TWM612723U

TWM612723U - Composite material layered structure

Info

Publication number: TWM612723U
Application number: TW110200902U
Authority: TW
Inventors: 謝曙旭
Original assignee: 晟銘電子科技股份有限公司
Priority date: 2021-01-25
Filing date: 2021-01-25
Publication date: 2021-06-01

Abstract

This utility model relates to a composite material layered structure, including a electroplating layer and a nitrided layer. Wherein the electroplating layer is located in the outer layer of the composite material layered structure, from the surface of the electroplating layer to the inside, it is formed by four metal layers of nickel-palladium alloy, nickel, copper, and nickel in sequence, the nitriding layer is located in the inner layer of the composite material layered structure, and it has an expanded Asada scattered iron structure. The composite material layered structure can be applied to wear-resistant workpieces such as mobile phone charging plugs, medical equipment, ship metal, molds, knives, and mechanical structural parts.

Description

複合材料層狀結構 Composite layered structure

本創作係關於一種複合材料層狀結構，特別是關於一種具有膨脹型麻田散鐵結構的滲氮層的複合材料層狀結構。 This creation is about a composite material layered structure, especially a composite material layered structure with a nitriding layer with an expanded Asada scattered iron structure.

由於科技的飛躍進展，人類所需的各種裝置及儀器越發精密，因此對應需要的金屬元件的尺寸與特性要求則越發嚴格。舉例而言，為了因應電子裝置的微型化，電子裝置內含金屬元件的尺寸亦必須微型化；或者，為了因應傳動裝置需能承受長時間且頻繁的磨耗，傳動裝置內含的金屬元件亦需具有良好的剛性及耐磨特性。 Due to the rapid development of science and technology, various devices and instruments required by human beings have become more and more sophisticated, so the size and characteristic requirements of the corresponding metal components have become more stringent. For example, in order to cope with the miniaturization of electronic devices, the size of the metal components contained in the electronic devices must also be miniaturized; or, in order to cope with the transmission device that needs to be able to withstand long-term and frequent wear, the metal components contained in the transmission device must also be miniaturized. Has good rigidity and wear resistance.

因此，能夠用來生產具有複雜形狀、高精密度、高性能的金屬元件之金屬射出成型(metal injection molding，MIM)技術至關重要。此外，金屬射出成型技術還能夠搭配析出硬化(precipitation hardening)製程及滲氮(nitriding)製程等熱處理技術，藉由提供滲氮層於金屬元件的表面，來進一步提升金屬元件的性能。 Therefore, metal injection molding (MIM) technology that can be used to produce metal components with complex shapes, high precision, and high performance is very important. In addition, the metal injection molding technology can also be used with heat treatment technologies such as precipitation hardening and nitriding processes to further improve the performance of the metal element by providing a nitriding layer on the surface of the metal element.

現今，市面上皆藉由調整進行滲氮製程的時間長短來調整滲氮層的厚度，而對應調整金屬元件的性能。然而，由於進行工業化大批量的生產時，經常是將金屬元件送入滲氮廠進行滲氮，而若需依據各金屬元件所需的表面亦度特性及滲氮層厚度來調整滲氮時間，則不能將需要進行不同滲氮時間處理的金屬元件於同一批中進行處理，致使製造成本提升。 Nowadays, the thickness of the nitriding layer is adjusted by adjusting the length of time for the nitriding process in the market, and the performance of the metal element is adjusted accordingly. However, due to the large-scale industrial production, the metal components are often sent to the nitriding plant for nitriding, and if necessary, the required surface of each metal component is also required. To adjust the nitriding time based on the characteristics of the nitriding layer and the thickness of the nitriding layer, it is impossible to process the metal elements that need to be processed for different nitriding times in the same batch, resulting in increased manufacturing costs.

鑒於上述問題，本創作之目的為提供一種複合材料層狀結構，其包含電鍍層及滲氮層；其中，電鍍層係作為複合材料層狀結構的外層，滲氮層係作為複合材料層狀結構的內層。滲氮層係為一成型體之表層，成型體係利用成型、析出硬化與低溫滲氮製程進行製備，並藉由調整銅佔射料粉末的重量百分比，在固定的滲氮時間下，來調整滲氮層的厚度，進而改善上述問題。 In view of the above problems, the purpose of this creation is to provide a composite material layered structure, which includes an electroplated layer and a nitrided layer; wherein the electroplated layer is used as the outer layer of the composite material layered structure, and the nitrided layer is used as the composite material layered structure的内层。 The inner layer. The nitriding layer is the surface layer of a molded body. The molding system is prepared by molding, precipitation hardening, and low-temperature nitriding processes. The nitriding layer is adjusted by adjusting the weight percentage of copper in the shot powder under a fixed nitriding time. The thickness of the nitrogen layer further improves the above-mentioned problems.

根據本創作之目的，提供一種複合材料層狀結構，其包含電鍍層及滲氮層。其中，電鍍層位於複合材料層狀結構的外層，由電鍍層表面至內部係依序由鎳-鈀合金、鎳、銅、鎳等四層金屬層所形成；而滲氮層位於複合材料層狀結構的內層，且其具有膨脹型麻田散鐵結構。滲氮層係為一成型體之表層，成型體包含滲氮層及基底層，基底層係由射料粉末與結合劑混煉造粒之射料加以成型為一成型體而形成，射料粉末包含鐵以及佔射料粉末為3~5wt%的銅，基底層的面心立方晶體結構佔基底層的0%~15%。滲氮層係將預成型體進行析出硬化製程，以使預成型體內的銅的至少一部份集中於預成型體的表面，並以低溫滲氮製程使滲氮層形成於基底層之表面，且滲氮層係具有膨脹型麻田散鐵結構。滲氮層的厚度係藉由調整銅佔該射料粉末的重量百分比來調整於1μm~100μm之間。 According to the purpose of this creation, a composite material layered structure is provided, which includes an electroplating layer and a nitriding layer. Among them, the electroplating layer is located in the outer layer of the composite material layered structure, from the surface of the electroplating layer to the inside, it is formed by four metal layers of nickel-palladium alloy, nickel, copper, and nickel in sequence; and the nitriding layer is located in the composite material layered structure. The inner layer of the structure, and it has an expanded Asada scattered iron structure. The nitriding layer is the surface layer of a molded body. The molded body includes a nitriding layer and a base layer. The base layer is formed by mixing and granulating the shot powder with the binder into a molded body. The shot powder Containing iron and copper occupying 3~5wt% of the shot powder, the face-centered cubic crystal structure of the base layer accounts for 0%~15% of the base layer. The nitriding layer performs a precipitation hardening process on the preform, so that at least a part of the copper in the preform is concentrated on the surface of the preform, and the nitriding layer is formed on the surface of the base layer by a low-temperature nitriding process, In addition, the nitriding layer has an expanded matian scattered iron structure. The thickness of the nitriding layer is adjusted between 1 μm and 100 μm by adjusting the weight percentage of copper in the shot powder.

