WO2019205335A1 - 一种界面增强的复合材料及其用途 - Google Patents

一种界面增强的复合材料及其用途 Download PDF

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Publication number
WO2019205335A1
WO2019205335A1 PCT/CN2018/098077 CN2018098077W WO2019205335A1 WO 2019205335 A1 WO2019205335 A1 WO 2019205335A1 CN 2018098077 W CN2018098077 W CN 2018098077W WO 2019205335 A1 WO2019205335 A1 WO 2019205335A1
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Prior art keywords
substrate
composite material
film layer
material according
polymer
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PCT/CN2018/098077
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English (en)
French (fr)
Inventor
程鑫
罗冰清
田野
黄兴隆
朴英哲
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Southern University of Science and Technology
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Southern University of Science and Technology
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    • 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/10—Glass or silica
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • 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
    • 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
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/028—Physical treatment to alter the texture of the substrate surface, e.g. grinding, polishing
    • 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
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • 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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00

Definitions

  • the present disclosure is in the field of composite materials, for example, in relation to an interface enhanced composite and its use.
  • Coating technology is widely used in the industrial field. Depending on the material of the coating, the methods available can be varied, including spray coating, spin coating, lifting, evaporation, sputtering and chemical vapor deposition. Coating on flexible or hard substrates to form a layered composite that integrates the properties of different materials to create new properties and applications.
  • the film produced by various coating techniques has different degrees of stress, including shrinkage stress and expansion stress, which may result in adhesion between the coating and the substrate. Strong, the coating is easy to fall off, peel off or crack, and the life is greatly shortened, which brings great obstacles to practical application.
  • the stability of the plating on the flexible substrate is worse than that of the hard substrate, mainly because the mechanical strength of the flexible substrate is low, large surface stress causes deformation of the material, and at the same time, since the flexible substrate is in use It will be repeatedly bent, resulting in fatigue effect, greatly reducing the service life of the coating.
  • the plating layer may be broken or detached from the substrate due to internal stress and low adhesion of the plating layer.
  • the coating or the substrate may be cracked, and the propagation of the crack causes a large-area coating to be broken, and the material properties are degraded or even completely lost.
  • the present disclosure provides an interface-reinforced composite material and a use thereof, which has strong interfacial bonding force, wear resistance, and can significantly reduce cracks generated by bending, has high service stability, and can be used for a blue LED (light emitting diode) device.
  • the present disclosure provides an interface-reinforced composite material comprising: a substrate and a film layer;
  • the surface of the substrate has a micro-nano scale recessed structure
  • a face having the recessed structure on the substrate is bonded to the film layer.
  • the present disclosure increases the total contact area between the film layer and the substrate by processing the micro-nano-scale recessed structure on the substrate, and improves the bonding strength of the two, thereby making the composite material resistant to crack generation during bending. Stronger; the interfacial structure in which the film layer and the substrate cross each other improves the wear resistance of the material, and can reduce or even eliminate the residual stress in the material and prolong the service life of the material.
  • the substrate is a hard substrate or a flexible substrate, and may be, for example, an organic glass substrate, a PC (polycarbonate) substrate, a silicone substrate or a sapphire substrate, or the like.
  • the film layer has a thickness of 10 nm to 1000 ⁇ m; for example, 10 nm, 20 nm, 50 nm, 100 nm, 200 nm, 300 nm, 500 nm, 800 nm, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m. 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 15 ⁇ m, 20 ⁇ m, 50 ⁇ m, 100 ⁇ m, 200 ⁇ m, 500 ⁇ m, 800 ⁇ m or 1000 ⁇ m or the like.
  • the film layer is a metal film layer, a ceramic film layer or a polymer film layer.
  • the material of the metal thin film layer is selected from one or a combination of at least two of gold, silver, platinum, nickel, chromium or copper; typical but non-limiting examples of the combination are: gold Combination with silver, combination of gold and platinum, combination of nickel and chromium, combination of chromium and copper.
  • the material of the ceramic film layer is selected from one or a combination of at least two of an oxide ceramic, a nitride ceramic or a halide ceramic; a typical but non-limiting example of the combination is an oxide.
  • the material of the polymer film layer is an engineering polymer material or a functional polymer material.
