CN109652853B - A method for preparing frosted surface on Zr-based bulk amorphous alloy - Google Patents
A method for preparing frosted surface on Zr-based bulk amorphous alloy Download PDFInfo
- Publication number
- CN109652853B CN109652853B CN201910150899.8A CN201910150899A CN109652853B CN 109652853 B CN109652853 B CN 109652853B CN 201910150899 A CN201910150899 A CN 201910150899A CN 109652853 B CN109652853 B CN 109652853B
- Authority
- CN
- China
- Prior art keywords
- amorphous alloy
- zirconium
- based amorphous
- preparing
- electrolyte
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 26
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 47
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003792 electrolyte Substances 0.000 claims abstract description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005260 corrosion Methods 0.000 claims abstract description 13
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 7
- 239000010439 graphite Substances 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 150000004673 fluoride salts Chemical class 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052790 beryllium Inorganic materials 0.000 claims abstract 2
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000008151 electrolyte solution Substances 0.000 claims 1
- 238000004381 surface treatment Methods 0.000 abstract description 4
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 description 22
- 229910045601 alloy Inorganic materials 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 10
- 239000011159 matrix material Substances 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 6
- 239000002344 surface layer Substances 0.000 description 6
- 238000007743 anodising Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000002048 anodisation reaction Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000013528 metallic particle Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000005300 metallic glass Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013526 supercooled liquid Substances 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
- C25F3/08—Etching of refractory metals
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
技术领域technical field
本发明属于非晶合金表面处理技术领域，具体地说，涉及一种Zr基大块非晶合金上制备磨砂表面的方法。The invention belongs to the technical field of amorphous alloy surface treatment, in particular to a method for preparing a frosted surface on a Zr-based bulk amorphous alloy.
背景技术Background technique
非晶合金又称金属玻璃，是通过极高冷却速度来使合金材料原子没有足够时间进行重排，不出现结晶而形成的一种处于亚稳态状态的材料。其原子在三维空间呈拓扑无序排列，具备独特的长程无序、短程有序的结构，因而表现出优异的物理、化学及力学性能。在非晶合金中，以Zr为主要元素的锆基非晶合金具有强大的玻璃形成能力(GFA)和宽大的过冷液相区，可以利用不太复杂的设备较为容易的制备出性能优异、尺寸较大、易于成型的块体非晶合金。因此，锆基非晶合金自被发现以来一直是非晶合金研究的重点和热点，在航空航天、军工、电子器件、生物医药、体育用品等领域受到广泛关注。Amorphous alloy, also known as metallic glass, is a material in a metastable state formed by extremely high cooling rate so that the atoms of the alloy material do not have enough time to rearrange and do not crystallize. Its atoms are topologically disordered in three-dimensional space, and have a unique long-range disorder and short-range order structure, thus showing excellent physical, chemical and mechanical properties. Among the amorphous alloys, zirconium-based amorphous alloys with Zr as the main element have strong glass forming ability (GFA) and a wide supercooled liquid phase region, and can be easily prepared with less complex equipment. Larger, easily formed bulk amorphous alloys. Therefore, zirconium-based amorphous alloys have been the focus and hotspot of amorphous alloy research since their discovery, and have received extensive attention in the fields of aerospace, military industry, electronic devices, biomedicine, and sporting goods.
但是，锆基非晶合金的表面处理技术发展时间较短，目前已知通过喷砂的方式可以使锆基非晶合金获得磨砂表面结构，例如，中国专利申请号为：201110421437.9，公开日为2012年5月2日的专利文献，公开了一种非晶合金表面处理工艺，该处理工艺利用金属颗粒和非金属颗粒对非晶合金表面进行喷射处理；其中，金属颗粒为钢丸、铁丸、钢砂、铁砂中一种或多种，非金属颗粒为陶瓷、玻璃的丸料或砂料中的一种或多种。该方法得到的非晶合金表面具有一定的粗糙度，但该工艺易导致非晶合金的局部出现弛豫晶化现象，同时会引入杂质元素。However, the surface treatment technology of zirconium-based amorphous alloys has been developed for a short period of time, and it is currently known that the zirconium-based amorphous alloys can obtain a frosted surface structure by sandblasting. The patent document dated May 2, 2008 discloses a surface treatment process for amorphous alloys, which utilizes metal particles and non-metallic particles to spray the surface of amorphous alloys; wherein the metal particles are steel shot, iron shot, One or more of steel sand and iron sand, and the non-metallic particles are one or more of ceramic, glass shot or sand. The surface of the amorphous alloy obtained by this method has a certain degree of roughness, but this process is likely to lead to local relaxation crystallization of the amorphous alloy, and at the same time, impurity elements will be introduced.