可選地，析出硬化製程係在480℃~650℃的溫度下進行。 Optionally, the precipitation hardening process is performed at a temperature of 480°C to 650°C.

可選地，低溫滲氮製程係在低於450℃的溫度下進行。 Optionally, the low-temperature nitriding process is performed at a temperature lower than 450°C.

可選地，射料粉末進一步包含碳、鉻、鎳、鈮、錳、矽、鉭、磷、硫或其組合。 Optionally, the shot powder further comprises carbon, chromium, nickel, niobium, manganese, silicon, tantalum, phosphorus, sulfur or a combination thereof.

可選地，射料粉末係為析出硬化型不銹鋼粉末。 Optionally, the shot powder is a precipitation hardening stainless steel powder.

可選地，結合劑包含聚縮醛、聚烯及蠟中的至少一種。 Optionally, the binding agent includes at least one of polyacetal, polyolefin, and wax.

本創作之複合材料層狀結構具有下述優點： The composite material layered structure of this creation has the following advantages:

(1)在本創作之複合材料層狀結構中，藉由調整銅佔射料粉末的重量百分比來調整滲氮層的厚度，因此能夠在不改變滲氮時間的情況下，製備具有不同滲氮層厚度的金屬元件，以配合不同應用所需之滲氮層厚度之規格，故而不受傳統滲氮廠需分別生產需要不同滲氮層厚度的金屬元件之問題，進而降低製備成本。 (1) In the composite material layered structure of this creation, the thickness of the nitriding layer is adjusted by adjusting the weight percentage of copper in the shot powder. Therefore, it is possible to prepare different nitriding layers without changing the nitriding time. The metal components with layer thicknesses can meet the specifications of the nitrided layer thickness required by different applications, so it is free from the problem that traditional nitriding plants need to separately produce metal components with different nitrided layer thicknesses, thereby reducing the production cost.

(2)在本創作之複合材料層狀結構中，以例如390℃之低溫滲氮製程，來製備具有膨脹型麻田散鐵(expanded martensite)結構的薄層滲氮層，因此除了能夠具有低能量耗損與低成本之優點外，還能夠符合未來金屬射出成型元件走向更為薄型化的趨勢。同時，由於膨脹型麻田散鐵比起燒結完成之一般型麻田散鐵具有更高硬度，因此具有係為膨脹型麻田散鐵的滲氮層具有高硬度，所以具有滲氮層的成型體能備有良好的表面耐磨耗特性。 (2) In the composite material layered structure of this creation, a low-temperature nitriding process at 390℃ is used to prepare a thin nitriding layer with an expanded martensite structure, so in addition to having low energy In addition to the advantages of loss and low cost, it can also meet the trend of thinner metal injection molding components in the future. At the same time, because the expanded Asada loose iron has a higher hardness than the sintered general Asada loose iron, the nitrided layer of the expanded Asada loose iron has high hardness, so the molded body with the nitrided layer can be equipped with Good surface wear characteristics.

(3)當滲氮層的厚度過厚時，會產生高應力，容易使滲氮層開裂；而當滲氮層的厚度過薄時，滲氮層的耐磨特性無法有效地展現，因此在本創作之複合材料層狀結構中，控制滲氮層的厚度在特定區間內，進而達到同時避免上述問題的目的。 (3) When the thickness of the nitriding layer is too thick, high stress will be generated and it is easy to crack the nitriding layer; and when the thickness of the nitriding layer is too thin, the wear resistance of the nitriding layer cannot be effectively displayed, so In the composite material layered structure of this creation, the thickness of the nitrided layer is controlled within a specific interval, thereby achieving the purpose of avoiding the above-mentioned problems at the same time.

(4)在本創作之複合材料層狀結構中，滲氮層係為一成型體之表層，成型體包含滲氮層及基底層。當選用的射料粉末中存在相對較高含量的銅時，由於先前能夠預先析出較多的銅，因此後續氮滲入表面的程度相對較低，滲氮層的厚度較薄。而又由於滲氮層雖為具高剛性的材料，但是滲氮層結構為膨脹型麻田散鐵結構，比原先基底的麻田散鐵結構晶格更為扭曲，而更易受到腐蝕，因此在滲氮層的厚度較薄的情況下，會與外界腐蝕來源起腐蝕反應的區域相對較少，比起厚滲氮層元件，薄的滲氮層的抗腐蝕性較佳。同時，選用的射料粉末中存在相對較高含量的銅時，由於銅係為沃斯田鐵(austenite)的穩定物質，因此能夠使得基底層存在較多具面心立方晶體結構的沃斯田鐵，面心立方對於抗腐蝕性比起麻田散鐵的體心立方結晶構造抗腐蝕性更佳，因此基底層的綜合抗腐蝕性較佳，且能增加強度、硬度、細化晶粒並提高切削性。所以，當選用的射料粉末中存在相對較高含量的銅時，無論是成型體的表面滲氮層或是其基底層的抗腐蝕性都較佳；此外，再藉由電鍍層作為抗腐蝕層覆蓋於滲氮層表面，可防止滲氮層遭受腐蝕而影響其耐磨耗特性，因此能夠獲得具加乘抗腐蝕效果的金屬元件。 (4) In the composite material layered structure of this creation, the nitriding layer is the surface layer of a molded body, and the molded body includes a nitriding layer and a base layer. When there is a relatively high content of copper in the selected shot powder, since more copper can be pre-precipitated, the degree of subsequent nitrogen infiltration into the surface is relatively low. The thickness of the nitriding layer is relatively thin. And because the nitriding layer is a material with high rigidity, the structure of the nitriding layer is an expanded Asada loose iron structure, which is more distorted than the original Asada loose iron structure, and is more susceptible to corrosion. Therefore, the nitriding layer is more susceptible to corrosion. When the thickness of the layer is thin, the area that will react with external corrosion sources is relatively small. Compared with the thick nitriding layer element, the thin nitriding layer has better corrosion resistance. At the same time, when there is a relatively high content of copper in the selected shot powder, because the copper system is a stable substance of austenite, it can make the base layer have more austenite with a face-centered cubic crystal structure. Iron, face-centered cubic has better corrosion resistance than the body-centered cubic crystal structure of Matian scattered iron, so the overall corrosion resistance of the base layer is better, and it can increase the strength, hardness, and refine the grain. Machinability. Therefore, when there is a relatively high content of copper in the selected shot powder, the corrosion resistance of either the surface nitriding layer or the base layer of the molded body is better; in addition, the electroplating layer is used as the corrosion resistance The layer covers the surface of the nitriding layer, which can prevent the nitriding layer from being corroded and affecting its wear resistance. Therefore, it is possible to obtain a metal element with an additional anti-corrosion effect.

