WO2016101704A1 - 超弹性镍钛合金-弹性树脂复合体和超弹性镍钛合金基材及其制备方法以及电子产品外壳 - Google Patents

超弹性镍钛合金-弹性树脂复合体和超弹性镍钛合金基材及其制备方法以及电子产品外壳 Download PDF

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WO2016101704A1
WO2016101704A1 PCT/CN2015/093244 CN2015093244W WO2016101704A1 WO 2016101704 A1 WO2016101704 A1 WO 2016101704A1 CN 2015093244 W CN2015093244 W CN 2015093244W WO 2016101704 A1 WO2016101704 A1 WO 2016101704A1
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Prior art keywords
titanium alloy
elastic resin
superelastic nickel
substrate
nickel
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English (en)
French (fr)
Inventor
章晓
陶乐天
孙剑
陈梁
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BYD Co Ltd
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BYD Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/68—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks
    • B29C70/78—Moulding material on one side only of the preformed part
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/68—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks
    • B29C70/84—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks by moulding material on preformed parts to be joined

Definitions

  • the present invention relates to a superelastic nickel-titanium alloy-elastic resin composite and a preparation method thereof, and to a surface treatment method of a superelastic nickel-titanium alloy substrate and a surface-treated superelastic nickel-titanium obtained by the method
  • An alloy substrate the invention further relates to an electronic product housing.
  • a commonly used method of combining metal and resin is the adhesive method.
  • the method combines a metal with a formed resin by a chemical adhesive to obtain a composite.
  • the bonding strength between the metal and the resin is poor, and the adhesive bonding layer is not resistant to acid and alkali, which affects the use of the composite.
  • the adhesive bonding layer has a certain thickness, it affects the size of the final product.
  • CN101578170B discloses a composite of metal and resin and a method for producing the same, which comprises surface-treating a titanium alloy substrate by chemical etching, and injecting a resin composition onto the surface of the surface-treated substrate to obtain a composite body.
  • the chemical etchant may be a halogen acid, sulfuric acid, a high temperature aqueous phosphoric acid solution, hydrofluoric acid or ammonium hydrogen fluoride, preferably ammonium hydrogen fluoride.
  • a superelastic nickel-titanium alloy-elastic resin composite formed by combining a superelastic nickel-titanium alloy substrate and an elastic resin can be used in a case where bending is required frequently, and thus a high bonding force between the substrate and the resin layer is required. Otherwise, it is easy to cause the resin layer to fall off and affect the service life of the product.
  • a superelastic nickel-titanium alloy substrate and an elastic resin are obtained by chemically etching a surface of a superelastic nickel-titanium alloy substrate by an acidic etching solution, and then molding the elastic resin.
  • the bonding between the layers is low and cannot be applied to applications where structural stability is required.
  • the object of the present invention is to overcome the technical problem that it is difficult to obtain a superelastic nickel-titanium alloy-elastic resin composite having high structural stability by using the existing preparation method, and to provide a superelastic nickel-titanium alloy-elastic resin composite and Its preparation method.
  • a superelastic nickel-titanium alloy-elastic resin composite comprising a superelastic nickel-titanium alloy substrate and attached to at least a portion of a surface of the substrate
  • the elastic resin layer, the surface of the substrate to which the elastic resin layer is attached is distributed with pits, and a part of the resin in the elastic resin layer extends downward and is filled in the pit.
  • a method of surface treatment of a superelastic nickel-titanium alloy substrate comprising a first etching step and a second etching step:
  • the superelastic nickel-titanium alloy substrate is immersed in the first etching solution, and the first etching solution is hydrochloric acid;
  • the first etched superelastic nickel-titanium alloy substrate is immersed in the second etching solution to obtain a surface-treated superelastic nickel-titanium alloy substrate, and the second etching solution contains at least one An alkali metal hydroxide.
  • a surface treated superelastic nitinol substrate at least part of the surface of the superelastic nitinol substrate being provided in accordance with the second aspect of the invention
  • the method is performed by etching to form a surface.
  • a process for producing a superelastic nickel-titanium alloy-elastic resin composite comprising the superelastic nickel-titanium alloy substrate provided according to the third aspect of the present invention
  • the treated surface is impregnated with a composition containing an elastic resin and a part of the composition is filled in the pit to form an elastic resin layer after molding.
  • a superelastic nickel-titanium alloy-elastic resin composite prepared by the method according to the fourth aspect of the invention.
  • an electronic product housing comprising a metal shell body and at least one resin member attached to at least a portion of the inner surface and/or at least a portion of the outer surface of the metal shell body
  • the material of the metal shell body is a superelastic nickel-titanium alloy
  • the material of the resin member is an elastic resin, wherein a surface of the metal shell body to which the resin member is attached is distributed with pits, and a part of the resin member The resin extends downward and fills the pit.
  • the superelastic nickel-titanium alloy-elastic resin composite provided by the invention has high structural stability and can meet the requirements for the use occasions with high structural stability requirements.
  • the surface treatment of the superelastic nickel-titanium alloy by the method of the invention can form densely distributed pits on the surface of the superelastic nickel-titanium alloy substrate without causing destructive corrosion on the superelastic nickel-titanium alloy substrate, and the obtained
  • the surface treated superelastic nitinol substrate is still relatively dense and has a high strength.
  • the metal substrate and the resin layer have a high bonding strength, and the reason may be
  • the surface of the superelastic nickel-titanium alloy obtained by the surface treatment of the superelastic nickel-titanium alloy by the method of the invention is not only densely distributed with uniformly uniform pits, so that the resin layer can be anchored in the substrate.
  • the surface treated superelastic nitinol surface has a high oxygen content, and these oxygen elements are not completely present in the form of metal oxides, some of which are in the form of hydroxides, when combined with the resin. It can interact with the resin, so that the finally prepared superelastic nickel-titanium alloy-elastic resin composite has higher bonding strength between the metal substrate and the resin layer, and is suitable as an outer casing of various electronic products.
  • the etchant used in the surface treatment method of the present invention has a wide range of sources and is inexpensive, and an etchant used at the same time.
  • the toxicity is not high and the operation safety is good.
  • the surface treatment method of the present invention is suitable for large-scale use.
  • FIG. 1 is a cross-sectional view for schematically explaining a casing of a mobile phone according to the present invention, including a front view and a plan view;
  • Fig. 2 is a cross-sectional view for schematically explaining a smart watch case according to the present invention.
  • opening 4 smart watch metal shell body
  • the present invention provides a superelastic nickel-titanium alloy-elastic resin composite comprising a superelastic nickel-titanium alloy substrate and an elastic resin layer attached to at least a part of a surface of the substrate to which the elasticity is attached
  • the surface of the substrate of the resin layer is distributed with pits, and a part of the resin in the elastic resin layer extends downward and is filled in the pits.
  • the superelasticity of nickel-titanium alloy refers to the phenomenon that the nickel-titanium shape memory alloy in the mother phase or the R phase state generates strain much larger than the elastic limit strain under external force, and the strain can be automatically recovered after unloading.
  • the superelastic nickel-titanium alloy is commercially available or can be prepared by a conventional method and will not be described in detail herein.
  • the surface of the superelastic nickel-titanium alloy substrate to which the elastic resin layer is attached is distributed with pits.
  • the pits are densely distributed on the surface of the substrate and can be formed by chemically etching the surface of the superelastic nitinol substrate.
  • a part of the resin in the elastic resin layer extends downward and is filled in the pit, and the elastic resin layer is anchored in the superelastic nickel-titanium alloy substrate.
  • the widths of the pits are each preferably from 10 to 100,000 nm, and the depths are each preferably from 10 to 5000 nm.
  • the elastic resin layer can be firmly anchored to the superelastic nickel-titanium alloy.
  • the elastic resin layer and the superelastic nickel-titanium alloy substrate have a high bonding force, so that the superelastic nickel-titanium alloy-elastic resin composite has high structural stability.
  • the width of the pits is more preferably from 300 to 30,000 nm, and the depth of the pits is more preferably from 100 to 3,000 nm, from the viewpoint of further increasing the bonding force between the elastic resin layer and the superelastic nickel-titanium alloy substrate.
  • the "width of the pit” means the maximum distance between two points on the contour line defined by the port of the pit on the surface of the substrate, and "the depth of the pit” means that the pit is located on the surface of the substrate. The vertical distance from the port to the bottom of the pit.
  • the width and depth of the pits can be determined by electron microscopy.
  • the superelastic nitinol base material has a surface oxygen element content of from 1 to 10% by weight. Compared with the superelastic nitinol base material having a surface oxygen content of less than 1% by weight, when the content of the surface oxygen element of the superelastic nickel-titanium alloy substrate is 1% by weight or more, the elasticity in the composite can be remarkably improved.
  • the bonding strength between the resin layer and the metal substrate Preferably, the superelastic nickel-titanium alloy substrate has a surface layer oxygen content of from 1 to 6% by weight. More preferably, the superelastic nickel-titanium alloy substrate has a surface oxygen content of 2 to 5% by weight.
  • the superelastic nickel-titanium alloy substrate has a surface oxygen content of 3-4% by weight.
  • the elemental composition of the surface of the superelastic nitinol substrate can be determined by energy spectrum analysis, and the percentage of the oxygen element to the total amount of the surface layer element is taken as the surface oxygen element content.
  • the elastic resin layer contains an elastic resin.
  • the elastic resin can be elastically deformed so that the elastic resin layer has Superelastic Nitinol matches the elasticity.
  • the elastic resin may be selected according to the elastic size of the superelastic nickel-titanium alloy so as to enable the elastic resin layer to have an elastic deformation ability compatible with the superelastic nickel-titanium alloy.