因此，开发新的在锆基非晶合金表面构建磨砂结构的方法具有重要意义。经检索，中国专利申请号为：201110179302.6，公开日为：2013年1月2日的专利文献，公开了一种锆基非晶合金复合材料，该复合材料包括锆基非晶合金基体，以及附着在所述锆基非晶合金基体表面上的陶瓷膜层，所述陶瓷膜层通过将锆基非晶合金基体置于盛有电解液(含有硫酸盐、硝酸盐、草酸盐中的一种或多种的水溶液，pH值为6～7)的电解槽中，以锆基非晶合金基体为阳极，以不锈钢板为阴极，在等离子体氧化的条件下形成，所述陶瓷膜层含有ZrO2。该陶瓷膜层的硬度高、耐腐蚀性和耐磨性能好，并且与锆基非晶合金基体的附着力好，但是该工艺采用等离子体氧化方法，能耗较高，而且该方法仅能获得普通致密的陶瓷膜，无法获得磨砂结构膜层。Therefore, it is of great significance to develop a new method to construct frosted structures on the surface of zirconium-based amorphous alloys. After retrieval, the Chinese patent application number is: 201110179302.6, and the publication date is: January 2, 2013. The patent document discloses a zirconium-based amorphous alloy composite material. The composite material includes a zirconium-based amorphous alloy matrix, and an adhesive The ceramic membrane layer on the surface of the zirconium-based amorphous alloy substrate, the ceramic membrane layer is formed by placing the zirconium-based amorphous alloy substrate in an electrolyte (containing one of sulfate, nitrate, and oxalate) or a variety of aqueous solutions, in an electrolytic cell with a pH value of 6 to 7), the zirconium-based amorphous alloy matrix is used as the anode, and the stainless steel plate is used as the cathode, formed under the condition of plasma oxidation, and the ceramic film layer contains ZrO 2 . The ceramic film layer has high hardness, good corrosion resistance and wear resistance, and good adhesion to the zirconium-based amorphous alloy matrix, but the process adopts the plasma oxidation method, which has high energy consumption, and this method can only obtain Ordinary dense ceramic membranes cannot obtain a frosted structure membrane.
发明内容SUMMARY OF THE INVENTION
1.要解决的问题1. The problem to be solved
针对现有在锆基非晶合金上制备磨砂表面层的方法容易导致非晶合金出现弛豫晶化现象，破坏基体性能，以及可能引入杂质的问题，本发明提供一种Zr基大块非晶合金上制备磨砂表面的方法，该方法通过电腐蚀的方式，能在锆基非晶合金上制备出结构致密、磨砂均匀、呈浅灰色的磨砂氧化膜。Aiming at the problems that the existing method for preparing a frosted surface layer on a zirconium-based amorphous alloy easily leads to relaxation crystallization of the amorphous alloy, destroys the performance of the matrix, and may introduce impurities, the present invention provides a Zr-based bulk amorphous alloy. The invention discloses a method for preparing a frosted surface on an alloy. The method can prepare a frosted oxide film with dense structure, uniform frosting and light gray color on the zirconium-based amorphous alloy by means of electric corrosion.
2.技术方案2. Technical solutions
为了解决上述问题，本发明所采用的技术方案如下：In order to solve the above problems, the technical scheme adopted in the present invention is as follows:
一种Zr基大块非晶合金上制备磨砂表面的方法，将锆基非晶合金置于盛有电解液的电解槽中，以锆基非晶合金为阳极，以石墨板或铂片为阴极，在恒流条件下进行电腐蚀；其中，所述的电解液中含有氟化盐；所述的锆基非晶合金中Zr元素的含量＞50％，其他元素为Cu、Ni、Ti、Al、Be中的3～4种。A method for preparing a frosted surface on a Zr-based bulk amorphous alloy, the zirconium-based amorphous alloy is placed in an electrolytic cell filled with electrolyte, the zirconium-based amorphous alloy is used as the anode, and the graphite plate or platinum sheet is used as the cathode. , conduct electric corrosion under constant current conditions; wherein, the electrolyte contains fluoride salt; the content of Zr element in the zirconium-based amorphous alloy is more than 50%, and other elements are Cu, Ni, Ti, Al , 3 to 4 kinds of Be.