1:複合材料層狀結構 1: Composite material layered structure

2:電鍍層 2: Electroplating layer

3:滲氮層 3: Nitriding layer

4:鎳-鈀合金 4: Nickel-palladium alloy

5:鎳 5: Nickel

6:銅 6: Copper

7:成型體 7: Molded body

8:基底層 8: basal layer

S100~S400:步驟 S100~S400: steps

第1圖係為本創作之複合材料層狀結構的一實例的電鍍層與滲氮層厚度分析圖。 Figure 1 is an analysis diagram of the thickness of the electroplating layer and the nitriding layer of an example of the composite material layered structure created by this invention.

第2圖係為本創作之複合材料層狀結構的一實例的分層結構圖，其係依據第1圖所描繪出複合材料層狀結構之電鍍層中各金屬層及滲氮層的相對關係。 Figure 2 is a layered structure diagram of an example of the composite material layered structure created by this creation. It is based on the first figure to depict the relative relationship between the metal layers and the nitriding layer in the electroplated layer of the composite material layered structure .

第3圖係為本創作之複合材料層狀結構中，具有滲氮層的成型體的製備方法的流程示意圖。 Figure 3 is a schematic flow diagram of the method for preparing a molded body with a nitriding layer in the composite material layered structure created.

第4(A)圖係為本創作實例1之複合材料層狀結構中，具有滲氮層的成型體的一實例的滲氮層厚度分析圖。 Figure 4(A) is an analysis diagram of the nitriding layer thickness of an example of a molded body with a nitriding layer in the composite material layered structure of Creative Example 1.

第4(B)圖係為本創作實例2之複合材料層狀結構中，具有滲氮層的成型體的一實例的滲氮層厚度分析圖。 Figure 4(B) is an analysis diagram of the nitriding layer thickness of an example of a molded body with a nitriding layer in the composite material layered structure of Creative Example 2.

第5(A)圖係為本創作實例1之複合材料層狀結構中，具有滲氮層的成型體的一實例的滲氮層抗腐蝕性分析圖。 Figure 5(A) is an analysis diagram of the corrosion resistance of the nitrided layer of an example of a molded body with a nitrided layer in the composite material layered structure of Creative Example 1.

第5(B)圖係為本創作實例2之複合材料層狀結構中，具有滲氮層的成型體的一實例的滲氮層抗腐蝕性分析圖。 Figure 5(B) is an analysis diagram of the corrosion resistance of the nitrided layer of an example of a molded body with a nitrided layer in the composite material layered structure of Creative Example 2.

第6圖係為本創作之複合材料層狀結構中，具有滲氮層的成型體的一實例的分層結構圖，其係依據第4(B)圖所描繪出具有滲氮層的成型體之滲氮層及基底層的相對關係。 Figure 6 is a layered structure diagram of an example of a molded body with a nitrided layer in the composite material layered structure created by this creation, which is based on Figure 4(B) depicts a molded body with a nitrided layer The relative relationship between the nitriding layer and the base layer.

為使上述目的、技術特徵及實際實施後之效益更易於使本領域具通常知識者所理解，將於下文中以實施例搭配圖式更詳細地說明。 In order to make the above objectives, technical features, and benefits after actual implementation easier to be understood by those with ordinary knowledge in the art, the embodiments will be described in more detail below with examples and drawings.

參照第1圖，其係為本創作之複合材料層狀結構1的一實例的電鍍層2與滲氮層3厚度分析圖。 Refer to Figure 1, which is an analysis diagram of the thickness of the electroplating layer 2 and the nitriding layer 3 of an example of the composite material layered structure 1 created for this creation.

第1圖係使用掃描式電子顯微鏡(Scanning Electron Microscope,SEM)所獲的本創作之複合材料層狀結構1的電鍍層2及滲氮層3厚度電子顯微鏡圖。圖中右側至左側係依序為複合材料層狀結構1的內層至外層，最右側係作為內層的滲氮層3，接著往左依序為由鎳5、銅6、鎳5、鎳-鈀合金4所形成作為外層的電鍍層2(請一併參照第2圖)。 Figure 1 is an electron microscope image of the thickness of the electroplating layer 2 and the nitriding layer 3 of the composite material layered structure 1 of this creation obtained by using a scanning electron microscope (Scanning Electron Microscope, SEM). From the right to the left in the figure are from the inner layer to the outer layer of the composite material layered structure 1, and the rightmost is the nitriding layer 3 as the inner layer, and then from the left to the left are nickel 5, copper 6, nickel 5, and nickel. -Plating layer 2 formed of palladium alloy 4 as an outer layer (please refer to Fig. 2 together).

由第1圖及第2圖可知，作為複合材料層狀結構1內層的滲氮層3，有許多密集的斑點狀集中於表面(即與電鍍層2的接觸面)，其為經低溫滲氮製程後，析出於表面的銅；如前文所述，雖滲氮層3具備良好的表面耐磨耗特性，但由於銅容易被氧化(腐蝕)，於較嚴苛的環境下使用將使耐磨耗特性降低，因此，需於滲氮層3外層作進一步的保護。在一實施例中，於滲氮層3外層以電鍍方式，依序鍍上鎳5、銅6、鎳5、鎳-鈀合金4等四層堆疊而成的電鍍層2作為保護層，防止滲氮層3的腐蝕。 It can be seen from Figures 1 and 2 that the nitrided layer 3, which is the inner layer of the composite material layered structure 1, has many dense spots concentrated on the surface (that is, the contact surface with the electroplating layer 2). After the nitrogen process, the copper precipitated on the surface; as mentioned above, although the nitriding layer 3 has good surface wear resistance characteristics, because the copper is easily oxidized (corroded), it will be resistant to use in harsher environments. The wear characteristics are reduced, therefore, the outer layer of the nitriding layer 3 needs to be further protected. In one embodiment, the outer layer of the nitriding layer 3 is electroplated, and the electroplating layer 2 composed of four layers of nickel 5, copper 6, nickel 5, and nickel-palladium alloy 4 is sequentially plated as a protective layer to prevent leaching. Corrosion of the nitrogen layer 3.