  • the engineering polymer is PC (polycarbonate), PMMA (polymethyl methacrylate), PS (polystyrene) or PEEK (polyether ether ketone).
  • the functional polymer material is a polymer semiconductor material, a polymer piezoelectric material, a polymer biodegradable material or a polymer magnetic material.
  • the depth of the recessed structure is greater than or equal to the thickness of the thin film layer.
  • the film layer When the depth of the recessed structure is greater than or equal to the thickness of the film layer, the film layer has a stronger bonding force with the substrate, and the composite material has better bending resistance.
  • the recessed structures are periodically arranged on the substrate.
  • the arrangement period of the recess structure is 20 nm to 1000 ⁇ m; for example, it may be 20 nm, 50 nm, 100 nm, 200 nm, 300 nm, 500 nm, 800 nm, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 15 ⁇ m, 20 ⁇ m, 50 ⁇ m, 100 ⁇ m, 200 ⁇ m, 500 ⁇ m, 800 ⁇ m or 1000 ⁇ m or the like.
  • the periodically arranged recessed structures can make the properties of the composite material more uniform, and the adhesion and bending resistance of the film layer are stronger.
  • the present disclosure is not particularly limited to the shape of the recessed structure.
  • the planar shape of the recessed structure (the shape presented on the surface of the substrate) may be a circle, a triangle, or a square; the recessed structure may be along the depth direction. Gradually expand, gradually shrink or remain unchanged.
  • the circular contour is more uniform, which helps to eliminate stress concentration, so the shape of the concave structure on the surface of the substrate is preferably circular; in order to further improve the adhesion of the thin film layer, the concave structure can be made along the depth The direction is gradually expanding.
  • a person skilled in the art can select the size of the recessed structure according to actual needs.
  • the recessed structure may have a depth of 10 nm to 1000 ⁇ m; when the planar shape of the recessed structure is circular, the diameter may be 10 nm to 1000 ⁇ m. When the shape of the recessed structure is irregular in plan view, the diameter of the circumscribed circle may be 10 nm to 1000 ⁇ m.
  • the method for forming the recess structure is selected from the group consisting of UV-cured nanoimprint, thermoplastic nanoimprint, planar nanoimprint, roll-to-roll nanoimprint, roll-to-plate nanoimprint, and reticle exposure.
  • UV-cured nanoimprint thermoplastic nanoimprint
  • planar nanoimprint planar nanoimprint
  • roll-to-roll nanoimprint roll-to-plate nanoimprint
  • reticle exposure One or a combination of at least two of projection exposure, near field exposure, laser interference, laser direct writing, or mechanical engraving.
  • the thin film layer is formed by magnetron sputtering, thermal evaporation, plasma chemical vapor deposition (PECVD), pulsed laser deposition (PLD), atomic layer deposition (ALD). ), liquid spin-coating, spray coating, dip coating, in situ polymerization or hot pressing.
  • PECVD plasma chemical vapor deposition
  • PLD pulsed laser deposition
  • ALD atomic layer deposition
  • the present disclosure provides the use of the above composite material.
  • the composite materials provided by the present disclosure can be used for different purposes by selecting different substrate and film layer materials. Illustratively, the following applications can be cited:
  • a micro-nano-scale recessed structure is processed on the surface of the ceramic substrate, and then a semiconductor film is plated.
  • a micro-nano-scale recessed structure is processed on the surface of a sapphire substrate, and then a GaN (gallium nitride) film is grown, and the composite material formed is an ideal substrate for a blue LED device.
  • GaN gallium nitride
  • micro-nano scale recessed structure is processed on the surface of the ceramic substrate, and then the polymer film is composited.
  • a micro-nano-scale concave structure is processed on the surface of the glass film substrate, and then the planar polymer material is pressed together; or the ultraviolet curing monomer is cast on the surface of the glass film substrate to form a composite material after polymerization.
  • micro-nano scale recessed structure is processed on the surface of the polymer substrate, and then the metal film is plated.
  • a micro-nano scale recessed structure is processed on a surface of a PI (polyimide) or PEN (polyethylene naphthalate) substrate, and then a copper thin film is vapor-deposited for use as a flexible circuit board.