优选地，所述的电解液为NH4F和Na2SO4的水溶液，其中，Na2SO4作为支持电解质主要起到增加电解液的电导率的作用。Preferably, the electrolyte is an aqueous solution of NH 4 F and Na 2 SO 4 , wherein Na 2 SO 4 is used as a supporting electrolyte to mainly increase the conductivity of the electrolyte.
优选地，所述电解液中F-的浓度为0.4～0.6mol/L，NH4F与Na2SO4摩尔比为(2～3):10。Preferably, the concentration of F - in the electrolyte is 0.4-0.6 mol/L, and the molar ratio of NH 4 F to Na 2 SO 4 is (2-3):10.
优选地，所述电解液的工作温度为：20～25℃。Preferably, the working temperature of the electrolyte is 20-25°C.
优选地，恒流阳极氧化的电流密度为8～14mA/cm2，时间为25～30min。Preferably, the current density of the constant-current anodic oxidation is 8-14 mA/cm 2 , and the time is 25-30 min.
优选地，所述阴极面积为阳极面积的1～1.5倍，以减少阳极样品的尖端放电。Preferably, the area of the cathode is 1-1.5 times the area of the anode to reduce tip discharge of the anode sample.
3.有益效果3. Beneficial effects
相比于现有技术，本发明的有益效果为：Compared with the prior art, the beneficial effects of the present invention are:
(1)本发明Zr基大块非晶合金上制备磨砂表面的方法所用电解液中的F-对于锆基非晶合金具有独特的刻蚀作用，其在较低的电位下就可以与Zr反应生成ZrF6 2-离子，从而锆基非晶合金在F-的腐蚀下形成孔洞，另一方面基体中Zr、Ti、Al三种阀型金属则钝化形成氧化膜，在腐蚀和氧化成膜的协同作用下，通过电化学阳极氧化能够构建磨砂表面，且制备得到的表面氧化膜结构致密、磨砂均匀、呈灰色，非晶合金的耐腐蚀性也得到了提高；(1) F in the electrolyte used in the method for preparing a frosted surface on a Zr-based bulk amorphous alloy of the present invention has a unique etching effect on the zirconium-based amorphous alloy, and it can react with Zr at a lower potential ZrF 6 2- ions are generated, so that the zirconium-based amorphous alloy forms pores under the corrosion of F- , on the other hand, the three valve metals Zr, Ti and Al in the matrix are passivated to form an oxide film, which is formed during corrosion and oxidation. Under the synergistic effect of anodic oxidation, the frosted surface can be constructed by electrochemical anodic oxidation, and the prepared surface oxide film has a dense structure, uniform frosting and gray color, and the corrosion resistance of the amorphous alloy is also improved;
(2)本发明Zr基大块非晶合金上制备磨砂表面的方法F-的浓度过高会导致腐蚀速率过大，无法形成氧化膜；F-浓度过低则会腐蚀速率不够，可以形成氧化膜但难以形成磨砂表面；而电流密度过大可以形成氧化膜，但难以形成磨砂表面，电流密度过小，则难以形成氧化膜；发明人通过大量的试验和分析，得到F-的浓度优选0.4～0.6mol/L，电流密度优选8～14mA/cm2时，腐蚀和氧化成膜的协同作用较好，从而能够形成磨砂表面；(2) The method for preparing a frosted surface on the Zr-based bulk amorphous alloy of the present invention . If the concentration of F- is too high, the corrosion rate will be too large, and an oxide film cannot be formed; if the concentration of F- is too low, the corrosion rate will be insufficient, and an oxide However, if the current density is too large, it is difficult to form an oxide film, but it is difficult to form a frosted surface. If the current density is too small, it is difficult to form an oxide film; the inventors have obtained through a lot of experiments and analysis. The concentration of F- is preferably 0.4 ～0.6mol/L, when the current density is preferably 8～14mA/cm 2 , the synergistic effect of corrosion and oxidation film formation is better, so that a frosted surface can be formed;
(3)本发明Zr基大块非晶合金上制备磨砂表面的方法所涉及的阳极氧化工艺，在常温下即可完成，合成温度低，不会使非晶基体产生晶化或弛豫现象而导致非晶合金性能遭到破坏；且阳极氧化是处在表面的基体金属直接同选定介质中的阴离子反应，使之形成自身转化的产物，实际上是受控金属的腐蚀过程，原位构建结合力强、重现性好。(3) The anodic oxidation process involved in the method for preparing the frosted surface on the Zr-based bulk amorphous alloy of the present invention can be completed at normal temperature, and the synthesis temperature is low, and the amorphous matrix will not be crystallization or relaxation phenomenon. It leads to the destruction of the properties of amorphous alloys; and anodization is the direct reaction of the matrix metal on the surface with the anions in the selected medium to form a self-transformed product, which is actually a controlled metal corrosion process, in-situ construction Strong binding force and good reproducibility.