需要說明的是，本創作所使用的電鍍層不限於此，所述技術領域中具通常知識者可以任何習知用於抗腐蝕材料作為電鍍層，且可視需求堆疊一層或一層以上。 It should be noted that the electroplating layer used in this creation is not limited to this. Those with ordinary knowledge in the technical field can use any conventional anti-corrosion material as the electroplating layer, and stack one or more layers as required.

參照第3圖，其係為本創作之複合材料層狀結構1中，具有滲氮層3的成型體7的製備方法的流程示意圖。 Referring to Fig. 3, it is a schematic flow diagram of the method for preparing the molded body 7 with the nitrided layer 3 in the composite material layered structure 1 created by this invention.

步驟S100中，將射料粉末與結合劑混煉造粒為射料。射料粉末可包含鐵(Fe)以及佔射料粉末為3~5wt%的銅(Cu)。射料粉末中的鐵係可作為射料粉末之主成分。較佳地，鐵碳佔射料粉末的含量可為至少大於60wt%、65wt%、70wt%或75wt%。射料粉末可包含佔射料粉末為3wt%、3.1wt%、3.2wt%、3.3wt%、3.4wt%、3.5wt%、3.6wt%、3.7wt%、3.8wt%、3.9wt%、4wt%、4.1wt%、4.2wt%、4.3wt%、4.4wt%、4.5wt%、4.6wt%、4.7wt%、4.8wt%、4.9wt%、5wt%、或其之間之任何重量百分比的銅。 In step S100, the shot powder and the binder are mixed and granulated into shots. The shot powder may contain iron (Fe) and copper (Cu) occupying 3~5wt% of the shot powder. The iron in the shot powder can be used as the main component of the shot powder. Preferably, the content of iron-carbon in the shot powder may be at least greater than 60wt%, 65wt%, 70wt% or 75wt%. The shot powder may comprise 3wt%, 3.1wt%, 3.2wt%, 3.3wt%, 3.4wt%, 3.5wt%, 3.6wt%, 3.7wt%, 3.8wt%, 3.9wt%, 4wt% of the shot powder. %, 4.1wt%, 4.2wt%, 4.3wt%, 4.4wt%, 4.5wt%, 4.6wt%, 4.7wt%, 4.8wt%, 4.9wt%, 5wt%, or any weight percentage in between copper.

射料粉末可進一步包含碳(C)、鉻(Cr)、鎳(Ni)、鈮(Nb)、錳(Mn)、矽(Si)、鉭(Ta)、磷(P)、硫(S)或其組合。較佳地，碳佔射料粉末的含量可為小於1wt%，更佳地為小於0.07wt%。較佳地，鉻佔射料粉末的含量可為大於11wt%，更佳地為15wt%~18wt%。較佳地，鎳佔射料粉末的含量可為2wt%~7wt%，更佳地為3wt%~5wt%。較佳地，鈮佔射料粉末的含量可為小於1wt%，更佳地為0.15wt%~0.45wt%。較佳地，錳佔射料粉末的含量可為小於2wt%，更佳地為小於1wt%。較佳地，矽佔射料粉末的含量可為小於2wt%，更佳地為小於1wt%。較佳地，射料粉末的其餘部分可為鐵，也就是說，若射料粉末包含鐵、銅、碳、鉻、鎳、鈮、錳及矽，則扣除銅、碳、鉻、鎳、鈮、錳及矽的含量之外的組分皆為鐵。射料粉末可為析出硬化型不銹鋼粉末。在一實施例中，射料粉末可為17-4PH合金(UNS S17400)粉末。在一實施例中，結合劑可包含聚縮醛、聚烯及蠟中的至少一種。 The shot powder may further include carbon (C), chromium (Cr), nickel (Ni), niobium (Nb), manganese (Mn), silicon (Si), tantalum (Ta), phosphorus (P), sulfur (S) Or a combination. Preferably, the content of carbon in the shot powder may be less than 1 wt%, more preferably less than 0.07 wt%. Preferably, the content of chromium in the shot powder may be greater than 11wt%, More preferably, it is 15wt%-18wt%. Preferably, the content of nickel in the shot powder may be 2wt%-7wt%, more preferably 3wt%-5wt%. Preferably, the content of niobium in the shot powder may be less than 1 wt%, more preferably 0.15 wt% to 0.45 wt%. Preferably, the content of manganese in the shot powder may be less than 2wt%, more preferably less than 1wt%. Preferably, the content of silicon in the shot powder may be less than 2wt%, more preferably less than 1wt%. Preferably, the rest of the shot powder can be iron, that is, if the shot powder contains iron, copper, carbon, chromium, nickel, niobium, manganese, and silicon, then copper, carbon, chromium, nickel, and niobium are deducted The components other than the content of, manganese and silicon are all iron. The shot powder can be precipitation hardening stainless steel powder. In one embodiment, the shot powder may be 17-4PH alloy (UNS S17400) powder. In one embodiment, the bonding agent may include at least one of polyacetal, polyolefin, and wax.

步驟S200中，將射料成型以獲得預成型體。成型可為金屬射出成型、或所述技術領域中具有通常知識者為習知的任何成型製程。在一實施例中，步驟S200進一步包含：將射料射出成型為生胚；將生胚進行脫脂；以及將經脫脂後的生胚燒結，以獲得預成型體的步驟。 In step S200, injection molding is performed to obtain a preform. The molding can be metal injection molding, or any molding process known to those with ordinary knowledge in the technical field. In one embodiment, step S200 further includes the steps of: injecting the shot material into a green embryo; defatting the green embryo; and sintering the defatted green embryo to obtain a preform.