  • the elastic resin may be at least one rubber and/or at least one elastomer, and the elastomer may be a thermoplastic elastomer and/or a thermosetting elastomer.
  • the elastic resin may be one or two or more of a rubber, a polyamide-type elastomer, a polyolefin-type elastomer, a polyurethane-type elastomer, a silicone-type elastomer, and a polyester-type elastomer, and is preferably Rubber and / or polyamide type elastomer.
  • the elastic resin layer may further contain at least one filler.
  • the type of the filler can be selected according to specific use requirements.
  • the filler may be a fibrous filler and/or a powder filler.
  • the fibrous filler may be one or more selected from the group consisting of glass fibers, carbon fibers, and aramid fibers.
  • the powder type filler may be one or more selected from the group consisting of calcium carbonate, magnesium carbonate, silica, heavy barium sulfate, talc, glass, and clay.
  • the content of the filler may be a conventional selection.
  • the filler may be included in an amount of 10 to 150 parts by weight, preferably 15 to 100 parts by weight, more preferably 20 to 50 parts by weight based on 100 parts by weight of the elastomeric resin.
  • the thickness of the superelastic nickel-titanium alloy substrate and the elastic resin layer may be selected according to the specific application of the superelastic nickel-titanium alloy-elastic resin composite to meet the requirements for use.
  • the elastic resin layer may have a thickness of 0.5 to 10 mm.
  • the superelastic nickel-titanium alloy-elastic resin composite can be prepared by etching a superelastic nickel-titanium alloy substrate, forming pits on the surface of the substrate, and then molding the elastic resin onto the surface of the substrate for integral molding.
  • the inventors of the present invention found that the superelastic nickel-titanium alloy substrate is first etched with an acidic etching solution, and then etched with an alkaline etching solution to integrally form the superelastic nickel-titanium alloy substrate and the elastic resin.
  • the elastic resin layer and the superelastic nickel-titanium alloy substrate have high bonding force and good structural stability.
  • the present invention provides a method of surface treatment of a superelastic nickel-titanium alloy substrate, the method comprising a first etching step and a second etching step:
  • the superelastic nickel-titanium alloy substrate is immersed in the first etching solution, and the first etching solution is hydrochloric acid;
  • the first etched superelastic nickel-titanium alloy substrate is immersed in the second etching solution to obtain a surface-treated superelastic nickel-titanium alloy substrate, and the second etching solution contains at least one An alkali metal hydroxide.
  • the surface of the surface-treated superelastic nitinol substrate formed after the first etching step and the second etching step is formed with pits which are densely distributed on the surface of the substrate.
  • the width of the pits may each be from 10 to 100,000 nm, preferably from 300 to 30,000 nm; the depth of the pits may each be from 10 to 5000 nm, preferably from 100 to 3000 nm.
  • the surface-treated superelastic nitinol substrate formed after the first etching step and the second etching step has a surface oxygen content of 1-10% by weight, which can significantly improve the surface area
  • the surface treated superelastic nitinol substrate has a surface layer oxygen content of from 1 to 6% by weight formed after the first etching step and the second etching step.
  • the surface treated superelastic nitinol substrate has a surface oxygen content of from 2 to 5% by weight formed after the first etching step and the second etching step. Further preferably, the surface treated superelastic nitinol substrate surface layer oxygen element formed after the first etching step and the second etching step The content is 3-4% by weight.
  • the first etching solution is hydrochloric acid, and may be hydrochloric acid having a concentration of 1 to 30% by weight.
  • the first etching solution is hydrochloric acid having a concentration of 5-20% by weight, such that the finally obtained surface-treated superelastic nickel-titanium alloy is integrally molded with an elastic resin, and superelastic nickel titanium is obtained.
  • the alloy substrate has a higher bonding strength between the elastic resin layer and a higher etching speed.
  • the solvent of the first etching solution may be conventionally selected, typically water.
  • the temperature of the first etchant may be selected according to the concentration of the first etchant to be able to obtain an etch rate that satisfies the use requirements without causing excessive corrosion.
  • the temperature of the first etching solution may be 15 to 50 ° C, preferably 15 to 40 ° C.
  • the soaking time of the superelastic nitinol substrate in the first etching solution may be from 5 to 300 minutes, preferably from 30 to 240 minutes, more preferably from 60 to 240 minutes.
  • the soaking time can also be optimized according to the concentration of the first etching solution. Specifically, when the concentration of the first etching liquid is low, a longer soaking time may be employed; conversely, when the concentration of the first etching liquid is high, the soaking time may be shortened accordingly.
  • the second etchant contains at least one alkali metal hydroxide.
  • the alkali metal hydroxide is preferably sodium hydroxide and/or potassium hydroxide.
  • the content of the alkali metal hydroxide in the second etching solution can be selected according to the desired etching rate.
  • the concentration of the alkali metal hydroxide in the second etching solution is 1-10 mol/L.
  • the concentration of the alkali metal hydroxide in the second etching solution is within the above range, not only the etched surface of the finally obtained surface-treated superelastic nitinol substrate has densely distributed pits but also a surface.
  • the etched surface of the treated superelastic nitinol substrate is still relatively dense. More preferably, the concentration of the alkali metal hydroxide in the second etching solution is 5-8 mol/L.
  • the second etching solution may further contain at least one buffer.
  • the second etchant does not contain a buffer, the object of the present invention can be achieved, but when the second etchant contains a buffer, the concentration of hydroxide ions in the second etchant can be made for a long time.
  • the internal stability is within a certain range, thereby obtaining a stable etching effect, which not only satisfies the requirements for large-scale production, but also can further improve the superelastic nickel-titanium alloy-elastic resin composite in the finally prepared superelastic nickel-titanium alloy-elastic resin composite.
  • the bonding force between the elastic resin layers is not only satisfies the requirements for large-scale production, but also can further improve the superelastic nickel-titanium alloy-elastic resin composite in the finally prepared superelastic nickel-titanium alloy-elastic resin composite.
  • the buffer may be a common variety of substances capable of stabilizing the concentration of hydroxide ions.
  • the buffering agent is one or more selected from the group consisting of boric acid, sodium borate, sodium carbonate, sodium dihydrocarbonate, trisodium phosphate, disodium hydrogen phosphate, and sodium citrate.
  • the buffer is present in an amount such that the hydroxide ion concentration can be stabilized within the expected range.
  • the concentration of the buffer is from 0.1 to 1.5 mol/L. More preferably, the buffer has a concentration of from 0.2 to 1 mol/L.
  • the solvent of the second etching solution may be conventionally selected, typically water.
  • the temperature of the second etching solution may be 15-70 °C.
  • the temperature of the second etching solution is from 15 to 35 ° C from the viewpoint of the bonding strength.
  • the temperature of the second etching liquid is preferably 40 to 70 ° C from the viewpoint of further increasing the etching rate and shortening the soaking time of the superelastic nickel-titanium alloy substrate in the etching liquid.
  • the soaking time of the first etched superelastic nitinol substrate in the second etching solution may be 0.5-24 hours, preferably 0.5-12 hours, more preferably 0.5-5 hours, further preferably 0.5-2 hours. .
  • the number of soaking may be one time, or may be multiple times, for example, 2-10 times.
  • the time of each soaking can be selected according to the number of soaking times, as long as the total soaking time satisfies the above requirements.
  • the superelastic nickel-titanium alloy substrate is generally cleaned (generally water, preferably deionized water) to remove the adhesion to the superelastic nickel-titanium alloy substrate.
  • An etchant on the surface can be 2 to 10 times.
  • the cleaning method may be that the superelastic nickel-titanium alloy substrate is immersed in water, and the immersion time may be 1-5 minutes; the superelastic nickel-titanium alloy substrate may also be washed with water, and the rinsing time may be 1-5 minutes. .
  • the entire surface of the superelastic nickel-titanium alloy substrate can be treated according to the method of the present invention, and a part of the surface of the superelastic nickel-titanium alloy substrate can also be treated.
  • a part of the surface of the superelastic nickel-titanium alloy substrate is treated, only the surface to be treated may be immersed in the etching liquid, or the superelastic nickel-titanium alloy may be formed after the mask is formed on the surface which is not required to be processed.
  • the entire substrate is immersed in an etchant.
  • the surface-treated superelastic nitinol substrate obtained by the method of the present invention has only pits distributed on the surface and the surface of the surface is deeper than before etching, and the size does not change much before and after etching. Moreover, the surface-treated superelastic nitinol substrate obtained by the method of the present invention has a shallow corrosion depth, and is easy to eliminate pits and discoloration in a surface region where no pits are formed, so that the finally obtained product has a better quality. Exterior.
  • the superelastic nickel-titanium alloy substrate and the elastic resin layer are provided between The high bonding strength makes the composite have high structural stability and can meet the requirements of various occasions.
  • the present invention also provides a surface treated superelastic nitinol substrate having at least a portion of its surface that is etched to form a surface using the surface treatment methods provided by the present invention.
  • the etched surface of the surface-treated superelastic nitinol substrate obtained by the surface treatment method of the present invention is distributed with densely distributed pits.
  • the width of the pits is generally from 10 to 100,000 nm each, preferably 300 to 30,000 nm each; the depth of the pits is generally from 10 to 5000 nm each, preferably from 100 to 3000 nm each.
  • the content of the surface layer oxygen element of the surface-treated superelastic nitinol base material obtained by the surface treatment method of the present invention is generally from 1 to 10% by weight, preferably from 1 to 6% by weight, more preferably from 2 to 5 parts by weight, further It is preferably 3-4% by weight.
  • the present invention further provides a method for preparing a superelastic nickel-titanium alloy-elastic resin composite, which comprises injecting an elastic layer into a treated surface of a surface-treated superelastic nitinol substrate provided by the present invention.