附图说明Description of drawings
图1为本发明Zr基大块非晶合金上制备磨砂表面的方法的流程图；Fig. 1 is the flow chart of the method for preparing frosted surface on Zr-based bulk amorphous alloy of the present invention;
图2为制备磨砂表面层前的锆基非晶合金片；Fig. 2 is the zirconium-based amorphous alloy sheet before preparing the frosted surface layer;
图3为制备磨砂表面层后的锆基非晶合金片；Figure 3 is a zirconium-based amorphous alloy sheet after preparing a frosted surface layer;
图4为制备磨砂表面层前的锆基非晶合金片的扫描电镜照片；Fig. 4 is the scanning electron microscope photograph of the zirconium-based amorphous alloy sheet before preparing the frosted surface layer;
图5为制备磨砂表面层后的锆基非晶合金片的扫描电镜照片；Fig. 5 is the scanning electron microscope photograph of the zirconium-based amorphous alloy sheet after preparing the frosted surface layer;
图6为制备磨砂表面层前后锆基非晶合金片的XRD图谱。FIG. 6 shows the XRD patterns of the zirconium-based amorphous alloy sheets before and after the preparation of the frosted surface layer.
具体实施方式Detailed ways
下面结合具体实施例对本发明进一步进行描述。The present invention will be further described below with reference to specific embodiments.
实施例1Example 1
如图1所示，经过前处理后的锆基非晶合金片(如图2所示)作为阳极，阴极为铂片，将阴阳极置于电解液中，在温度为20℃、电流密度为14mA/cm2、电解时间为30分钟的条件下进行阳极氧化，取出阳极合金片经乙醇清洗后自然晾干，能在锆基非晶合金上制备磨砂表面(如图3所示)。其中，铂片阴极面积为合金片阳极面积的1.5倍，所用电解液由NH4F和Na2SO4溶解于水中制得，NH4F与Na2SO4溶解后的摩尔比为2:10，F-的浓度为0.4mol/L。As shown in Figure 1, the pretreated zirconium-based amorphous alloy sheet (as shown in Figure 2) is used as the anode, and the cathode is a platinum sheet. Anodizing was carried out under the conditions of 14 mA/cm 2 and an electrolysis time of 30 minutes, and the anode alloy sheet was taken out, washed with ethanol, and then air-dried naturally to prepare a frosted surface on the zirconium-based amorphous alloy (as shown in Figure 3). Among them, the cathode area of the platinum sheet is 1.5 times the anode area of the alloy sheet, and the electrolyte used is prepared by dissolving NH 4 F and Na 2 SO 4 in water, and the molar ratio of NH 4 F and Na 2 SO 4 after dissolving is 2:10 , the concentration of F - is 0.4mol/L.
本实施例制备得到的锆基非晶合金表面呈磨砂结构，且氧化膜层结构致密、磨砂均匀、表面呈浅灰色。在扫描电镜下观察，阳极氧化后表面出现大量的晶粒，晶粒均匀分布，且结晶致密。从XRD图谱可看出，阳极氧化后锆基非晶合金表面出现了晶态ZrO2和Al2O3的衍射峰。The surface of the zirconium-based amorphous alloy prepared in this example has a frosted structure, and the oxide film has a dense structure, uniform frosting, and a light gray surface. Observed under the scanning electron microscope, a large number of grains appeared on the surface after anodization, the grains were uniformly distributed, and the crystals were dense. It can be seen from the XRD pattern that the diffraction peaks of crystalline ZrO 2 and Al 2 O 3 appear on the surface of the zirconium-based amorphous alloy after anodization.