步驟S300中，將預成型體進行析出硬化製程，以使預成型體內的銅的至少一部份集中於預成型體的表面。事實上，預成型體內的銅係均勻析出在預成型體內部及表面，然而由於後續低溫滲氮製程的時間並非無限大，因此僅針對於析出於預成型體的表面的一部份的銅進行探討。在一實施例中，所屬技術領域中具有通常知識者可進一步使用習知的固溶處理步驟。較佳地，析出硬化製程係在480℃~650℃的溫度下進行；更佳地為550~650℃；又更佳地為570~620℃。較佳地，析出硬化製程係在1000~1300℉的溫度下進行；更佳地為1075~1225℉；又更佳地為1100~1200℉，在一實施例中，所屬技術領域中具有通常知識者可進一步使用依照所需的機械性質不同來調整固溶溫度與析出硬化參數。在一實施例中，析出硬化製程係為熱處理規範代號為H1150之析出硬化製程。 In step S300, the preform is subjected to a precipitation hardening process, so that at least a part of the copper in the preform is concentrated on the surface of the preform. In fact, the copper in the preform is uniformly precipitated inside and on the surface of the preform. However, since the time of the subsequent low-temperature nitriding process is not infinite, it is only performed on the copper precipitated on the surface of the preform. Explore. In one embodiment, those with ordinary knowledge in the technical field can further use the conventional solution treatment step. Preferably, the precipitation hardening process is performed at a temperature of 480°C to 650°C; more preferably 550 to 650°C; and more preferably 570 to 620°C. Preferably, the precipitation hardening process is carried out at a temperature of 1000~1300°F; more preferably 1075~1225°F; still more preferably 1100~1200°F. In one embodiment, there is general knowledge in the technical field. You can further adjust the solution temperature and precipitation hardening according to the required mechanical properties parameter. In one embodiment, the precipitation hardening process is a precipitation hardening process whose heat treatment specification code is H1150.

步驟S400中，將經析出硬化製程的預成型體進行低溫滲氮製程，以使氮擴散，亦或是稱為滲入其中而獲得具有滲氮層3的成型體7(請一併參照第6圖)。滲氮層3可具有膨脹型麻田散鐵結構。較佳地，低溫滲氮製程係在低於450℃的溫度下進行；更佳地為低於440℃；又更佳地為低於400℃，其中當溫度過低時，會導致原先的麻田散鐵結構的滲氮量偏低，不會轉成膨脹型麻田散鐵結構；而當溫度過高時，會導致則膨脹型麻田散鐵結構不穩定，可能會轉變成Fe₂N、Fe₃N及/或Fe₄N，且以一般金屬射出成型廠的成本角度而言，高溫滲氮製程不符合經濟效益。在一實施例中，低溫滲氮製程在390℃的溫度下進行。在一實施例中，低溫滲氮製程的持續時間越長，滲氮層3的厚度越厚，然而製造成本也會因時間過長而無謂地增加。 In step S400, the preform that has undergone the precipitation hardening process is subjected to a low-temperature nitriding process to diffuse nitrogen, or it is called infiltration, to obtain a molded body 7 having a nitriding layer 3 (please also refer to Figure 6). ). The nitriding layer 3 may have an expanded Asada loose iron structure. Preferably, the low-temperature nitriding process is carried out at a temperature lower than 450°C; more preferably lower than 440°C; and even more preferably lower than 400°C, wherein when the temperature is too low, it will cause the original hemp The nitriding amount of the loose iron structure is too low, and it will not be converted into an expanded Asada loose iron structure; and when the temperature is too high, the expanded Asada loose iron structure will be unstable and may be transformed into Fe ₂ N, Fe ₃ N and/or Fe ₄ N, and from the perspective of the cost of a general metal injection molding plant, the high-temperature nitriding process is not economical. In one embodiment, the low-temperature nitriding process is performed at a temperature of 390°C. In one embodiment, the longer the duration of the low-temperature nitriding process, the thicker the thickness of the nitriding layer 3, however, the manufacturing cost will increase unnecessarily due to the long time.

在一實施例中，滲氮層3的厚度可藉由調整銅佔射料粉末的重量百分比來調整。當射料粉末包含佔射料粉末3~5wt%的銅時，滲氮層3的厚度較佳地為1μm~100μm；更佳地為5μm~70μm；又更佳地為10μm~50μm，其中當滲氮層3的厚度小於1μm時，會導致難以展現耐磨耗性質之負面影響；而當滲氮層3的厚度大於100μm時，會導致應力過大滲氮層3表面容易開裂之負面影響。 In one embodiment, the thickness of the nitriding layer 3 can be adjusted by adjusting the weight percentage of copper in the shot powder. When the shot powder contains 3~5wt% of copper, the thickness of the nitriding layer 3 is preferably 1μm~100μm; more preferably 5μm~70μm; and more preferably 10μm~50μm. When the thickness of the nitriding layer 3 is less than 1 μm, it will be difficult to exhibit the negative effect of wear resistance; and when the thickness of the nitriding layer 3 is greater than 100 μm, it will cause the negative effect of excessive stress on the surface of the nitriding layer 3 and easy cracking.

請一併參照第6圖，在一實施例中，成型體7可進一步包含基底層8。基底層8係為即使經過低溫滲氮製程後，因為擴散作用的限制，所以氮未滲入其中的層。較佳地，基底層8的面心立方晶體結構可佔基底層8的0%~15%；更佳地為1%~12%；又更佳地為2%~10%，其中當面心立方晶體結構佔基底層8的比例過小時，會導致抗腐蝕能力越差之負面影響。 Please also refer to FIG. 6. In one embodiment, the molded body 7 may further include a base layer 8. The base layer 8 is a layer in which nitrogen does not penetrate even after the low-temperature nitriding process, due to the limitation of diffusion. Preferably, the face-centered cubic crystal structure of the base layer 8 can account for 0% to 15% of the base layer 8; more preferably, 1% to 12%; and more preferably 2% to 10%, where the face-centered cubic crystal structure If the ratio of the crystal structure to the base layer 8 is too small, it will lead to a negative effect of poorer corrosion resistance.

以下搭配實例，詳細地說明本創作之製備方法及其複合材料層狀結構。 The following examples are used to illustrate the preparation method of this creation and its composite material layered structure in detail.