  • PI polyimide
  • PEN polyethylene naphthalate
  • micro-nano scale recessed structure is processed on the surface of the polymer substrate, and then the ceramic film is plated.
  • a micro-nano-scale recessed structure is processed on the surface of the PMMA substrate, and a silicon dioxide film is coated for the OLED or QLED package; a micro-nano-scale recessed structure is processed on the surface of the PC substrate, and a silicon oxide film is coated. On the windshield.
  • micro-nano scale recessed structure is processed on the surface of the polymer substrate, and then the polymer film is composited.
  • a micro-nano scale recessed structure is processed on the surface of the PC or PMMA substrate at a temperature between the two Tg, and the hot pressed PEEK (poly Ether ether ketone), PPO (polyphenylene ether) or PI film to form a composite film that combines the advantages of both materials; a micro-nano-scale recessed structure is treated on the surface of the cured epoxy resin, and then a functional coating is applied for Aircraft body, car body or baffle.
  • PEEK poly Ether ether ketone
  • PPO polyphenylene ether
  • the present disclosure has the following beneficial effects:
  • Forming a micro-nano-scale recessed structure on the surface of the substrate has the following advantages: (1) increasing the total contact area between the thin film layer and the substrate material, increasing the adhesion of the thin film layer on the substrate; and (2) the thin film layer and The substrates cross each other to increase the frictional force between the film layer and the substrate in the horizontal direction, and greatly enhance the friction resistance and service stability of the film layer in the case of horizontal friction or repeated bending of the substrate; (3)
  • the coating technique leaves more or less residual stress in the film layer, and the micro-nano-scale recess structure can effectively reduce or even eliminate the residual stress in the film layer, making the film layer more stable on the substrate surface, and at the same time The reduction and elimination of the residual stress also causes the thick film layer to not be broken due to too much residual stress; (4) the micro/nano structure itself can bring about novel optical or electrical properties, such as a structure with a period of several hundred nanometers, Strong scattering of natural light; or the conductive film layer will increase the conductivity of the film
  • FIG. 1 is a schematic cross-sectional structural view of a composite material provided in Examples 1-3;
  • 11 is a substrate
  • 12 is a film layer
  • d is a substrate thickness
  • t is a film layer thickness
  • h is a hole depth
  • w is a hole diameter
  • p is a hole period.
  • Figure 2b is a surface SEM photograph of the composite provided in Example 1.
  • Figure 2c is a surface SEM photograph of the composite provided in Example 2.
  • Figure 2d is a surface SEM photograph of the composite provided in Example 3.
  • Figure 3 is a graph showing the relationship between the nanoindentation load and the indentation depth of the composite materials provided in Examples 1-3 and Comparative Example 1.
  • Figure 5 is a graph of surface hardness data for composites provided in Examples 1-3 and Comparative Example 1.
  • Glass materials are widely used in vehicle windows or on the surface of electronic devices because of their transparency.
  • the disadvantage of glass materials is that they are fragile and heavy. Modern vehicle lightweighting can save energy consumption of vehicles and reduce environmental pollution, so it is receiving more and more attention.
  • Engineering plastics, such as PMMA and PC are lightweight, transparent and non-fragile, making them ideal glass substitutes.
  • the mechanical properties of polymer materials are relatively poor, such as Young's modulus, hardness, and surface scratch resistance, making them incapable of completely replacing glass.
  • the windshield of a car due to the back and forth scraping of the wiper, the surface quickly scratches, affecting the line of sight.
  • a possible solution is to deposit an inorganic film on the surface of the polymer.
  • the surface hardness and scratch resistance of the material can be significantly improved.
  • the coating film has disadvantages such as poor adhesion and easy falling off. When the coating reaches a certain thickness, the bending of the polymer substrate causes the coating to be pressed in the plane to cause cracks.
  • the embodiment provides an interface-enhanced composite material, as shown in FIG. 1, comprising a substrate (PC) 11 and a thin film layer (silicon dioxide) 12, and the substrate 11 has a nano-imprinting technique.
  • a substrate PC
  • a thin film layer silicon dioxide
  • the substrate 11 has a nano-imprinting technique.