实施例2Example 2
如图1所示，经过前处理后的锆基非晶合金片作为阳极，阴极为石墨板，将阴阳极置于电解液中，在温度为25℃、电流密度为14mA/cm2、电解时间为30分钟的条件下进行阳极氧化，取出阳极合金片经乙醇清洗后自然晾干，能在锆基非晶合金上制备磨砂表面。其中，石墨阴极面积与合金片阳极面积相等，所用电解液由NH4F和Na2SO4溶解于水中制得，NH4F与Na2SO4溶解后的摩尔比为2:10，F-的浓度为0.5mol/L。As shown in Figure 1 , the zirconium-based amorphous alloy sheet after pretreatment is used as the anode, and the cathode is a graphite plate. Anodizing is carried out under the condition of 30 minutes, and the anode alloy sheet is taken out, washed with ethanol, and then air-dried naturally, and the frosted surface can be prepared on the zirconium-based amorphous alloy. Among them, the area of the graphite cathode is equal to that of the anode of the alloy sheet. The electrolyte used is prepared by dissolving NH 4 F and Na 2 SO 4 in water. The molar ratio of NH 4 F and Na 2 SO 4 after dissolving is 2:10 . The concentration of 0.5mol/L.
本实施例制备得到的锆基非晶合金表面呈磨砂结构，且氧化膜层结构致密、磨砂均匀、表面呈浅灰色。The surface of the zirconium-based amorphous alloy prepared in this example has a frosted structure, and the oxide film has a dense structure, uniform frosting, and a light gray surface.
实施例3Example 3
如图1所示，经过前处理后的锆基非晶合金片作为阳极，阴极为铂片，将阴阳极置于电解液中，在温度为20℃、电流密度为8mA/cm2、电解时间为25分钟的条件下进行阳极氧化，取出阳极合金片经乙醇清洗后自然晾干，能在锆基非晶合金上制备磨砂表面。其中，铂片阴极面积为合金片阳极面积的1.5倍，所用电解液由NH4F和Na2SO4溶解于水中制得，NH4F与Na2SO4溶解后的摩尔比为3:10，F-的浓度为0.6mol/L。As shown in Figure 1, the pre-treated zirconium - based amorphous alloy sheet was used as the anode, and the cathode was a platinum sheet. Anodizing is carried out under the condition of 25 minutes, and the anode alloy sheet is taken out, washed with ethanol, and then air-dried naturally, so that the frosted surface can be prepared on the zirconium-based amorphous alloy. Among them, the cathode area of the platinum sheet is 1.5 times the anode area of the alloy sheet, and the electrolyte used is prepared by dissolving NH 4 F and Na 2 SO 4 in water, and the molar ratio of NH 4 F and Na 2 SO 4 after dissolving is 3:10 , the concentration of F - is 0.6mol/L.
本实施例制备得到的锆基非晶合金表面呈磨砂结构，且氧化膜层结构致密、磨砂均匀、表面呈浅灰色。The surface of the zirconium-based amorphous alloy prepared in this example has a frosted structure, and the oxide film has a dense structure, uniform frosting, and a light gray surface.
实施例4Example 4
如图1所示，经过前处理后的锆基非晶合金片作为阳极，阴极为石墨板，将阴阳极置于电解液中，在温度为20℃、电流密度为8mA/cm2、电解时间为30分钟的条件下进行阳极氧化，取出阳极合金片经乙醇清洗后自然晾干，能在锆基非晶合金上制备磨砂表面。其中，石墨阴极面积与合金片阳极面积相等，所用电解液由NH4F和Na2SO4溶解于水中制得，NH4F与Na2SO4溶解后的摩尔比为3:10，F-的浓度为0.6mol/L。As shown in Figure 1 , the zirconium-based amorphous alloy sheet after pretreatment is used as the anode, and the cathode is a graphite plate. Anodizing is carried out under the condition of 30 minutes, and the anode alloy sheet is taken out, washed with ethanol, and then air-dried naturally, and the frosted surface can be prepared on the zirconium-based amorphous alloy. The area of the graphite cathode is equal to that of the anode of the alloy sheet. The electrolyte used is prepared by dissolving NH 4 F and Na 2 SO 4 in water. The molar ratio of NH 4 F and Na 2 SO 4 after dissolving is 3:10 . The concentration of 0.6mol/L.