  • the composition of the resin is filled with a part of the composition in the pit, and an elastic resin layer is formed after molding.
  • the kind of the elastic resin in the elastic resin-containing composition can be selected according to the elastic size of the superelastic nickel-titanium alloy substrate to enable the elastic resin layer to have elastic deformation ability compatible with the superelastic nickel-titanium alloy substrate.
  • the elastic resin may be at least one rubber and/or at least one elastomer, and the elastomer may be a thermoplastic elastomer and/or a thermosetting elastomer.
  • the elastic resin may be a rubber or a polyamide elastomer,
  • One or two or more kinds of the polyolefin-type elastomer, the polyurethane-type elastomer, the silicone-type elastomer, and the polyester-type elastomer are preferably rubber and/or polyamide-type elastomers.
  • the resin-containing composition may contain, in addition to the elastic resin, at least one filler and/or at least one fluidity improver.
  • the type of the filler can be selected according to specific use requirements.
  • the filler may be a variety of fibrous fillers and/or powdered fillers.
  • the fibrous filler may be one or more selected from the group consisting of glass fibers, carbon fibers, and aramid fibers.
  • the powder type filler may be one or more selected from the group consisting of calcium carbonate, magnesium carbonate, silica, heavy barium sulfate, talc, glass, and clay.
  • the content of the filler may be a conventional selection.
  • the filler may be included in an amount of 10 to 150 parts by weight, preferably 15 to 100 parts by weight, more preferably 20 to 50 parts by weight based on 100 parts by weight of the elastomeric resin.
  • the fluidity improver is used to improve the flowability of the elastic resin, and further improve the bonding force between the superelastic nickel-titanium alloy substrate and the elastic resin and the processability of the elastic resin.
  • the fluidity improver may be any of various substances capable of achieving the above effects, and is preferably a cyclic polyester.
  • the fluidity improver is used in an amount to increase the flowability of the elastic resin.
  • the fluidity improver is contained in an amount of from 1 to 5 parts by weight based on 100 parts by weight of the elastomeric resin.
  • the elastic resin-containing composition may further contain various various auxiliary agents such as a coloring agent and/or an antioxidant according to specific use requirements to improve the elastic resin in the finally formed superelastic nickel-titanium alloy-elastic resin composite.
  • various auxiliary agents such as a coloring agent and/or an antioxidant according to specific use requirements to improve the elastic resin in the finally formed superelastic nickel-titanium alloy-elastic resin composite.
  • the properties of the layer either impart new properties to the elastic resin layer.
  • the elastic resin-containing composition can be obtained by uniformly mixing an elastic resin as a host resin, an optional filler, an optional fluidity improver, and an optional auxiliary.
  • an elastic resin, an optional filler, an optional fluidity improver, and an optional auxiliary agent may be uniformly mixed and obtained by extrusion granulation.
  • the elastic resin-containing composition may be injected into the etched surface of the surface-treated superelastic nitinol substrate by various conventional methods.
  • the surface-treated superelastic nitinol substrate is placed in a mold, and the surface of the surface treated superelastic nitinol substrate is etched by injection molding.
  • the elastic resin-containing composition is injected.
  • the conditions of the injection molding may be selected depending on the kind of the elastic resin in the composition containing the elastic resin.
  • the injection amount of the elastic resin-containing composition can be selected in accordance with the intended thickness of the resin layer.
  • the elastomer resin-containing composition is injected in an amount such that the formed elastic resin layer has a thickness of 0.5 to 10 mm.
  • an etching surface which does not require formation of a resin layer can be treated to remove surface pits and due to etching
  • the surface color is changed, and the treatment may be performed before the injection molding step or after the injection molding step, and is not particularly limited.
  • the elastic resin layer and the superelastic nickel-titanium alloy substrate have high bonding force and high structural stability.
  • the present invention also provides a superelastic nickel-titanium alloy-elastic resin composite prepared by the method according to the present invention.
  • the composite includes a superelastic nitinol substrate and an elastic resin attached to at least a portion of the surface of the substrate In the layer, the surface of the substrate to which the elastic resin layer is attached is distributed with pits, and a part of the resin in the elastic resin layer extends downward and fills the pit.
  • the superelastic nickel-titanium alloy-elastic resin composite according to the present invention can be used in various applications in which a superelastic nickel-titanium alloy and an elastic resin are integrally molded, such as an outer casing of an electronic product.
  • the superelastic nickel-titanium alloy can be molded into various shapes, and the surface on which the resin layer needs to be formed is subjected to surface treatment, and then the elastic resin is injection-molded to form an elastic resin layer.
  • the present invention also provides an electronic product housing including a metal shell body and at least one resin member attached to at least a portion of the inner surface and/or at least a portion of the outer surface of the metal shell body, the metal shell
  • the material of the body is a superelastic nickel-titanium alloy
  • the material of the resin member is an elastic resin, wherein a surface of the metal shell body to which the resin member is attached is distributed with a pit, and a part of the resin in the resin member extends downward and Filled in the pit.
  • the outer casing includes not only an outer casing which is a sheet-like structure but also various frame structures such as an outer frame.
  • the pit may have a width of 10 to 100,000 nm, preferably 300 to 30,000 nm; and the pit may have a depth of 10 to 5000 nm, preferably 100 to 3000 nm.
  • the content of the surface oxygen element of the metal shell body to which the resin member is attached may be from 1 to 10% by weight, preferably from 1 to 6% by weight, more preferably from 2 to 5 parts by weight, still more preferably from 3 to 3% by weight.
  • At least one opening may be disposed on the metal casing body to cover the components of the metal casing body at a corresponding position of the opening.
  • the position of at least a portion of the opening may correspond to a mounting position of the component that emits and/or receives a signal (eg, an electromagnetic signal), wherein the opening position is preferably set.
  • a resin member is filled with a part of the resin in the resin member, and an element emitting and/or receiving a signal may be mounted on the resin member.
  • the metal shell body may be an integral structure or a splicing structure.
  • the splicing structure means that the metal shell body includes at least two portions that are disconnected from each other, and the two portions are spliced together to form a metal shell body.
  • the adjacent two portions may be bonded together with an adhesive.
  • the splicing positions of two adjacent portions are provided with the resin member, and the resin members respectively overlap the adjacent two portions and cover the splicing position (ie, the resin member bridges the adjacent two Partly), the bonding strength of the splicing position can be improved; and the metal shell body can be divided into a plurality of portions according to the internal structure of the electronic product, and the resin member functions to form the metal shell body as a whole. It can also be used as a mounting base for some electronic components.
  • At least a part of the outer surface of the metal shell body may be attached with a resin member, which may cover the entire outer surface, or may cover a part of the outer surface of the metal shell body to form a pattern, such as decoration. Sexual pattern.
  • the resin member when the inner surface of the metal shell body is attached with a resin member, the resin member can be disposed at one or more positions required.
  • the resin member is attached to the entire inner surface of the metal shell body, and the resin member is preferably a unitary structure. According to the preferred embodiment, it is particularly suitable for the case where the metal shell body is a spliced structure.
  • the electronic product casing according to the present invention may be an electronic product casing that requires a metal as a casing, for example: The outer casing or outer frame of the mobile terminal, the outer casing or the outer frame of the wearable electronic device.
  • the mobile terminal refers to a device that can be in a mobile state and has a wireless transmission function, such as a mobile phone, a portable computer (including a laptop and a tablet).
  • the wearable electronic device refers to an intelligent wearable device, such as a smart watch or a smart bracelet.
  • the electronic product may specifically be, but not limited to, one or more of a mobile phone, a portable computer (such as a notebook computer and a tablet), a smart watch, and a smart wristband.
  • Fig. 1 shows a front view and a top view of an embodiment of the electronic product casing when it is a casing of a mobile phone.
  • a plurality of openings 3 are formed in the metal shell body 1 of the mobile phone.
  • the position of the opening 3 may correspond to the position where the antenna is mounted and the position at which various buttons are mounted.
  • the resin layer 2 is attached to the entire inner surface of the metal shell body 1 of the mobile phone, the resin layer 2 is an integral structure, and a part of the resin in the resin layer 2 is filled in the opening 3.
  • Fig. 2 shows a front view of an embodiment of the outer casing of the electronic product being a smart watch.
  • the smart watch metal shell body 4 is provided with a signal element opening 6 corresponding to the mounting signal emitting element and/or the signal receiving element, and the inner surface of the smart watch metal shell body 4 is adhered with a resin inner liner 5, resin A part of the resin in the inner liner 5 is filled in the signal element opening 6, and the signal element can be mounted at a corresponding position on the resin inner liner 5.
  • the superelastic nickel-titanium alloy-elastic resin composite in the superelastic nickel-titanium alloy-elastic composite was measured between the superelastic nickel-titanium alloy substrate and the elastic resin layer in a tensile mode on a universal tester model 3369 from Inster.
  • the average shear strength wherein the ratio between the tensile stress measured when the composite is fractured and the bonded area is taken as the average shear strength, and the bonded area is the area of the joint between the metal substrate and the resin layer.
  • the surface and cross section of the surface-treated superelastic nitinol substrate were observed with a metallographic microscope and the width and depth of the formed pits were determined.
  • the metallographic microscope used was purchased from Zeiss, model number. For Axio Imager A1m.
  • the surface element content was measured by field emission scanning electron microscopy and an accessory energy spectrometer.
  • the energy spectrum meter was purchased from JEOL Ltd., model number JSM-7600F, in which 10 points were selected on the surface of the sample to be tested.
  • 10 points were distributed at different positions on the surface of the sample, and the average value of the oxygen content obtained from the 10 points was taken as the surface oxygen element content of the sample.