需先說明的是，析出硬化型不銹鋼材料係為一種於美國鋼鐵協會(AISI)編號為600系不銹鋼的材料。析出硬化型不銹鋼材料中的組分中除了包含鉻與鎳之外，還進一步包含能夠被析出硬化的元素，例如：銅、鋁、鈦等元素。因此，當對析出硬化型不銹鋼材料進行析出硬化製程時，能夠增加材料的降伏強度。其中，析出硬化製程至少包含固溶熱處理與析出熱處理。固溶熱處理將欲析出的第二相固溶於基底相中而形成單一相。析出熱處理則是將第二相析出，而使得材料的表面硬化並提升強度與剛性。 It should be noted that the precipitation-hardening stainless steel material is a material numbered 600 series stainless steel by the American Iron and Steel Institute (AISI). In addition to chromium and nickel, the composition of the precipitation hardening stainless steel material also further contains elements that can be precipitation hardened, such as copper, aluminum, titanium and other elements. Therefore, when the precipitation hardening stainless steel material is subjected to a precipitation hardening process, the yield strength of the material can be increased. Among them, the precipitation hardening process includes at least solution heat treatment and precipitation heat treatment. The solution heat treatment dissolves the second phase to be precipitated in the base phase to form a single phase. Precipitation heat treatment is to precipitate the second phase, so that the surface of the material is hardened and the strength and rigidity are improved.

另一方面，滲氮製程係指在特定溫度下，於特定介質中，使得氮原子滲入元件表面的熱處理方法，並藉由滲入元件表面的氮原子改變元件表面的化學成分及晶格排列，而獲得具有更高硬度與耐磨特性的表面。一般而言，滲氮製程依據不同溫度分為高溫滲氮製程與低溫滲氮製程。高溫滲氮製程的溫度約為500~700℃之間，而低溫滲氮製程則於低於500℃，甚至是更低的溫度下進行。在不同溫度下進行滲氮製程所產生的化合物或結構不同。其中，在高溫滲氮製程處理後，會產生其的特性穩定且耐蝕性高的化合物Fe₄N；而在低溫滲氮製程處理後，則因氮原子***晶格中，導致晶格扭曲，也因為溫度相對低，能量不足，因此無法形成穩定的化合物，並致使其較為容易被腐蝕。 On the other hand, the nitriding process refers to a heat treatment method in which nitrogen atoms infiltrate the surface of the device at a specific temperature and in a specific medium, and the chemical composition and lattice arrangement of the surface of the device are changed by the nitrogen atoms that infiltrate the surface of the device. Obtain a surface with higher hardness and wear resistance. Generally speaking, the nitriding process is divided into a high-temperature nitriding process and a low-temperature nitriding process according to different temperatures. The temperature of the high-temperature nitriding process is about 500-700°C, while the low-temperature nitriding process is performed at a temperature lower than 500°C or even lower. The compounds or structures produced by the nitriding process at different temperatures are different. Among them, after the high temperature nitriding process, the compound Fe ₄ N with stable characteristics and high corrosion resistance will be produced; and after the low temperature nitriding process, the nitrogen atoms are inserted into the crystal lattice, resulting in distortion of the crystal lattice. Because the temperature is relatively low and the energy is insufficient, stable compounds cannot be formed, making it easier to be corroded.

在以下實例及比較例中，射料粉末選用17-4PH合金(UNS S17400)粉末，其中以射料粉末的總重量為基準，銅的含量3wt%~5wt%；為碳的含量

0.07wt%；鉻的含量為15wt%~17.5wt%；鎳的含量為3wt%~5wt%；鈮的含量0.15wt%~0.45wt%；錳的含量

1wt%；矽的含量

1wt%；且其餘為鐵。結合劑選用組成為60至80wt%POM、2至5wt%高密度聚乙烯(HDPE)、2至5wt%經順丁烯二酸酐改質的線性低密度聚乙烯(maleic anhydride modified low-density polyethylene，OREVAC^® 18302N，密度為0.912g/cm³)、2至6wt%硬脂酸(SA，Stearic Acid)、4至20wt%褐媒蠟(Montan wax)及1至5wt%乙烯-醋酸乙烯共聚物(ethylene vinyl acetate copolymer,EVA)的結合劑。將射料粉末與結合劑混煉造粒為射料，並將射料射出成型、脫脂及燒結，以獲得預成型體。接著，將預成型體進行析出硬化製程與低溫滲氮製程並獲得具有滲氮層3及基底層8之成型體7。其中，析出硬化製程選用H1150之析出硬化製程；以及低溫滲氮製程選用的溫度為390℃且持續時間為8小時及9.5小時。其詳細參數示於表1。 In the following examples and comparative examples, the shot powder is selected from 17-4PH alloy (UNS S17400) powder, which is based on the total weight of the shot powder, and the content of copper is 3wt%~5wt%; it is the content of carbon

0.07wt%; the content of chromium is 15wt%~17.5wt%; the content of nickel is 3wt%~5wt%; the content of niobium is 0.15wt%~0.45wt%; the content of manganese

1wt%; content of silicon

1wt%; and the rest is iron. The binder is composed of 60 to 80wt% POM, 2 to 5wt% high density polyethylene (HDPE), 2 to 5wt% maleic anhydride modified low-density polyethylene (maleic anhydride modified low-density polyethylene, OREVAC ^® 18302N, density 0.912g/cm ³ ), 2 to 6wt% stearic acid (SA, Stearic Acid), 4 to 20wt% Montan wax and 1 to 5wt% ethylene-vinyl acetate copolymer ( ethylene vinyl acetate copolymer, EVA) binder. The injection powder and the binder are mixed and granulated into the injection material, and the injection material is injection molded, degreased and sintered to obtain a preform. Next, the preform is subjected to a precipitation hardening process and a low-temperature nitriding process to obtain a molded body 7 having a nitriding layer 3 and a base layer 8. Among them, the precipitation hardening process adopts the precipitation hardening process of H1150; and the low temperature nitriding process adopts a temperature of 390°C and a duration of 8 hours and 9.5 hours. The detailed parameters are shown in Table 1.

參照第4圖，其係為本創作之複合材料層狀結構1的一實例的滲氮層3厚度分析圖。第4(A)圖及第4(B)圖係分別為使用電子微探儀(Electron Probe X-Ray Microanalyzer，EPMA)所獲的本創作的實例1及實例2的滲氮層3厚度影像映射(mapping image)的分析圖。 Refer to Figure 4, which is an analysis diagram of the thickness of the nitriding layer 3 of an example of the composite material layered structure 1 created for this creation. Figure 4(A) and Figure 4(B) are respectively the image mapping of the nitride layer 3 thickness of Example 1 and Example 2 of this creation obtained by using Electron Probe X-Ray Microanalyzer (EPMA) (mapping image) analysis graph.