  • Periodically arranged circular holes, the size of the holes remaining unchanged in the depth direction, and the film layer 12 is plated on the surface of the substrate 11 having the above holes by magnetron sputtering;
  • the thickness d of the substrate 11 was 0.3 mm; the thickness t of the thin film layer 12 was 2 ⁇ m; the diameter w of the holes was 10 ⁇ m, the depth h was 0.1 ⁇ m, and the period p was 30 ⁇ m.
  • Embodiment 1 The difference from Embodiment 1 is that the depth h of the hole is 1 ⁇ m.
  • Embodiment 1 The difference from Embodiment 1 is that the depth h of the hole is 2 ⁇ m.
  • Embodiment 1 The difference from Embodiment 1 is that the surface of the PC substrate is flat and has no recessed structure.
  • the silicon dioxide layer is still a substantially continuous film, so the silicon dioxide film is still cracked, and the crack length is long, but the cracking direction is concentrated in In the direction perpendicular to the direction of the bend, the cracks in the other directions are substantially disappeared; as can be seen from Fig. 2c, the silica film in Example 2 is partially continuous after filling the holes, in which case the crack starts at One hole, ending in the other hole, is completely different from the long crack in Example 1; as can be seen from Fig.
  • Example 3 the silicon oxide film in Example 3 is completely broken (discontinuous) at the hole, in which case the crack It disappears substantially and is effectively suppressed, indicating that the depth of the recessed structure on the substrate 11 is greater than or equal to the thickness of the thin film layer 12, and the crack of the plating layer can be eliminated very effectively. Extend the service period of the material.