  • SMA superelastic nickel-titanium shape memory alloy plate (purchased from Dongguan Guangshengda Hardware Co., Ltd.) with a thickness of 0.8mm was cut into 15mm ⁇ 80mm rectangular pieces, which were polished in a polishing machine and then removed. Oil, water washing and drying to obtain a superelastic nickel-titanium alloy sheet.
  • the superelastic nickel-titanium alloy sheet obtained in the step (1) was immersed in a 500 mL etching solution at 25 ° C for 120 minutes, and then the superelastic nickel-titanium alloy sheet was taken out and washed three times with deionized water.
  • the etching solution is hydrochloric acid having a concentration of 10% by weight.
  • the superelastic nickel-titanium alloy sheet obtained in the step (2.1) was immersed in a 500 mL etching solution at 25 ° C for 60 minutes, the superelastic nickel-titanium alloy sheet was taken out and washed three times with deionized water. Then, it was dried in an oven at 65 ° C to obtain a surface-treated superelastic nickel-titanium alloy sheet.
  • the etching solution is a mixed aqueous solution of sodium hydroxide and boric acid, the concentration of sodium hydroxide is 7 mol/L, and the concentration of boric acid is 0.5 mol/L.
  • the surface of the surface-treated superelastic nitinol sheet was observed by a metallographic microscope, and it was confirmed that the surface of the surface-treated superelastic nitinol sheet was formed with densely distributed pits each having a width of In the range of 300-30000 nm, the depths are each in the range of 100-3000 nm.
  • the surface of the surface-treated superelastic nickel-titanium alloy sheet was subjected to energy spectrum analysis by scanning electron microscopy, and the content of each element was determined to determine the oxygen content. The results are shown in Table 1.
  • the surface-treated superelastic nickel-titanium alloy sheet obtained in the step (2.2) is placed in a mold, and then the polyamide-containing elastic resin (purchased from Dongguan City Foundation Engineering Plastic Co., Ltd., grade TR90) and glass fiber are injection molded into the mold.
  • the composition was formed into a resin layer on one surface of a superelastic nickel-titanium alloy sheet, thereby obtaining a superelastic nickel-titanium alloy-elastic resin composite (the thickness of the elastic resin layer was 3 mm).
  • the content of the glass fiber is 20 parts by weight based on 100 parts by weight of the polyamide elastic resin.
  • the average shear strength between the superelastic nitinol substrate and the resin layer is listed in Table 2.
  • the surface of the surface-treated superelastic nickel-titanium alloy sheet was observed by a metallographic microscope, and it was confirmed that the surface of the obtained surface-treated nickel-titanium alloy sheet was formed with densely distributed pits each having a width of 300- In the range of 30000 nm, the depths are each in the range of 100-3000 nm.
  • the surface of the surface-treated superelastic nickel-titanium alloy sheet was subjected to energy spectrum analysis by scanning electron microscopy, and the content of each element was determined to determine the oxygen content. The results are shown in Table 1.
  • a surface of the surface-treated superelastic nickel-titanium alloy sheet obtained in the step (2) is injection-molded with a composition containing the polyamide elastic resin and the glass fiber in the same manner as in the step (3) of the first embodiment, and is molded.
  • the superelastic nickel-titanium alloy-elastic resin composite was obtained in which the average shear strength between the superelastic nickel-titanium alloy substrate and the elastic resin layer is listed in Table 2.
  • the surface of the superelastic nickel-titanium alloy sheet was observed by a metallographic microscope, and no obvious pits were observed on the surface of the surface-treated superelastic nickel-titanium alloy sheet.
  • the superelastic nickel-titanium alloy sheet obtained in the step (1) is subjected to surface treatment in the same manner as in the step (2.1) of the first embodiment to obtain a surface-treated superelastic nickel-titanium alloy sheet, except that the soaking time is It is 320 minutes.
  • the surface and the cross section of the superelastic nickel-titanium alloy sheet were observed by a metallographic microscope, and it was confirmed that the surface of the surface-treated superelastic nitinol sheet was formed with densely distributed pits each having a width of 100,000. In the range of -150000 nm, the depths are each in the range of 40,000 to 80,000 nm.
  • the surface of the superelastic nickel-titanium alloy sheet was analyzed by energy spectroscopy using a scanning electron microscope to determine the content of each element and determine the oxygen content. The results are shown in Table 1.
  • a surface of the surface-treated superelastic nickel-titanium alloy sheet obtained in the step (2) is injection-molded with a composition containing the polyamide elastic resin and the glass fiber in the same manner as in the step (3) of the first embodiment, and is molded.
  • the superelastic nickel-titanium alloy-elastic resin composite was obtained in which the average shear strength between the superelastic nickel-titanium alloy substrate and the elastic resin layer is listed in Table 2.
  • the superelastic nickel-titanium alloy sheet obtained in the step (1) was immersed in a 500 mL etching solution at 15 ° C for 240 minutes, the superelastic nickel-titanium alloy sheet was taken out and washed three times with deionized water.
  • the etching solution was hydrochloric acid having a concentration of 5% by weight.
  • the superelastic nickel-titanium alloy sheet obtained in the step (2.1) was immersed in a 500 mL etching solution at 25 ° C for 45 minutes, and then the superelastic nickel-titanium alloy sheet was taken out and washed three times with deionized water. Then, it was dried in an oven at 65 ° C to obtain a surface-treated superelastic nickel-titanium alloy sheet.
  • the etching solution is a mixed aqueous solution of sodium hydroxide and disodium hydrogen phosphate, the concentration of sodium hydroxide is 7 mol/L, and the concentration of disodium hydrogen phosphate is 1 mol/L.
  • the surface of the surface-treated superelastic nitinol sheet was observed by a metallographic microscope, and it was confirmed that the surface of the surface-treated superelastic nitinol sheet was formed with densely distributed pits each having a width of 300-30000nm Within the range, the depths are each in the range of 100-3000 nm.
  • the surface of the surface-treated superelastic nickel-titanium alloy sheet was subjected to energy spectrum analysis by scanning electron microscopy, and the content of each element was determined to determine the oxygen content. The results are shown in Table 1.
  • a surface of the surface-treated superelastic nickel-titanium alloy sheet obtained in the step (2) is injection-molded with a composition containing the polyamide elastic resin and the glass fiber in the same manner as in the step (1) of the first embodiment, and is molded.
  • the superelastic nickel-titanium alloy-elastic resin composite (the thickness of the elastic resin layer was 3 mm) was obtained, wherein the average shear strength between the superelastic nickel-titanium alloy substrate and the elastic resin layer is listed in Table 2.
  • the superelastic nickel-titanium alloy sheet obtained in the step (1) was immersed in a 500 mL etching solution at 35 ° C for 90 minutes, and then the superelastic nickel-titanium alloy sheet was taken out and washed three times with deionized water.
  • the etching solution was hydrochloric acid having a concentration of 15% by weight.
  • the superelastic nickel-titanium alloy sheet obtained in the step (2.1) was immersed in a 500 mL etching solution at 35 ° C for 90 minutes, the superelastic nickel-titanium alloy sheet was taken out and washed three times with deionized water. Then, it was dried in an oven at 65 ° C to obtain a surface-treated superelastic nickel-titanium alloy sheet.
  • the etching solution is a mixed aqueous solution of sodium hydroxide and sodium carbonate, the concentration of sodium hydroxide is 6 mol/L, and the concentration of sodium carbonate is 0.2 mol/L.
  • the surface of the surface-treated superelastic nitinol sheet was observed by a metallographic microscope, and it was confirmed that the surface of the surface-treated superelastic nitinol sheet was formed with densely distributed pits each having a width of In the range of 300-30000 nm, the depths are each in the range of 100-3000 nm.
  • the surface of the surface-treated superelastic nickel-titanium alloy sheet was subjected to energy spectrum analysis by scanning electron microscopy, and the content of each element was determined to determine the oxygen content. The results are shown in Table 1.
  • a surface of the surface-treated superelastic nickel-titanium alloy sheet obtained in the step (2) is injection-molded with a composition containing the polyamide elastic resin and the glass fiber in the same manner as in the step (1) of the first embodiment, and is molded.
  • the superelastic nickel-titanium alloy-elastic resin composite was obtained in which the average shear strength between the superelastic nickel-titanium alloy substrate and the elastic resin layer is listed in Table 2.
  • the hydrochloric acid-etched superelastic nickel-titanium alloy sheet obtained in the step (2.1) is etched in the same manner as in the step (2.2) of the first embodiment, except that the etching solution is an aqueous sodium hydroxide solution and sodium hydroxide.
  • the concentration is 7 mol/L.
  • the surface of the surface-treated superelastic nitinol sheet was observed by a metallographic microscope, and it was confirmed that the surface of the surface-treated superelastic nitinol sheet was formed with densely distributed pits each having a width of 10-100000nm Within the range, the depths are each in the range of 10-5000 nm.
  • the surface of the surface-treated superelastic nickel-titanium alloy sheet was subjected to energy spectrum analysis by scanning electron microscopy, and the content of each element was determined to determine the oxygen content. The results are shown in Table 1.
  • a surface of the surface-treated superelastic nickel-titanium alloy sheet obtained in the step (2) is injection-molded with a composition containing the polyamide elastic resin and the glass fiber in the same manner as in the step (1) of the first embodiment, and is molded.
  • the superelastic nickel-titanium alloy-elastic resin composite was obtained in which the average shear strength between the superelastic nickel-titanium alloy substrate and the elastic resin layer is listed in Table 2.
  • the superelastic nickel-titanium alloy sheet obtained in the step (1) is subjected to surface treatment in the same manner as in the step (2) of the first embodiment, except that in the step (2.2), the temperature of the etching liquid is 45 ° C.