如第4圖所示，可知實例1的滲氮層3厚度為25μm，且實例2的滲氮層3厚度為15μm。另外，比較例1的滲氮層3厚度亦為15μm(未圖示)。代表，如實例1與比較例1所示，目前業界係採用控制滲氮製程的時間長短來控制滲氮層3厚度，也就是說滲氮時間越長，所獲得的滲氮層3的厚度越厚。然而，如實例1與實例2所示，在本創作之複合材料層狀結構1中，藉由控制射料粉末中的銅含量的多寡來控制滲氮層3的厚度，也就是說，銅含量越高，滲氮層3厚度越薄。其可能的原因為，17-4PH合金粉末中的銅在H1150熱處理析出硬化製程中，會與基底層8的麻田散鐵形成整合型界面(coherent interface)，當銅含量越多，析出的量會越多，進而影響後續在低溫滲氮製程中的氮原子活性，亦即當銅濃度越高時，導致氮原子活性會相對變低，進而導致氮原子擴散進入成型體7的表面的深度會變淺，因此獲得厚度較薄的滲氮層3。 As shown in FIG. 4, it can be seen that the thickness of the nitrided layer 3 of Example 1 is 25 μm, and the thickness of the nitrided layer 3 of Example 2 is 15 μm. In addition, the thickness of the nitrided layer 3 of Comparative Example 1 was also 15 μm (not shown). Representative, as shown in Example 1 and Comparative Example 1, the industry currently uses the length of the nitriding process to control the thickness of the nitriding layer 3. That is to say, the longer the nitriding time, the greater the thickness of the nitriding layer 3 obtained. thick. However, as shown in Examples 1 and 2, in the composite material layered structure 1 of this creation, the thickness of the nitriding layer 3 is controlled by controlling the amount of copper in the shot powder, that is, the copper content The higher the thickness, the thinner the nitriding layer 3 is. The possible reason is that the copper in the 17-4PH alloy powder will form a coherent interface with the Asada scattered iron of the base layer 8 during the H1150 heat treatment and precipitation hardening process. When the copper content is more, the amount of precipitation will decrease. The more, it will affect the nitrogen atom activity in the subsequent low-temperature nitriding process, that is, when the copper concentration is higher, As a result, the activity of nitrogen atoms will be relatively low, and the depth of diffusion of nitrogen atoms into the surface of the molded body 7 will become shallow, so that a nitrided layer 3 with a thinner thickness is obtained.

接續上述，將實例1及2進行硬度測試。硬度測試係使用維氏硬度儀，且其測試結果示於表2。一般而言，硬度數值與耐磨耗特性呈正相關，硬度越高則耐磨耗特性越佳。 Following the above, the hardness test of Examples 1 and 2 was carried out. The hardness test system uses a Vickers hardness tester, and the test results are shown in Table 2. Generally speaking, the value of hardness is positively correlated with wear resistance. The higher the hardness, the better the wear resistance.

如表2所示，滲氮後結構為膨脹型麻田散鐵結構，因此由H1150析出硬化熱處理後的硬度由300Hv~400Hv提高到滲氮後的800Hv~900Hv，所以能夠提升耐磨耗特性。同時，在金屬射出成型技術中，由於膨脹型麻田散鐵結構是由氮元素大量固溶於麻田散鐵內而造成嚴重晶格扭曲，雖然具有高硬度，但是滲氮後整體金屬元件的耐腐蝕性係為一個重要的課題。 As shown in Table 2, the structure after nitriding is an expanded Asada loose iron structure, so the hardness after H1150 precipitation hardening heat treatment is increased from 300Hv~400Hv to 800Hv~900Hv after nitriding, so the wear resistance characteristics can be improved. At the same time, in the metal injection molding technology, because the structure of the expanded Asada loose iron is caused by a large amount of nitrogen in the Asada loose iron, the crystal lattice is distorted. Although it has high hardness, the overall metal components are corrosion resistant after nitriding. Sexuality is an important topic.

參照第5圖，係為本創作之成型體7的一實例的滲氮層3抗腐蝕性分析圖。第5(A)圖及第5(B)圖係分別為本創作的實例1及實例2的抗腐蝕性光學顯微鏡圖。其中，選用乙醇(ethanol，100ml)、HCl(40ml)與CuCl₂(5g)的混合液體作為腐蝕液，進行抗腐蝕測試。 Refer to Fig. 5, which is an analysis diagram of the corrosion resistance of the nitriding layer 3 of an example of the molded body 7 of this creation. Fig. 5(A) and Fig. 5(B) are the corrosion-resistant optical microscope images of Example 1 and Example 2 of this creation, respectively. Among them, a mixed liquid of ethanol (100ml), HCl (40ml) and CuCl ₂ (5g) was selected as the corrosive liquid for the corrosion resistance test.

如第5圖所示，實例2之滲氮層3的抗腐蝕性明顯優於實例1。實例1之滲氮層3在腐蝕3分鐘後即明顯變暗，但實例2之滲氮層3則仍維持原先白色的狀態，當腐蝕時間增加到6分鐘才明顯變暗。 As shown in Figure 5, the corrosion resistance of the nitrided layer 3 of Example 2 is significantly better than that of Example 1. The nitriding layer 3 of Example 1 was obviously darkened after 3 minutes of etching, but the nitriding layer 3 of Example 2 still maintained the original white state, and it became significantly darker when the etching time was increased to 6 minutes.

接續上述，將實例1與實例2進行電子背向散射繞射(EBSD)進行相分率(phase fraction)分析。且其測試結果示於表3。 Following the above, Example 1 and Example 2 were subjected to electron backscatter diffraction (EBSD) for phase fraction analysis. And its test results are shown in Table 3.