  • the surface mechanical properties of the PC substrate, the composite materials provided in Comparative Example 1 and Examples 1-3 were characterized by a nanoindenter, and the results are shown in Figures 3-5; 0.1 ⁇ m, 1 ⁇ m, and 2 ⁇ m represent the composite materials provided in Comparative Example 1, Example 1, Example 2, and Example 3. 4 and FIG. 5, after the surface of the PC substrate having micro/nano holes is coated with a silicon dioxide film (Example 1-3), the surface Young's modulus is about 4 times that of PC, and the hardness is about PC.
  • the properties of the coating material and the polymer substrate material can be organically combined, thereby enhancing the surface hardness and scratch resistance of the polymer material, and effectively preventing The coating layer is cracked or detached from the substrate, enabling new properties that cannot be achieved with a single material system, resulting in new applications with high added value.

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Abstract

本公开提供了一种界面增强的复合材料及其用途。所述复合材料包括：衬底和薄膜层；所述衬底表面具有微纳米尺度的凹陷结构；所述衬底上具有所述凹陷结构的面与所述薄膜层贴合。本公开提供的复合材料在弯曲时抵抗裂纹产生的能力更强，耐磨性好，残余应力小，服役期长，可用于蓝光LED器件的衬底、柔性电路板、OLED或QLED封装、挡风玻璃、飞机机体或汽车车身等领域。

Description

一种界面增强的复合材料及其用途 技术领域
本公开属于复合材料技术领域，例如涉及一种界面增强的复合材料及其用途。
背景技术
镀膜技术在工业领域中广泛应用。根据镀层材料的不同，可采用的方法非常多样，包括喷涂、旋涂、提拉、蒸发、溅射和化学气相沉积等。在柔性或硬质衬底上镀膜，形成层状复合材料，能将不同材料的性能集成在一起，形成新的性能和应用。
但是，由于镀层和衬底属两种不同材料，同时各种各样的镀膜技术生成的薄膜带有不同程度的应力，包括收缩应力和扩张应力，会导致镀层与衬底之间的附着力不强，镀层易脱落、剥离或产生裂痕，寿命大为缩短，给实际应用带来巨大的障碍。
而且，相较于硬质衬底，柔性衬底上的镀层稳定性会更差，主要是因为柔性衬底的机械强度低，大的表面应力会导致材料变形，同时由于柔性衬底在使用过程中会受到反复的弯曲，产生疲劳效应，大大减短镀层的服役寿命。
此外，在复合材料切割的过程中，由于镀层的内应力和低附着力，也会导致镀层破裂或脱离衬底。在拉伸过程中，镀层或衬底会产生裂痕，裂痕的传播导致大面积的镀层破裂，材料性能下降，甚至完全丧失。
因此，如何提高镀层在衬底材料上的稳定性和服役寿命，是本领域亟待解决的问题。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
本公开提供一种界面增强的复合材料及其用途，该复合材料界面结合力强，耐磨，能明显减少弯曲产生的裂纹，具有较高的服役稳定性，可用于蓝光LED(发光二极管)器件的衬底、柔性电路板、OLED(有机发光二极管)或QLED(量子点发光二极管)封装、挡风玻璃、飞机机体或汽车车身等领域。
一方面，本公开提供一种界面增强的复合材料，包括：衬底和薄膜层；
所述衬底表面具有微纳米尺度的凹陷结构；
所述衬底上具有所述凹陷结构的面与所述薄膜层贴合。