本实施例制备得到的锆基非晶合金表面呈磨砂结构，且氧化膜层结构致密、磨砂均匀、表面呈浅灰色。The surface of the zirconium-based amorphous alloy prepared in this example has a frosted structure, and the oxide film has a dense structure, uniform frosting, and a light gray surface.
实施例5Example 5
如图1所示，经过前处理后的锆基非晶合金片作为阳极，阴极为铂片，将阴阳极置于电解液中，在温度为25℃、电流密度为14mA/cm2、电解时间为25分钟的条件下进行阳极氧化，取出阳极合金片经乙醇清洗后自然晾干，能在锆基非晶合金上制备磨砂表面。其中，铂片阴极面积为合金片阳极面积的1.5倍，所用电解液由NH4F和Na2SO4溶解于水中制得，NH4F与Na2SO4溶解后的摩尔比为3:10，F-的浓度为0.5mol/L。As shown in Figure 1, the pre-treated zirconium - based amorphous alloy sheet is used as the anode, and the cathode is a platinum sheet. Anodizing is carried out under the condition of 25 minutes, and the anode alloy sheet is taken out, washed with ethanol, and then air-dried naturally, so that the frosted surface can be prepared on the zirconium-based amorphous alloy. Among them, the cathode area of the platinum sheet is 1.5 times the anode area of the alloy sheet, and the electrolyte used is prepared by dissolving NH 4 F and Na 2 SO 4 in water, and the molar ratio of NH 4 F and Na 2 SO 4 after dissolving is 3:10 , the concentration of F - is 0.5mol/L.
本实施例制备得到的锆基非晶合金表面呈磨砂结构，且氧化膜层结构致密、磨砂均匀、表面呈浅灰色。The surface of the zirconium-based amorphous alloy prepared in this example has a frosted structure, and the oxide film has a dense structure, uniform frosting, and a light gray surface.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910150899.8A CN109652853B (en) | 2019-02-28 | 2019-02-28 | A method for preparing frosted surface on Zr-based bulk amorphous alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910150899.8A CN109652853B (en) | 2019-02-28 | 2019-02-28 | A method for preparing frosted surface on Zr-based bulk amorphous alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109652853A CN109652853A (en) | 2019-04-19 |
| CN109652853B true CN109652853B (en) | 2020-07-28 |
Family
ID=66123325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910150899.8A Active CN109652853B (en) | 2019-02-28 | 2019-02-28 | A method for preparing frosted surface on Zr-based bulk amorphous alloy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109652853B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109930087B (en) * | 2019-05-08 | 2021-04-02 | 常州世竟液态金属有限公司 | Preparation method of zirconium-based amorphous alloy surface nano-structure layer |
| CN111058076B (en) * | 2019-12-30 | 2020-11-20 | 安徽工业大学 | A Zr-based high-entropy alloy material and a method for synthesizing a porous spherical structure on the surface of a Zr-based high-entropy alloy |
| CN113293412A (en) * | 2021-05-21 | 2021-08-24 | 重庆沛轩精密电子有限公司 | Manufacturing method of frosted feeling of aluminum alloy notebook computer shell |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100549997B1 (en) * | 2004-02-10 | 2006-02-08 | 학교법인 포항공과대학교 | Manufacturing method of amorphous surface composite material using high energy accelerated electron beam |
| CN1957114B (en) * | 2004-05-28 | 2010-08-18 | 日本碍子株式会社 | Method for coloring surface of zirconium-based metallic glass product |
| CN100457934C (en) * | 2007-03-16 | 2009-02-04 | 北京科技大学 | Method for preparing porous blocks of metallic glass by electrochemical eroding metal fibers |
| CN102851719B (en) * | 2011-06-29 | 2016-01-27 | 比亚迪股份有限公司 | A kind of Zirconium-base non-crystalline alloy compound material and preparation method thereof |
| CN102560594B (en) * | 2011-12-27 | 2014-06-04 | 西安交通大学 | A Fluoride Ion Precipitation Anodic Oxidation Method for Improving the Binding Strength of ZrO2 Nanotubes |
| CN104389002B (en) * | 2014-11-28 | 2016-08-24 | 东莞市莞信企业管理咨询有限公司 | A kind of Nano tube of zirconium dioxide and preparation method thereof |
| CN108284562A (en) * | 2017-01-10 | 2018-07-17 | 优尔材料工业（深圳）有限公司 | Zirconium-based amorphous alloy part and plastic part composite and preparation method thereof |
| CN106894072B (en) * | 2017-03-23 | 2019-07-30 | 北京航空航天大学 | A method of oxide nanotube array layer is prepared on zirconium-base amorphous alloy surface |
-
2019