  • the soaking time is 40 minutes.
  • the surface of the surface-treated superelastic nitinol sheet was observed by a metallographic microscope, and it was confirmed that the surface of the surface-treated superelastic nitinol sheet was formed with densely distributed pits each having a width of In the range of 300-30000 nm, the depths are each in the range of 100-3000 nm.
  • the surface of the surface-treated superelastic nickel-titanium alloy sheet was subjected to energy spectrum analysis by scanning electron microscopy, and the content of each element was determined to determine the oxygen content. The results are shown in Table 1.
  • a surface of the surface-treated superelastic nickel-titanium alloy sheet obtained in the step (2) is injection-molded with a composition containing the polyamide elastic resin and the glass fiber in the same manner as in the step (1) of the first embodiment, and is molded.
  • the superelastic nickel-titanium alloy-elastic resin composite was obtained in which the average shear strength between the superelastic nickel-titanium alloy substrate and the elastic resin layer is listed in Table 2.
  • Example 1 17.65 Comparative example 1 /* Comparative example 2 1.19 Comparative example 3 /* Comparative example 4 1.68
  • Example 2 16.72
  • Example 3 16.24
  • Example 4 15.06
  • Example 5 16.39
  • the average shear strength between the superelastic nickel-titanium alloy substrate and the elastic resin layer is high, indicating superelastic nickel-titanium.
  • the alloy substrate and the elastic resin layer have a high bonding strength, and thus the superelastic nickel-titanium alloy-elastic resin composite of the present invention has good structural stability.

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Abstract

本公开是关于一种超弹性镍钛合金-弹性树脂复合体及制备方法，该复合体包括超弹性镍钛合金基材以及附着于基材的至少部分表面上的弹性树脂层，附着有弹性树脂层的基材表面分布有凹坑，弹性树脂层中的部分树脂填充于凹坑中。本公开还关于一种经表面处理的超弹性镍钛合金及其制备方法，包括将超弹性镍钛合金先后用酸和碱进行蚀刻。本公开还关于一种电子产品外壳。采用本公开的方法对超弹性镍钛合金进行表面处理，能够在超弹性镍钛合金表面形成密集分布的凹坑，制备的超弹性镍钛合金-弹性树脂复合体中，树脂层与超弹性镍钛合金基材之间具有较高的结合力，适于作为各种电子产品的外壳。

Description

超弹性镍钛合金-弹性树脂复合体和超弹性镍钛合金基材及其制备方法以及电子产品外壳
相关申请的交叉引用
本申请基于申请号为201410821592.3、申请日为2014/12/25的中国专利申请提出，并要求该中国专利申请的优先权，该中国专利申请的全部内容在此引入本申请作为参考。
技术领域
本发明涉及一种超弹性镍钛合金-弹性树脂复合体及其制备方法，本发明还涉及一种超弹性镍钛合金基材表面处理方法及由该方法得到的经表面处理的超弹性镍钛合金基材，本发明进一步涉及一种电子产品外壳。
背景技术
在汽车、家用电器制品、工业机器等的零件制造领域中，需要金属与树脂一体化成型技术。
目前常用的将金属和树脂相结合的方法是胶粘剂法。该方法通过化学胶粘剂将金属与已成型树脂结合在一起得到复合体。但是，由该方法得到的复合体中，金属与树脂的结合力较差，且胶粘剂结合层不耐酸碱，影响复合体的使用场合。另外，由于胶粘剂结合层具有一定的厚度，因而会影响最终产品的尺寸。
针对胶粘剂法存在的上述不足，研究人员开发了多种用于将金属与树脂结合的方法。
CN101578170B公开了一种金属和树脂的复合体及其制造方法，该方法采用化学蚀刻的方法对钛合金基材进行表面处理，并向经表面处理的基材表面注射树脂组合物，从而得到复合体。其中，化学蚀刻剂可以为卤酸、硫酸、高温的磷酸水溶液、氢氟酸以及氟化氢铵，优选为氟化氢铵。
发明内容
将超弹性镍钛合金基材与弹性树脂结合而形成的超弹性镍钛合金-弹性树脂复合体可以用于需要经常进行弯折的场合，因而要求基材与树脂层之间具有高的结合力，否则极易造成树脂层脱落，影响产品使用寿命。
但是，本发明的发明人在实践过程中发现，单纯采用酸性蚀刻液对超弹性镍钛合金基材表面进行化学蚀刻后注塑弹性树脂形成的复合体中，超弹性镍钛合金基材与弹性树脂层之间的结合力较低，无法应用于对结构稳定性要求较高的使用场合。
本发明的目的在于克服采用现有的制备方法很难获得具有较高结构稳定性的超弹性镍钛合金-弹性树脂复合体的技术问题，提供一种超弹性镍钛合金-弹性树脂复合体及其制备方法。
根据本发明的第一个方面，本发明提供了一种超弹性镍钛合金-弹性树脂复合体，该复合体包括超弹性镍钛合金基材以及附着于所述基材的至少部分表面上的弹性树脂层，附着有所述弹性树脂层的基材表面分布有凹坑，所述弹性树脂层中的部分树脂向下延伸并填充于所述凹坑中。
根据本发明的第二个方面，本发明提供了一种超弹性镍钛合金基材表面处理方法，该方法包括第一蚀刻步骤和第二蚀刻步骤：
在第一蚀刻步骤中，将超弹性镍钛合金基材浸泡于第一蚀刻液中，所述第一蚀刻液为盐酸；
在第二蚀刻步骤中，将经第一蚀刻的超弹性镍钛合金基材浸泡于第二蚀刻液中，得到经表面处理的超弹性镍钛合金基材，所述第二蚀刻液含有至少一种碱金属氢氧化物。
根据本发明的第三个方面，本发明提供了一种经表面处理的超弹性镍钛合金基材，该超弹性镍钛合金基材的至少部分表面为采用根据本发明的第二个方面提供的方法进行蚀刻而形成的表面。
根据本发明的第四个方面，本发明提供了一种超弹性镍钛合金-弹性树脂复合体的制备方法，该方法包括向根据本发明的第三个方面提供的超弹性镍钛合金基材的经处理的表面注入一种含弹性树脂的组合物并使部分组合物填充在所述凹坑中，成型后形成弹性树脂层。
根据本发明的第五个方面，本发明提供了一种由根据本发明的第四方面所述方法制备的超弹性镍钛合金-弹性树脂复合体。
根据本发明的第六个方面，本发明提供了一种电子产品外壳，该外壳包括金属壳本体以及附着于所述金属壳本体的至少部分内表面和/或至少部分外表面的至少一个树脂件，所述金属壳本体的材质为超弹性镍钛合金，所述树脂件的材质为弹性树脂，其中，附着有所述树脂件的金属壳本体表面分布有凹坑，所述树脂件中的部分树脂向下延伸并填充于所述凹坑中。
本发明提供的超弹性镍钛合金-弹性树脂复合体具有较高的结构稳定性，能够满足对结构稳定性要求较高的使用场合的要求。