本公开通过在衬底上处理出微纳米尺度的凹陷结构，增加了薄膜层与衬底之间的总接触面积，提高了二者的结合强度，从而使得复合材料在弯曲时抵抗裂纹产生的能力更强；薄膜层与衬底相互交叉的界面结构则使得材料的耐磨性能提高，且能够减小甚至消除材料中的残余应力，延长材料的服役期。
在本文一实施方式中，所述衬底为硬质衬底或柔性衬底，例如可以是有机玻璃衬底、PC(聚碳酸酯)衬底、有机硅衬底或蓝宝石衬底等。
在本文一实施方式中，所述薄膜层的厚度为10nm-1000μm；例如可以是10nm、20nm、50nm、100nm、200nm、300nm、500nm、800nm、1μm、2μm、3μm、4μm、5μm、6μm、7μm、8μm、9μm、10μm、15μm、20μm、50μm、100μm、200μm、500μm、800μm或1000μm等。
在本文一实施方式中，所述薄膜层为金属薄膜层、陶瓷薄膜层或高分子薄膜层。
在本文一实施方式中，所述金属薄膜层的材料选自金、银、铂金、镍、铬或铜中的一种或至少两种的组合；所述组合典型但非限制性实例有：金与银的组合、金与铂金的组合、镍与铬的组合、铬与铜的组合等。
在本文一实施方式中，所述陶瓷薄膜层的材料选自氧化物陶瓷、氮化物陶瓷或卤化物陶瓷中的一种或至少两种的组合；所述组合典型但非限制性实例有氧化物陶瓷与氮化物陶瓷的组合、氧化物陶瓷与卤化物陶瓷的组合、氮化物陶瓷与卤化物陶瓷的组合等。
在本文一实施方式中，所述高分子薄膜层的材料为工程高分子材料或功能高分子材料。
在本文一实施方式中，所述工程高分子为PC(聚碳酸酯)、PMMA(聚甲基丙烯酸甲酯)、PS(聚苯乙烯)或PEEK(聚醚醚酮)。
在本文一实施方式中，所述功能高分子材料为高分子半导体材料、高分子压电材料、高分子生物可降解材料或高分子磁性材料。
在本文一实施方式中，所述凹陷结构的深度大于等于所述薄膜层的厚度。
当凹陷结构的深度大于等于薄膜层的厚度时，薄膜层与衬底之间具有更强的结合力，复合材料具有更好的耐弯折性。
在本文一实施方式中，所述凹陷结构在所述衬底上周期性排列。
在本文一实施方式中，所述凹陷结构的排列周期为20nm-1000μm；例如可以是20nm、50nm、100nm、200nm、300nm、500nm、800nm、1μm、2μm、3μm、4μm、5μm、6μm、7μm、8μm、9μm、10μm、15μm、20μm、50μm、100μm、200μm、500μm、800μm或1000μm等。
相对于无序排列的凹陷结构，周期性排列的凹陷结构能够使得复合材料的性质更加均匀，薄膜层的附着力和耐弯折性更强。
本公开对于所述凹陷结构的形状没有特殊限定，示例性地，所述凹陷结构的俯视形状(在衬底表面呈现的形状)可以是圆形、三角形或正方形；所述凹陷结构沿深度方向可以逐渐扩大、逐渐缩小或保持不变。其中，圆形的轮廓更加均匀，有助于消除应力集中，因此所述凹陷结构在衬底表面的形状优选为圆形；为了进一步提高薄膜层的附着力，则可以使所述凹陷结构沿深度方向逐渐扩大。本领域技术人员可以根据实际需要选择凹陷结构的尺寸，示例性地，所述凹陷结构的深度可以是10nm-1000μm；当所述凹陷结构的俯视形状为圆形时，其直径可以是10nm-1000μm，当所述凹陷结构的俯视形状不规则时，则可使其外接圆的直径为10nm-1000μm。
在本文一实施方式中，所述凹陷结构的形成方法选自紫外固化纳米压印、 热塑纳米压印、平面纳米压印、卷对卷纳米压印、卷对板纳米压印、光罩曝光、投影曝光、近场曝光、激光干涉、激光直写或机械雕刻中的一种或至少两种的组合。
在本文一实施方式中，所述薄膜层的形成方法为磁控溅射(sputtering)、热蒸发(evaporation)、等离子体化学气相沉积(PECVD)、脉冲激光沉积(PLD)、原子层沉积(ALD)、液体旋涂(spin-coating)、液体喷涂(spray coating)、悬拉涂布(dip coating)、原位聚合或热压。
另一方面，本公开提供一种上述复合材料的用途。本公开提供的复合材料可以通过选择不同的衬底和薄膜层材料获得不同的用途，示例性地，可以列举以下应用：
1、在陶瓷衬底表面处理出微纳米尺度的凹陷结构，然后镀半导体薄膜。
例如：在蓝宝石衬底表面处理出微纳米尺度的凹陷结构，然后生长GaN(氮化镓)薄膜，形成的复合材料是蓝光LED器件的理想衬底。
2、在陶瓷衬底表面处理出微纳米尺度的凹陷结构，然后复合高分子薄膜。