- 2019-02-28 CN CN201910150899.8A patent/CN109652853B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109652853A (en) | 2019-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cheng et al. | Corrosion-resistant high-entropy alloy coatings: a review | |
| CN104562128B (en) | A kind of method for preparing thermal protection ceramic layer on metal or metallic composite surface | |
| CN109652853B (en) | A method for preparing frosted surface on Zr-based bulk amorphous alloy | |
| Shriram et al. | Electrodeposition of nanocrystalline nickel—A brief review | |
| CN104911642B (en) | RE-Ni-Mo/GO nano composite deposition liquid as well as preparation method and application thereof | |
| CN108570703A (en) | Preparation method of tungsten/copper laminated composite material based on tungsten sheet surface nanocrystallization | |
| CN106835219A (en) | A kind of super-hydrophobic stainless steel watch finishing coat and preparation method thereof | |
| Junli et al. | Study on characteristics of Ni-WB composites containing CeO2 nano-particles prepared by pulse electrodeposition | |
| Raj et al. | Comparative study of hydrogen evolution behavior of Nickel Cobalt and Nickel Cobalt Magnesium alloy film prepared by pulsed electrodeposition | |
| CN104313655A (en) | Method for electroplating Ni-Fe alloy with ionic liquid | |
| CN105018999A (en) | Method for growing layered doubled hydroxide on aluminum alloy micro-arc oxidation film in situ | |
| CN104451819A (en) | Method for constructing superhydrophobic aluminum surface with high stability | |
| CN101985766B (en) | Method for electroplating Zn-Ti alloy by ionic liquid | |
| CN102877102B (en) | A kind of recombining process of valve metal material quick differential arc oxidation | |
| Zhen et al. | Micromorphology and texture of niobium coating electrodeposited in NaCl—KCl—CsCl molten salt system | |
| CN105967740B (en) | A kind of laser melting coating and the chemical de- compound method for preparing micro nano structure block silicon materials of alloy | |
| CN101008078A (en) | Method for precipitating large area amorphous, nanocrystalline alloy layer using magnesium alloy surface glow plasma | |
| CN110714219A (en) | Method for electroplating nickel on magnesium alloy micro-arc oxidation surface | |
| CN103436921B (en) | A kind of method of ionic liquid electrodeposition aluminium manganese-titanium | |
| CN102673040B (en) | Cu-Ni functionally gradient material and preparation method thereof | |
| CN105385989B (en) | A kind of salt melting system, compound cocatalyst and the application of the binary permeation of molybdenum or molybdenum alloy | |
| WO2020258366A1 (en) | Method for preparing high-li-content lithium alloy | |
| CN101220425A (en) | A kind of high-strength nano-scale crystalline nickel material and its preparation method | |
| CN116770242A (en) | Amorphous copper-tungsten alloy for producing hydrogen by water electrolysis and preparation method thereof | |
| CN102041543A (en) | Preparation method of fullerene/metal composite film on metal surface |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200909 Address after: 213000 Factory Building No. 1-1 of Changzhou Science and Education City Intelligent Digital Industrial Park, No. 18-65 Changwu Middle Road, Changzhou City, Jiangsu Province Patentee after: CHANGZHOU SHIJING LIQUID METAL Co.,Ltd. Address before: 243002 Anhui city in Ma'anshan Province, Huashan District East Lake Road No. 59 Patentee before: ANHUI University OF TECHNOLOGY |
|
| TR01 | Transfer of patent right | ||
| CP02 | Change in the address of a patent holder |
Address after: No.14 factory building, innovation park, 377 Wuyi South Road, Wujin national high tech Industrial Development Zone, Changzhou City, Jiangsu Province, 213000 Patentee after: CHANGZHOU SHIJING LIQUID METAL Co.,Ltd. Address before: 213000 Factory Building No. 1-1 of Changzhou Science and Education City Intelligent Digital Industrial Park, No. 18-65 Changwu Middle Road, Changzhou City, Jiangsu Province Patentee before: CHANGZHOU SHIJING LIQUID METAL Co.,Ltd. |
|
| CP02 | Change in the address of a patent holder |