采用本发明的方法对超弹性镍钛合金进行表面处理，能够在超弹性镍钛合金基材表面形成密集分布的凹坑，不会对超弹性镍钛合金基材产生破坏性腐蚀，得到的经表面处理的超弹性镍钛合金基材表面仍然较为致密，具有较高的强度。并且，采用本发明的方法对超弹性镍钛合金进行表面处理，然后注塑弹性树脂进行一体化成型而得到的复合体中，金属基材与树脂层之间具有较高的结合强度，其原因可能在于：采用本发明的方法对超弹性镍钛合金进行表面处理得到的经表面处理的超弹性镍钛合金表面不仅密集分布有尺寸较为均一的凹坑，从而能将树脂层锚定在基材中；而且，经表面处理的超弹性镍钛合金表面具有较高的氧含量，这些氧元素并不完全以金属氧化物的形式存在，其中的一部分以氢氧根的形式存在，在与树脂结合时能与树脂发生相互作用，使得最终制备的超弹性镍钛合金-弹性树脂复合体中金属基材与树脂层之间具有更高的结合强度，适于作为各种电子产品的外壳。
本发明的表面处理方法中所使用的蚀刻剂的来源广泛且价格低廉，同时所使用的蚀刻剂 的毒性不高，操作安全性好。因而，本发明的表面处理方法适于大规模使用。
附图说明
图1为用于示意性地说明根据本发明的手机外壳的剖视图，包括主视图和俯视图；
图2为用于示意性地说明根据本发明的智能表外壳的剖视图。
<附图标记说明>
1：手机金属壳本体             2：树脂层
3：开口                       4：智能表金属壳本体
5：树脂内衬层                 6：信号元件开口
具体实施方式
本发明提供了一种超弹性镍钛合金-弹性树脂复合体，该复合体包括超弹性镍钛合金基材以及附着于所述基材的至少部分表面上的弹性树脂层，附着有所述弹性树脂层的基材表面分布有凹坑，所述弹性树脂层中的部分树脂向下延伸并填充于所述凹坑中。
本文中，镍钛合金的超弹性是指处于母相或R相状态的镍钛形状记忆合金在外力作用下产生远大于其弹性极限应变量的应变，卸载后应变可自动恢复的现象。所述超弹性镍钛合金可以商购得到，也可以采用常规方法制备得到，本文不再详述。
所述超弹性镍钛合金基材的附着有弹性树脂层的表面分布有凹坑。所述凹坑在基材表面呈密集分布，可以通过对超弹性镍钛合金基材的表面进行化学蚀刻而形成。所述弹性树脂层中的部分树脂向下延伸并填充于所述凹坑中，将弹性树脂层锚定于超弹性镍钛合金基材中。
所述凹坑的宽度各自优选为10-100000nm，深度各自优选为10-5000nm，在所述凹坑的尺寸处于上述范围之内时，能将弹性树脂层稳固地锚定在超弹性镍钛合金基材中，使弹性树脂层与超弹性镍钛合金基材之间具有较高的结合力，从而使得超弹性镍钛合金-弹性树脂复合体具有较高的结构稳定性。从进一步提高弹性树脂层与超弹性镍钛合金基材之间的结合力的角度出发，所述凹坑的宽度各自更优选为300-30000nm，所述凹坑的深度各自更优选为100-3000nm。本发明中，“凹坑的宽度”是指由凹坑位于基材表面的端口确定的轮廓线上的两个点之间的最大距离，“凹坑的深度”是指凹坑位于基材表面的端口至凹坑底部的垂直距离。所述凹坑的宽度和深度可以采用电镜法测定。
根据本发明的复合体，所述超弹性镍钛合金基材的表层氧元素的含量为1-10重量％。与超弹性镍钛合金基材的表层氧元素含量为低于1重量％相比，在超弹性镍钛合金基材的表层氧元素的含量为1重量％以上时，能明显提高复合体中弹性树脂层与金属基材之间的结合强度。优选地，所述超弹性镍钛合金基材表层氧元素的含量为1-6重量％。更优选地，所述超弹性镍钛合金基材表层氧元素的含量为2-5重量％。进一步优选地，所述超弹性镍钛合金基材表层氧元素的含量为3-4重量％。可以通过采用能谱分析法测定超弹性镍钛合金基材表面的元素组成，并将氧元素占表层元素总量的百分比作为表层氧元素含量。
所述弹性树脂层含有弹性树脂。所述弹性树脂能发生弹性形变，以使弹性树脂层具有与 超弹性镍钛合金相匹配的弹性。所述弹性树脂可以根据超弹性镍钛合金的弹性大小进行选择，以能够使得弹性树脂层具有与超弹性镍钛合金相适应的弹性变形能力为准。具体地，所述弹性树脂可以为至少一种橡胶和/或至少一种弹性体，所述弹性体可以为热塑性弹性体和/或热固性弹性体。具体地，所述弹性树脂可以为橡胶、聚酰胺型弹性体、聚烯烃型弹性体、聚氨酯型弹性体、有机硅型弹性体和聚酯型弹性体中的一种或两种以上，优选为橡胶和/或聚酰胺型弹性体。
所述弹性树脂层还可以含有至少一种填料。所述填料的种类可以根据具体的使用要求进行选择。所述填料可以为纤维型填料和/或粉末型填料。所述纤维型填料可以为选自玻璃纤维、碳纤维和芳族聚酰胺纤维中的一种或两种以上。所述粉末型填料可以为选自碳酸钙、碳酸镁、二氧化硅、重质硫酸钡、滑石粉、玻璃和粘土中的一种或两种以上。所述填料的含量可以为常规选择。一般地，以100重量份弹性树脂为基准，所述填料的含量可以为10-150重量份，优选为15-100重量份，更优选为20-50重量份。
所述超弹性镍钛合金基材和所述弹性树脂层的厚度可以根据该超弹性镍钛合金-弹性树脂复合体的具体应用场合进行选择，以能满足使用要求为准。一般地，所述弹性树脂层的厚度可以为0.5-10mm。
所述超弹性镍钛合金-弹性树脂复合体可以通过对超弹性镍钛合金基材进行蚀刻，在基材表面形成凹坑，然后将弹性树脂注塑在基材表面进行一体化成型而制备。本发明的发明人发现：先用酸性蚀刻液对超弹性镍钛合金基材进行蚀刻，然后再用碱性蚀刻液进行蚀刻，将该超弹性镍钛合金基材与弹性树脂一体化成型而得到的复合体中，弹性树脂层与超弹性镍钛合金基材之间具有较高的结合力，结构稳定性好。
因此，本发明提供了一种超弹性镍钛合金基材表面处理方法，该方法包括第一蚀刻步骤和第二蚀刻步骤：
在第一蚀刻步骤中，将超弹性镍钛合金基材浸泡于第一蚀刻液中，所述第一蚀刻液为盐酸；
在第二蚀刻步骤中，将经第一蚀刻的超弹性镍钛合金基材浸泡于第二蚀刻液中，得到经表面处理的超弹性镍钛合金基材，所述第二蚀刻液含有至少一种碱金属氢氧化物。
根据本发明的方法，经过第一蚀刻步骤和第二蚀刻步骤后形成的经表面处理的超弹性镍钛合金基材表面形成有凹坑，所述凹坑在基材表面为密集分布。所述凹坑的宽度各自可以为10-100000nm，优选为300-30000nm；所述凹坑的深度各自可以为10-5000nm，优选为100-3000nm。根据本发明的方法，经过第一蚀刻步骤和第二蚀刻步骤后形成的经表面处理的超弹性镍钛合金基材表层氧元素的含量为1-10重量％，这样能够明显提高由该经表面处理的超弹性镍钛合金基材与弹性树脂形成的复合体中，超弹性镍钛合金基材与弹性树脂层之间的结合强度。优选地，经过第一蚀刻步骤和第二蚀刻步骤后形成的，经表面处理的超弹性镍钛合金基材表层氧元素的含量为1-6重量％。更优选地，经过第一蚀刻步骤和第二蚀刻步骤后形成的，经表面处理的超弹性镍钛合金基材表层氧元素的含量为2-5重量％。进一步优选地，经过第一蚀刻步骤和第二蚀刻步骤后形成的，经表面处理的超弹性镍钛合金基材表层氧元素 的含量为3-4重量％。
所述第一蚀刻液为盐酸，可以为浓度为1-30重量％的盐酸。优选地，所述第一蚀刻液为浓度为5-20重量％的盐酸，这样最终得到的经表面处理的超弹性镍钛合金与弹性树脂一体化成型而得到的复合体中，超弹性镍钛合金基材与弹性树脂层之间具有更高的结合强度，同时也能获得较高的蚀刻速度。
所述第一蚀刻液的溶剂可以为常规选择，一般为水。
所述第一蚀刻液的温度可以根据第一蚀刻液的浓度进行选择，以能够获得满足使用要求的蚀刻速度，同时又不会造成过度腐蚀为准。一般地，所述第一蚀刻液的温度可以为15-50℃，优选为15-40℃。
所述超弹性镍钛合金基材在所述第一蚀刻液中的浸泡时间可以为5-300分钟，优选为30-240分钟，更优选为60-240分钟。另外，还可以根据第一蚀刻液的浓度对浸泡时间进行优化。具体地，在所述第一蚀刻液的浓度较低时，可以采用较长的浸泡时间；反之，在所述第一蚀刻液的浓度较高时，可以相应缩短浸泡时间。
所述第二蚀刻液含有至少一种碱金属氢氧化物。所述碱金属氢氧化物优选为氢氧化钠和/或氢氧化钾。
所述第二蚀刻液中碱金属氢氧化物的含量可以根据预期的蚀刻速度进行选择。优选地，所述第二蚀刻液中，碱金属氢氧化物的浓度为1-10mol/L。在所述第二蚀刻液中碱金属氢氧化物的浓度处于上述范围之内时，不仅最终得到的经表面处理的超弹性镍钛合金基材的蚀刻表面具有密集分布的凹坑，而且经表面处理的超弹性镍钛合金基材的蚀刻表面仍然较为致密。更优选地，所述第二蚀刻液中，碱金属氢氧化物的浓度为5-8mol/L。
优选地，所述第二蚀刻液还可以含有至少一种缓冲剂。尽管所述第二蚀刻液不含缓冲剂也可以实现本发明的目的，但是在所述第二蚀刻液含有缓冲剂时，能够将第二蚀刻液中氢氧根离子的浓度在较长的时间内稳定在一定范围内，从而获得稳定的蚀刻效果，不仅能够满足大规模生产的需求，而且能够进一步提高最终制备的超弹性镍钛合金-弹性树脂复合体中，超弹性镍钛合金基材与弹性树脂层之间的结合力。