在內部的基底層8結構中，由於銅元素是沃斯田鐵的穩定元素，因此含有高銅含量的射料粉末將會使基底層8內的FCC相的沃斯田鐵較多。又因FCC相的沃斯田鐵本身的抗腐蝕性佳，因此含有越多FCC的相沃斯田鐵，越具抗腐蝕性。如表3所示，實例2中存在FCC相的殘留沃斯田鐵(retained austenite)比例是實例1的將近4倍，因此在基底層8中，實例2具有更佳的抗腐蝕性。 In the internal base layer 8 structure, since copper is a stable element of austenitic iron, the shot powder with high copper content will increase the austenitic iron in the FCC phase in the base layer 8. In addition, because FCC-phase austenitic iron has good corrosion resistance, the more FCC-phase austenitic iron is contained, the more corrosion-resistant it is. As shown in Table 3, the ratio of retained austenite with FCC phase in Example 2 is nearly 4 times that of Example 1. Therefore, in the base layer 8, Example 2 has better corrosion resistance.

接續上述，基於實例1與實例2的滲氮層3與基底層8的抗腐蝕性，觀察實例1與實例2的整個成型體7的抗腐蝕性，其結果如表4所示。 Following the above, based on the corrosion resistance of the nitrided layer 3 and the base layer 8 of Example 1 and Example 2, the corrosion resistance of the entire molded body 7 of Example 1 and Example 2 was observed. The results are shown in Table 4.

如表4所示，在實例1中，由於高度易受腐蝕的滲氮層3的厚度較厚，因此抗腐蝕性較差；又由於在基底層8中的FCC的相沃斯田鐵含量較少，因此抗腐蝕性亦較差。然而，在實例2中，由於高度易受腐蝕的滲氮層3的厚度較薄，因此抗腐蝕性較佳；又由於在基底層8中的FCC的相沃斯田鐵含量較多，因此抗腐蝕性亦較佳。因此整體觀之，實例2的抗腐蝕性優於實例1。 As shown in Table 4, in Example 1, because the thickness of the nitriding layer 3, which is highly susceptible to corrosion, is thicker, the corrosion resistance is poor; and because the FCC phase austenitic iron content in the base layer 8 is less ,because This corrosion resistance is also poor. However, in Example 2, since the thickness of the nitriding layer 3, which is highly susceptible to corrosion, is thinner, the corrosion resistance is better; and because the FCC phase austenitic iron content in the base layer 8 is higher, it is resistant to corrosion. Corrosion is also better. Therefore, overall, the corrosion resistance of Example 2 is better than that of Example 1.

以上所述僅為舉例性，而非為限制性者。任何未脫離本創作之精神與範疇，而對其進行之等效修改或變更，均應包含於申請專利範圍中。 The above descriptions are merely illustrative and not restrictive. Any equivalent modifications or changes made without departing from the spirit and scope of this creation shall be included in the scope of the patent application.

1:複合材料層狀結構 1: Composite material layered structure

2:電鍍層 2: Electroplating layer

3:滲氮層 3: Nitriding layer

4:鎳-鈀合金 4: Nickel-palladium alloy

5:鎳 5: Nickel

6:銅 6: Copper

Claims

一種複合材料層狀結構，其包含：一電鍍層；以及一滲氮層，其中，該電鍍層係作為該複合材料層狀結構的外層，該滲氮層係作為該複合材料層狀結構的內層。 A composite material layered structure, comprising: an electroplating layer; and a nitriding layer, wherein the electroplating layer is used as the outer layer of the composite material layered structure, and the nitriding layer is used as the inner layer of the composite material layered structure Floor.

如請求項1所述之複合材料層狀結構，其中該電鍍層表面至內部係依序由鎳-鈀合金、鎳、銅、鎳等四層金屬層所形成。 The composite material layered structure according to claim 1, wherein the surface to the inside of the electroplating layer are sequentially formed of four metal layers such as nickel-palladium alloy, nickel, copper, and nickel.

如請求項1所述之複合材料層狀結構，其中該滲氮層係為一成型體之表層，該成型體包含該滲氮層及一基底層。 The composite material layered structure according to claim 1, wherein the nitrided layer is a surface layer of a molded body, and the molded body includes the nitrided layer and a base layer.

如請求項3所述之複合材料層狀結構，其中該基底層係由一射料粉末與一結合劑混煉造粒之一射料加以成型為一預成型體而形成，該射料粉末包含鐵以及佔該射料粉末為3~5wt%的銅，該基底層的面心立方晶體結構佔該基底層的0%~15%；以及該滲氮層係將該預成型體進行一析出硬化製程，以使該預成型體內的銅的至少一部份集中於該預成型體的表面，並以一低溫滲氮製程使該滲氮層形成於該基底層之表面，該滲氮層係具有膨脹型麻田散鐵結構，該滲氮層的厚度係藉由調整銅佔該射料粉末的重量百分比來調整於1μm~100μm之間。 The composite material layered structure according to claim 3, wherein the base layer is formed by kneading a shot powder and a binder to form a preform, and the shot powder comprises Iron and copper occupying 3~5wt% of the shot powder, the face-centered cubic crystal structure of the base layer accounts for 0%~15% of the base layer; and the nitriding layer performs a precipitation hardening on the preform Process to make at least part of the copper in the preform concentrated on the surface of the preform, and a low-temperature nitriding process is used to form the nitriding layer on the surface of the base layer, and the nitriding layer has Expanded Asada scattered iron structure, the thickness of the nitriding layer is adjusted between 1 μm and 100 μm by adjusting the weight percentage of copper in the shot powder.

如請求項4所述之複合材料層狀結構，其中該析出硬化製程係在500~700℃的溫度下進行。 The composite material layered structure according to claim 4, wherein the precipitation hardening process is performed at a temperature of 500 to 700°C.

如請求項4所述之複合材料層狀結構，其中該低溫滲氮製程係在低於480℃的溫度下進行。 The composite material layered structure according to claim 4, wherein the low-temperature nitriding process is It is carried out at a temperature below 480°C.

如請求項4所述之複合材料層狀結構，其中該射料粉末進一步包含碳、鉻、鎳、鈮、錳、矽、鉭、磷、硫或其組合。 The composite material layered structure according to claim 4, wherein the shot powder further comprises carbon, chromium, nickel, niobium, manganese, silicon, tantalum, phosphorus, sulfur or a combination thereof.

如請求項4所述之複合材料層狀結構，其中該射料粉末係為析出硬化型不銹鋼粉末。 The composite material layered structure according to claim 4, wherein the shot powder is a precipitation hardening stainless steel powder.

如請求項4所述之複合材料層狀結構，其中該結合劑包含聚縮醛、聚烯及蠟中的至少一種。 The composite material layered structure according to claim 4, wherein the bonding agent comprises at least one of polyacetal, polyolefin, and wax.