例如：在玻璃薄膜衬底表面处理出微纳米尺度的凹陷结构，然后将平面的高分子材料压合上去；或者在玻璃薄膜衬底表面浇注紫外固化单体，聚合后形成复合材料。
3、在高分子衬底表面处理出微纳米尺度的凹陷结构，然后镀金属薄膜。
例如：在PI(聚酰亚胺)或PEN(聚萘二甲酸乙二醇酯)衬底表面处理出微纳米尺度的凹陷结构，然后蒸镀铜薄膜，用作柔性电路板。
4、在高分子衬底表面处理出微纳米尺度的凹陷结构，然后镀陶瓷薄膜。
例如：在PMMA衬底表面处理出微纳米尺度的凹陷结构，镀二氧化硅薄膜，用于OLED或QLED封装；在PC衬底表面处理出微纳米尺度的凹陷结构，镀二氧化硅薄膜，用于挡风玻璃。
5、在高分子衬底表面表面处理出微纳米尺度的凹陷结构，然后复合高分子薄膜。
例如：利用衬底和薄膜层材料的Tg(玻璃化转变温度)不同，在二者Tg之间的温度下，在PC或PMMA衬底表面处理出微纳米尺度的凹陷结构，热压PEEK(聚醚醚酮)、PPO(聚苯醚)或PI薄膜，形成兼合两种材料优点的复合薄膜；在固化的环氧树脂表面处理出微纳米尺度的凹陷结构，然后涂覆功能涂料，用于飞机机体、汽车车身或挡板等。
与相关技术相比，本公开具有以下有益效果：
在衬底表面形成微纳米尺度的凹陷结构，具有以下优点：(1)增加薄膜层与衬底材料之间的总接触面积，增加薄膜层在衬底上的附着力；(2)薄膜层与衬底相互交叉，增加薄膜层与衬底之间水平方向上的摩擦力，在有水平摩擦或衬底反复弯曲的情况下，大大增强薄膜层的耐摩擦性能和服役稳定性；(3)各种镀膜技术会在薄膜层中留下或多或少的残余应力，而微纳米尺度的凹陷结构能有效降低，甚至消除薄膜层中的残余应力，使得薄膜层在衬底表面上更加稳定，同时残余应力的减低与消除，也使得厚的薄膜层不致因太大的残余应力而破裂；(4)微纳结构本身可带来新颖的光学或电学性能，比如周期在几百纳米的结构，可以对自然光产生强烈的散射；或者导电薄膜层会因等效厚度的增加而提升薄膜层的导电率。
在阅读并理解了附图和详细描述后，可以明白其他方面。
附图说明
图1为实施例1-3提供的复合材料的剖面结构示意图；
其中，11为衬底，12为薄膜层，d为衬底厚度，t为薄膜层厚度，h为孔洞深度，w为孔洞直径，p为孔洞周期。
图2a为对比例1提供的复合材料的表面SEM照片。
图2b为实施例1提供的复合材料的表面SEM照片。
图2c为实施例2提供的复合材料的表面SEM照片。
图2d为实施例3提供的复合材料的表面SEM照片。
图3为实施例1-3和对比例1提供的复合材料的纳米压痕载荷与压入深度的 关系数据图。
图4为实施例1-3和对比例1提供的复合材料的表面杨氏模量数据图。
图5为实施例1-3和对比例1提供的复合材料的表面硬度数据图。
具体实施方式
下面结合附图并通过具体实施方式来进一步说明本公开的技术方案。本领域技术人员应该明了，所述具体实施方式仅仅是帮助理解本公开，不应视为对本公开的具体限制。
实施例1
玻璃材料因其透明，被广泛用于交通工具窗口，或电子设备的表面。但是玻璃材料的缺点是易碎、重量大。现代汽车轻量化可以节约交通工具的能源消耗，同时减少环境污染，因此越来越受到重视。工程塑料，如PMMA、PC，具有重量轻、透明及不易碎裂的特点，是理想的玻璃替代材料。但是，高分子材料的力学特性相对较差，如杨氏模量、硬度、表面抗刮擦的能力低，使得它们不能完全替代玻璃。比如汽车的挡风玻璃，由于雨刷的来回刮擦，表面很快起刮痕，影响视线。为解决这一问题，一个可能的解决方案是在高分子表面镀无机薄膜。如采用磁控溅射镀上几百纳米到几微米的二氧化硅薄膜，可以使得材料表面硬度、抗刮擦能力显著提高。但是，由于二氧化硅薄膜与高分子衬底材料性质差异特别大，且镀膜过程中经常产生薄膜内应力，导致镀膜存在粘附力差、易脱落等缺点。当镀膜达到一定的厚度时，高分子衬底的弯曲会导致镀膜受平面内挤压而产生裂纹。
有鉴于此，本实施例提供一种界面增强的复合材料，如图1所示，包括衬底(PC)11和薄膜层(二氧化硅)12，衬底11上具有通过纳米压印技术制作的周期性排列的圆形孔洞，孔洞的大小在深度方向上保持不变，薄膜层12是通过磁控溅射法镀在衬底11具有上述孔洞的面上；
其中，衬底11的厚度d为0.3mm；薄膜层12的厚度t为2μm；孔洞的直径w为10μm，深度h为0.1μm，周期p为30μm。
实施例2
与实施例1的区别在于，孔洞的深度h为1μm。
实施例3
与实施例1的区别在于，孔洞的深度h为2μm。
对比例1
与实施例1的区别在于，PC衬底表面平整，没有凹陷结构。