所述缓冲剂可以为常见的各种能够稳定氢氧根离子浓度的物质。优选地，所述缓冲剂为选自硼酸、硼酸钠、碳酸钠、碳酸二氢钠、磷酸三钠、磷酸氢二钠和柠檬酸钠中的一种或两种以上。
所述缓冲剂的含量以能够将氢氧根离子浓度稳定在预期范围内为准。优选地，所述缓冲剂的浓度为0.1-1.5mol/L。更优选地，所述缓冲剂的浓度为0.2-1mol/L。
所述第二蚀刻液的溶剂可以为常规选择，一般为水。
所述第二蚀刻液的温度可以为15-70℃。从进一步提高得到的经表面处理的超弹性镍钛合金基材与弹性树脂一体化成型而得到的超弹性镍钛合金-弹性树脂复合体中，超弹性镍钛合金基材与弹性树脂层之间的结合强度的角度出发，所述第二蚀刻液的温度为15-35℃。从进一步提高蚀刻速度，缩短超弹性镍钛合金基材在蚀刻液中的浸泡时间的角度出发，所述第二蚀刻液的温度优选为40-70℃。
经第一蚀刻的超弹性镍钛合金基材在第二蚀刻液中的浸泡时间可以为0.5-24小时，优选为0.5-12小时，更优选为0.5-5小时，进一步优选为0.5-2小时。
所述第一蚀刻步骤和第二蚀刻步骤中，浸泡次数可以为1次，也可以为多次，例如2-10次。每次浸泡的时间可以根据浸泡次数进行选择，只要总的浸泡时间满足上述要求即可。
无论是第一蚀刻步骤，还是第二蚀刻步骤，每次浸泡后，一般对超弹性镍钛合金基材进行清洗(一般用水，优选去离子水)，以除去附着在超弹性镍钛合金基材表面上的蚀刻液。清洗的次数可以为2到10次。清洗的方式可以是将超弹性镍钛合金基材浸泡于水中，浸泡的时间可以为1-5分钟；也可以用水对超弹性镍钛合金基材进行冲洗，冲洗的时间可以为1-5分钟。
根据本发明的方法可以对超弹性镍钛合金基材的整个表面进行处理，也可以对超弹性镍钛合金基材的部分表面进行处理。在将超弹性镍钛合金基材的部分表面进行处理时，可以仅将需要进行处理的表面浸泡于蚀刻液液中，也可以在无需进行处理的表面形成掩模后，将超弹性镍钛合金基材整体浸泡于蚀刻液中。
采用本发明的方法得到的经表面处理的超弹性镍钛合金基材与蚀刻前相比，仅表面分布有凹坑且表面的颜色有所加深，尺寸在蚀刻前后则变化不大。并且，采用本发明的方法得到的经表面处理的超弹性镍钛合金基材的腐蚀深度浅，易于消除无需形成凹坑的表面区域内的凹坑及变色，使最终得到的产品具有较好的外观。更重要的是，采用本发明的方法得到的经表面处理的超弹性镍钛合金基材与弹性树脂一体化成型而得到的复合体中，超弹性镍钛合金基材与弹性树脂层之间具有较高的结合强度，因而复合体具有较高的结构稳定性，能满足多种场合的使用要求。
由此，本发明还提供了一种经表面处理的超弹性镍钛合金基材，该超弹性镍钛合金基材的至少部分表面为采用本发明提供的表面处理方法进行蚀刻而形成表面。
由本发明的表面处理方法得到的经表面处理的超弹性镍钛合金基材的蚀刻表面分布有密集分布的凹坑。所述凹坑的宽度一般各自为10-100000nm，优选条件下各自为300-30000nm；所述凹坑的深度一般各自为10-5000nm，优选条件下各自为100-3000nm。
由本发明的表面处理方法得到的经表面处理的超弹性镍钛合金基材表层氧元素的含量一般为1-10重量％，优选为1-6重量％，更优选为2-5重量份，进一步优选为3-4重量％。
本发明进一步提供了一种超弹性镍钛合金-弹性树脂复合体的制备方法，该方法包括向本发明提供的经表面处理的超弹性镍钛合金基材的经处理的表面注入一种含弹性树脂的组合物并使部分组合物填充于所述凹坑中，成型后形成弹性树脂层。
所述经表面处理的超弹性镍钛合金基材及其制备方法在前文已经进行了详细地描述，此处不再详述。
所述含弹性树脂的组合物中的弹性树脂的种类可以根据超弹性镍钛合金基材的弹性大小进行选择，以能够使得弹性树脂层具有与超弹性镍钛合金基材相适应的弹性变形能力为准。具体地，所述弹性树脂可以为至少一种橡胶和/或至少一种弹性体，所述弹性体可以为热塑性弹性体和/或热固性弹性体。具体地，所述弹性树脂可以为橡胶、聚酰胺型弹性体、 聚烯烃型弹性体、聚氨酯型弹性体、有机硅型弹性体和聚酯型弹性体中的一种或两种以上，优选为橡胶和/或聚酰胺型弹性体。
所述含树脂的组合物除含有弹性树脂外，还可以含有至少一种填料和/或至少一种流动性改进剂。
所述填料的种类可以根据具体的使用要求进行选择。所述填料可以为各种纤维型填料和/或粉末型填料。所述纤维型填料可以为选自玻璃纤维、碳纤维和芳族聚酰胺纤维中的一种或两种以上。所述粉末型填料可以为选自碳酸钙、碳酸镁、二氧化硅、重质硫酸钡、滑石粉、玻璃和粘土中的一种或两种以上。
所述填料的含量可以为常规选择。优选地，以100重量份弹性树脂为基准，所述填料的含量可以为10-150重量份，优选为15-100重量份，更优选为20-50重量份。
所述流动性改进剂用于提高弹性树脂的流动能力，进一步提高超弹性镍钛合金基材与弹性树脂之间的结合力以及弹性树脂的加工性能。所述流动性改进剂可以为各种能够实现上述效果的物质，优选为环状聚酯。
所述流动性改进剂的用量以能够提高弹性树脂的流动能力为准。优选地，相对于100重量份弹性树脂，所述流动性改进剂的含量为1-5重量份。
所述含弹性树脂的组合物根据具体使用要求还可以含有常见的各种助剂，如着色剂和/或抗氧剂，以改善最终形成的超弹性镍钛合金-弹性树脂复合体中弹性树脂层的性能或者赋予所述弹性树脂层以新的性能。
所述含弹性树脂的组合物可以通过将作为主体树脂的弹性树脂、任选的填料、任选的流动性改进剂以及任选的助剂混合均匀而获得。一般地，可以将弹性树脂、任选的填料、任选的流动性改进剂以及任选的助剂混合均匀，并进行挤出造粒而得到。
可以采用常用的各种方法向经表面处理的超弹性镍钛合金基材的蚀刻表面注入所述含弹性树脂的组合物。在本发明的一种优选的实施方式中，将所述经表面处理的超弹性镍钛合金基材置于模具中，通过注塑的方法向经表面处理的超弹性镍钛合金基材的蚀刻表面注入所述含弹性树脂的组合物。
所述注塑的条件可以根据含弹性树脂的组合物中弹性树脂的种类进行选择。
所述含弹性树脂的组合物的注入量可以根据预期的树脂层厚度进行选择。一般地，所述含弹性树脂的组合物的注入量使得形成的弹性树脂层的厚度为0.5-10mm。
根据本发明的方法，仅在经表面处理的超弹性镍钛合金基材的部分表面形成树脂层时，可以对无需形成树脂层的蚀刻表面进行处理，以除去表面凹坑以及由于蚀刻而引起的表面颜色变化，该处理可以在注塑成型步骤之前进行，也可以在注塑成型步骤之后进行，没有特别限定。
采用本发明的方法制备的超弹性镍钛合金-弹性树脂复合体中，弹性树脂层与超弹性镍钛合金基材之间的结合力高，具有较高的结构稳定性。
由此，本发明还提供了一种由根据本发明的方法制备的超弹性镍钛合金-弹性树脂复合体。该复合体包括超弹性镍钛合金基材以及附着于所述基材的至少部分表面上的弹性树脂 层，附着有所述弹性树脂层的基材表面分布有凹坑，所述弹性树脂层中的部分树脂向下延伸并填充于所述凹坑。
根据本发明的超弹性镍钛合金-弹性树脂复合体可以用于各种需要将超弹性镍钛合金与弹性树脂一体成型的场合，例如电子产品的外壳。在具体应用时，可以将超弹性镍钛合金成型为各种形状，并对需要形成树脂层的表面进行表面处理，然后注塑弹性树脂，形成弹性树脂层。
由此，本发明还提供了一种电子产品外壳，该外壳包括金属壳本体以及附着于所述金属壳本体的至少部分内表面和/或至少部分外表面的至少一个树脂件，所述金属壳本体的材质为超弹性镍钛合金，所述树脂件的材质为弹性树脂，其中，附着有所述树脂件的金属壳本体表面分布有凹坑，所述树脂件中的部分树脂向下延伸并填充于所述凹坑中。本发明中，所述外壳不仅包括为片状结构的外壳，也包括各种框架结构，如外框。
所述凹坑的宽度可以为10-100000nm，优选为300-30000nm；所述凹坑的深度可以为10-5000nm，优选为100-3000nm。
附着有所述树脂件的金属壳本体的表层氧元素的含量可以为1-10重量％，优选为1-6重量％，更优选为2-5重量份，进一步优选为3-4重量％。
根据本发明的电子产品外壳，根据具体需要，所述金属壳本体上可以设置有至少一个开口，以在该开口的对应位置安装电子产品的需要避开金属壳本体的元件。在一种实施方式中，由于金属对电磁信号具有屏蔽作用，因此至少部分开口的位置可以对应于发射和/或接受信号(如电磁信号)的元件的安装位置，此时所述开口位置优选设置树脂件，并使所述树脂件中的部分树脂填充于所述开口中，发射和/或接受信号的元件可以安装在所述树脂件上。
根据本发明的电子产品外壳，所述金属壳本体可以为一体结构，也可以为拼接结构。所述拼接结构是指所述金属壳本体包括相互断开的至少两个部分，两个部分相互拼接在一起形成金属壳本体。
在所述金属壳本体为拼接结构时，相邻两个部分可以用胶粘剂粘结在一起。在一种优选的实施方式中，相邻两部分的拼接位置设置有所述树脂件，该树脂件分别与相邻两部分搭接并覆盖所述拼接位置(即该树脂件桥接该相邻两部分)，这样能够提高拼接位置的结合强度；并且，可以根据电子产品的内部结构，将金属壳本体分成多个部分，所述树脂件在起到使金属壳本体形成为一个整体的作用的同时，还能用作一些电子元件的安装基体。
