is a graph showing the results of performance tests on the anti-scaling copper shells prepared in example 1 and comparative examples 1-2;
wherein,
FIG. 1 (a) 1 is a topographical view of a sample of comparative example 1 prior to testing;
FIG. 1 (a) 2 is a topographical view of a sample of example 1 prior to testing;
FIG. 1 (a) 3 is a topographical view of a sample of comparative example 2 prior to testing;
FIGS. 1 (b) 1 and 1 (c) 1 are topographical maps of comparative example 1 samples after testing;
FIGS. 1 (b) 2 and 1 (c) 2 are topographical maps of samples of example 1 after testing;
FIGS. 1 (b) 3 and 1 (c) 3 are topographical maps of the comparative example 2 sample after testing.
As can be seen from table 1 and fig. 1, the anti-scaling copper shells prepared in comparative examples 1 and 2 have unsatisfactory anti-scaling performance due to non-ion implantation treatment or modification of the PVDF film on the surface, and generate a large amount of scale on the surface after testing, which affects normal use; the anti-scaling copper shell prepared in the embodiment 1 of the invention has strong surface hydrophobicity, greatly reduces the surface energy of the product through synergistic effect, effectively avoids the deposition of scales, has excellent anti-scaling performance and good application prospect.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. The anti-scaling copper shell is characterized in that the anti-scaling copper shell is made of a Cu/Ni/Ti alloy material, the anti-scaling copper shell is subjected to ion implantation treatment, and the surface of the anti-scaling copper shell contains a modified PVDF coating;
wherein the modified PVDF coating is prepared by the reaction of PVDF and dodecafluoroheptyl methacrylate.
2. The anti-scaling copper shell as recited in claim 1, wherein the mass ratio of Cu, ni and Ti in the Cu/Ni/Ti alloy material is (40-60): (20-30): (10-20).
3. The anti-scaling copper shell according to claim 1, wherein the ion implantation treatment ions are selected from one or more of Cr, F, C and N ions.
4. A method of making an anti-scaling copper shell according to any of claims 1 to 3, comprising the steps of:
(1) Ion implantation process
Polishing the copper shell, ultrasonically cleaning, and then placing the copper shell into an ion implanter for ion implantation treatment to obtain an ion implantation modified copper shell;
(2) Preparation of modified PVDF coatings
S1, adding PVDF into a KOH solution, heating for reaction, washing, filtering and drying to obtain PVDF subjected to alkali treatment;
s2, adding the PVDF subjected to alkali treatment and an initiator into a dodecafluoroheptyl methacrylate solution, stirring and heating to react under the nitrogen atmosphere, washing, filtering, distilling and purifying, and drying in vacuum to obtain modified PVDF;
s3, adding the modified PVDF into an organic solvent, heating and stirring to obtain a modified PVDF coating solution;
(3) And (3) putting the ion-implanted modified copper shell into the modified PVDF coating solution, soaking and drying to obtain the anti-scaling copper shell.
5. The method for preparing the anti-scaling copper shell according to claim 4, wherein in the step (1), the implantation energy of the ion implantation treatment is 50 to 100 kev.
6. The method for preparing the anti-scaling copper shell according to claim 4, wherein in the step (1), the implantation concentration of the ion implantation treatment is (2 x 10) 15 )-(2×10 17 ) ions/cm 2 。
7. The method for preparing the anti-scaling copper shell according to claim 4, wherein in the step (1), the ion implantation treatment reduces the surface energy of the copper shell.
8. The method for preparing the anti-scaling copper shell according to claim 4, wherein in the step S2, the molar ratio of the PVDF and the dodecafluoroheptyl methacrylate after the alkali treatment is 1 (1-3).
9. The method for preparing the anti-scaling copper shell according to claim 4, wherein in the step S2, the heating reaction temperature is 70-80 ℃ and the reaction time is 8-16 h.
10. Use of the anti-scaling copper shell according to any one of claims 1 to 3 in paraffin wax incubators.
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|---|---|---|---|---|
| US4125152A (en) * | 1977-09-19 | 1978-11-14 | Borg-Warner Corporation | Scale resistant heat transfer surfaces and a method for their preparation |
| CN1206459A (en) * | 1995-11-02 | 1999-01-27 | 萨里大学 | Modification of metal surfaces |
| CN1748877A (en) * | 2005-09-30 | 2006-03-22 | 大连理工大学 | Process for preparing functional heat transfer surface |
| CN102277741A (en) * | 2010-06-12 | 2011-12-14 | 中国科学院上海应用物理研究所 | Super-hydrophobic fabric or super-hydrophobic non-woven fabric and preparation method thereof |
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2022
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|---|---|---|---|---|
| US4125152A (en) * | 1977-09-19 | 1978-11-14 | Borg-Warner Corporation | Scale resistant heat transfer surfaces and a method for their preparation |
| CN1206459A (en) * | 1995-11-02 | 1999-01-27 | 萨里大学 | Modification of metal surfaces |
| CN1748877A (en) * | 2005-09-30 | 2006-03-22 | 大连理工大学 | Process for preparing functional heat transfer surface |
| CN102277741A (en) * | 2010-06-12 | 2011-12-14 | 中国科学院上海应用物理研究所 | Super-hydrophobic fabric or super-hydrophobic non-woven fabric and preparation method thereof |
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