将上述对比例1和实施例1-3提供的复合材料反复弯曲10次(固定复合材料相对的两条边，以1mm/s的速率向内挤压复合材料使其弯曲，直至达到5.25毫米的曲率半径)，然后用SEM(扫描电子显微镜)对其表面形貌进行表征，结果分别如图2a、2b、2c和2d所示。由图2a可知，对比例1提供的复合材料在反复弯曲后，二氧化硅表面开裂，裂纹数量多，长度长，且裂纹方向多样，除了与弯曲方向垂直的裂纹之外，还有很多杂乱取向的裂纹；由图2b可知，由于实施例1中衬底11上孔洞的深度较浅，二氧化硅层还是基本连续的薄膜，因此二氧化硅薄膜依旧开裂，裂纹长度长，但开裂方向集中在与弯曲方向垂直的方向上，而其他方向的裂纹基本上消失不见；由图2c可知，实施例2中二氧化硅薄膜填满孔洞后还会有一部分连续，这种情况下，裂纹起始于一个孔洞，结束于另一个孔洞，完全不同于实施例1中的长裂纹；由图2d可知，实施例3中二氧化硅薄膜在孔洞处完全断开(不连续)，这种情况下，裂纹基本消失，被非常有效地抑制住，表明衬底11上的凹陷结构的深度大于等于薄膜层12的厚度时，能非常有效地消除镀层裂纹，可大大延长材料的服役期。
另外，采用纳米压痕仪对PC衬底、上述对比例1和实施例1-3提供的复合材料的表面力学性能进行表征，结果如图3-5所示；其中，分别以孔洞的深度0、0.1μm、1μm和2μm代表对比例1、实施例1、实施例2和实施例3提供的复合材料。由图4和图5可知，在具有微纳米级孔洞的PC衬底表面镀二氧化硅薄膜后(实施例1-3)，其表面杨氏模量约为PC的4倍，硬度约为PC的15倍；且杨氏模量和硬度的提升效果更优于表面平整的PC衬底制备的复合材料(对比例 1)；而不同深度的孔洞(实施例1-3)则对复合材料的表面杨氏模量和硬度影响不大。
综上可知，通过在衬底上形成微纳米尺度的孔洞，能够让镀膜材料与高分子衬底材料的性能有机结合起来，既增强高分子材料的表面硬度和抗刮擦能力，又能有效防止镀膜层开裂或与衬底脱离，实现单个材料体系无法实现的新性能，从而带来高附加值的新用途。

Claims (15)

  1. 一种界面增强的复合材料，包括：衬底和薄膜层；
    所述衬底表面具有微纳米尺度的凹陷结构；
    所述衬底上具有所述凹陷结构的面与所述薄膜层贴合。
  2. 根据权利要求1所述的复合材料，其中，所述衬底为硬质衬底或柔性衬底。
  3. 根据权利要求1或2所述的复合材料，其中，所述薄膜层的厚度为10nm-1000μm。
  4. 根据权利要求1-3任一项所述的复合材料，其中，所述薄膜层为金属薄膜层、陶瓷薄膜层或高分子薄膜层。
  5. 根据权利要求4所述的复合材料，其中，所述金属薄膜层的材料选自金、银、铂金、镍、铬或铜中的一种或至少两种的组合。
  6. 根据权利要求4或5所述的复合材料，其中，所述陶瓷薄膜层的材料选自氧化物陶瓷、氮化物陶瓷或卤化物陶瓷中的一种或至少两种的组合。
  7. 根据权利要求4-6任一项所述的复合材料，其中，所述高分子薄膜层的材料为工程高分子材料或功能高分子材料。
  8. 根据权利要求7所述的复合材料，其中，所述工程高分子为PC、PMMA、PS或PEEK。
  9. 根据权利要求7所述的复合材料，其中，所述功能高分子材料为高分子半导体材料、高分子压电材料、高分子生物可降解材料或高分子磁性材料。
  10. 根据权利要求1-9任一项所述的复合材料，其中，所述凹陷结构的深度大于等于所述薄膜层的厚度。
  11. 根据权利要求1-10任一项所述的复合材料，其中，所述凹陷结构在所述衬底上周期性排列。
  12. 根据权利要求11所述的复合材料，其中，所述凹陷结构的排列周期为20nm-1000μm。
  13. 根据权利要求1-12任一项所述的复合材料，其中，所述凹陷结构的形 成方法选自紫外固化纳米压印、热塑纳米压印、平面纳米压印、卷对卷纳米压印、卷对板纳米压印、光罩曝光、投影曝光、近场曝光、激光干涉、激光直写或机械雕刻中的一种或至少两种的组合。
  14. 根据权利要求1-13任一项所述的复合材料，其中，所述薄膜层的形成方法为磁控溅射、热蒸发、等离子体化学气相沉积、脉冲激光沉积、原子层沉积、液体旋涂、液体喷涂、悬拉涂布、原位聚合或热压。
  15. 一种如权利要求1-14任一项所述的复合材料的用途，所述复合材料用于蓝光LED器件的衬底、柔性电路板、OLED或QLED封装、挡风玻璃、飞机机体或汽车车身领域。
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