根据本发明的电子产品外壳，所述金属壳本体的至少部分外表面可以附着有树脂件，所述树脂件可以覆盖整个外表面，也可以覆盖金属壳本体的部分外表面以形成图案，例如装饰性图案。
根据本发明的电子产品外壳，所述金属壳本体的内表面附着有树脂件时，所述树脂件可以设置在需要的一个或多个位置。在一种优选的实施方式中，所述树脂件附着于所述金属壳本体的整个内表面，此时所述树脂件优选为一体结构。根据该优选的实施方式，特别适用于金属壳本体为拼接结构的场合。
根据本发明的电子产品外壳，可以为各种需要以金属作为外壳的电子产品外壳，例如： 移动终端的外壳或者外框，可穿戴电子设备的外壳或者外框。所述移动终端是指可以处于移动状态且具有无线传输功能的设备，例如：移动电话、便携式电脑(包括笔记本电脑和平板电脑)。所述可穿戴电子设备是指智能化的穿戴设备，例如：智能表、智能手环。所述电子产品具体可以为但不限于移动电话、便携式电脑(如笔记本电脑和平板电脑)、智能表和智能手环中的一种或两种以上。
图1示出了所述电子产品外壳为手机外壳时的一种实施方式的主视图和俯视图。如图1所示，在手机金属壳本体1上开设有多个开口3，开口3的位置可以对应于安装天线的位置以及安装各种按键的位置。树脂层2附着在手机金属壳本体1的整个内表面，树脂层2为一体结构并且树脂层2中的部分树脂填充于开口3中。
图2示出了所述电子产品外壳为智能表的外壳的一种实施方式的主视图。如2所示，智能表金属壳本体4上设置有对应于安装信号发射元件和/或信号接收元件的信号元件开口6，智能表金属壳本体4的内表面附着有树脂内衬层5，树脂内衬层5中的部分树脂填充在信号元件开口6中，信号元件可以安装在树脂内衬层5上的相应位置。
以下结合实施例详细说明本发明，但并不因此限制本发明的目的。
以下实施例和对比例中，在购自英斯特的型号为3369的万能试验机上以拉伸模式测定超弹性镍钛合金-弹性树脂复合体中超弹性镍钛合金基材与弹性树脂层之间的平均剪切强度，其中，将复合体发生断裂时测得的拉伸应力与结合面积之间的比值作为平均剪切强度，结合面积为金属基材与树脂层之间的结合面的面积。
以下实施例和对比例中，采用金相显微镜观察经表面处理的超弹性镍钛合金基材的表面和断面并确定形成的凹坑的宽度和深度，所使用的金相显微镜购自蔡司，型号为Axio Imager A1m。
以下实施例和对比例中，采用场发射扫描电镜及附件能谱仪测试表层元素含量，能谱仪购自日本电子株式会社，型号为JSM-7600F，其中，在被测样品表面选择10个点进行能谱分析，10个点分布在样品表面的不同位置，将由这10个点得到的氧元素含量的平均值作为该样品的表层氧元素含量。
实施例1-5用于说明本发明。
实施例1
(1)前处理
将厚度为0.8mm的SMA超弹性镍钛形状记忆合金板(购自东莞广升达五金有限公司)，切成15mm×80mm的长方形片，将其放入抛光机内打磨抛光，再依次进行除油、水洗和烘干，得到超弹性镍钛合金片。
(2)表面处理
(2.1)第一蚀刻步骤
将步骤(1)得到的超弹性镍钛合金片置于500mL蚀刻液中于25℃浸泡120分钟后，将超弹性镍钛合金片取出，用去离子水洗涤3次。其中，蚀刻液为浓度为10重量％的盐酸。
(2.2)第二蚀刻步骤
将步骤(2.1)得到的超弹性镍钛合金片置于500mL蚀刻液中于25℃浸泡60分钟后，将超弹性镍钛合金片取出，用去离子水洗涤3次。然后放入烘箱中于65℃烘干，得到经表面处理的超弹性镍钛合金片。其中，蚀刻液为氢氧化钠和硼酸的混合水溶液，氢氧化钠的浓度为7mol/L，硼酸的浓度为0.5mol/L。
采用金相显微镜对经表面处理的超弹性镍钛合金片的表面进行观察，确定得到的经表面处理的超弹性镍钛合金片表面形成有密集分布的凹坑，所述凹坑的宽度各自在300-30000nm的范围内，深度各自在100-3000nm的范围内。采用扫描电镜对该经表面处理的超弹性镍钛合金片的表面进行能谱分析，测定各元素含量并确定氧元素含量，结果见表1。
(3)注入成型
将步骤(2.2)得到的经表面处理的超弹性镍钛合金片放入模具中，然后向模具中注塑含聚酰胺弹性树脂(购自东莞市基石工程塑料有限公司，牌号为TR90)和玻璃纤维的组合物，在超弹性镍钛合金片的一个表面形成树脂层，从而得到超弹性镍钛合金-弹性树脂复合体(弹性树脂层的厚度为3mm)。其中，相对于100重量份聚酰胺弹性树脂，玻璃纤维的含量为20重量份。该复合体中，超弹性镍钛合金基材与树脂层之间的平均剪切强度在表2中列出。
对比例1
(1)采用与实施例1步骤(1)相同的方法进行前处理。
(2)采用与实施例1步骤(3)相同的方法向经前处理的超弹性镍钛合金片的表面注塑含聚酰胺弹性树脂的组合物并进行成型，以得到超弹性镍钛合金-弹性树脂复合体，其中，超弹性镍钛合金基材与弹性树脂层之间的平均剪切强度在表2中列出。
对比例2
(1)采用与实施例1步骤(1)相同的方法进行前处理。
(2)采用与实施例1步骤(2.1)相同的方法对步骤(1)得到的超弹性镍钛合金片进行表面处理，得到经表面处理的镍钛合金片。
采用金相显微镜对经表面处理的超弹性镍钛合金片的表面进行观察，确定得到的经表面处理的镍钛合金片表面形成有密集分布的凹坑，所述凹坑的宽度各自在300-30000nm的范围内，深度各自在100-3000nm的范围内。采用扫描电镜对该经表面处理的超弹性镍钛合金片的表面进行能谱分析，测定各元素含量并确定氧元素含量，结果见表1。
(3)采用与实施例1步骤(3)相同的方法向步骤(2)得到的经表面处理的超弹性镍钛合金片的表面注塑含聚酰胺弹性树脂和玻璃纤维的组合物并进行成型，以得到超弹性镍钛合金-弹性树脂复合体，其中，超弹性镍钛合金基材与弹性树脂层之间的平均剪切强度在表2中列出。
对比例3
(1)采用与实施例1步骤(1)相同的方法进行前处理。
(2)采用与实施例1步骤(2.2)相同的方法对步骤(1)得到的超弹性镍钛合金片进行表面处理，得到经表面处理的镍钛合金片。
采用金相显微镜对该超弹性镍钛合金片的表面进行观察，在经表面处理的超弹性镍钛合金片表面没有发现明显的凹坑。
(3)采用与实施例1步骤(3)相同的方法向步骤(2)得到的经表面处理的超弹性镍钛合金片的表面注塑含聚酰胺弹性树脂的组合物并进行成型，以得到超弹性镍钛合金-弹性树脂复合体，其中，超弹性镍钛合金基材与弹性树脂层之间的平均剪切强度在表2中列出。
对比例4
(1)采用与实施例1步骤(1)相同的方法进行前处理。
(2)采用与实施例1步骤(2.1)相同的方法对步骤(1)得到的超弹性镍钛合金片进行表面处理，得到经表面处理的超弹性镍钛合金片，不同的是，浸泡时间为320分钟。
采用金相显微镜对该超弹性镍钛合金片的表面和断面进行观察，确定得到的经表面处理的超弹性镍钛合金片表面形成有密集分布的凹坑，所述凹坑的宽度各自在100000-150000nm的范围内，深度各自在40000-80000nm的范围内。采用扫描电镜对该超弹性镍钛合金片表面进行能谱分析，测定各元素含量并确定氧元素含量，结果见表1。
(3)采用与实施例1步骤(3)相同的方法向步骤(2)得到的经表面处理的超弹性镍钛合金片的表面注塑含聚酰胺弹性树脂和玻璃纤维的组合物并进行成型，以得到超弹性镍钛合金-弹性树脂复合体，其中，超弹性镍钛合金基材与弹性树脂层之间的平均剪切强度在表2中列出。
实施例2
(1)采用与实施例1步骤(1)相同的方法进行前处理。
(2)表面处理
(2.1)第一蚀刻步骤
将步骤(1)得到的超弹性镍钛合金片置于500mL蚀刻液中于15℃浸泡240分钟后，将超弹性镍钛合金片取出，用去离子水洗涤3次。其中，蚀刻液为浓度为5重量％的盐酸。
(2.2)第二蚀刻步骤
将步骤(2.1)得到的超弹性镍钛合金片置于500mL蚀刻液中于25℃浸泡45分钟后，将超弹性镍钛合金片取出，用去离子水洗涤3次。然后放入烘箱中于65℃烘干，得到经表面处理的超弹性镍钛合金片。其中，蚀刻液为氢氧化钠和磷酸氢二钠的混合水溶液，氢氧化钠的浓度为7mol/L，磷酸氢二钠的浓度为1mol/L。
采用金相显微镜对经表面处理的超弹性镍钛合金片的表面进行观察，确定得到的经表面处理的超弹性镍钛合金片表面形成有密集分布的凹坑，所述凹坑的宽度各自在300-30000nm 的范围内，深度各自在100-3000nm的范围内。采用扫描电镜对该经表面处理的超弹性镍钛合金片的表面进行能谱分析，测定各元素含量并确定氧元素含量，结果见表1。
(3)采用与实施例1步骤(1)相同的方法向步骤(2)得到的经表面处理的超弹性镍钛合金片的表面注塑含聚酰胺弹性树脂和玻璃纤维的组合物并进行成型，以得到超弹性镍钛合金-弹性树脂复合体(弹性树脂层的厚度为3mm)，其中，超弹性镍钛合金基材与弹性树脂层之间的平均剪切强度在表2中列出。
实施例3
(1)采用与实施例1步骤(1)相同的方法进行前处理。
(2)表面处理
(2.1)第一蚀刻步骤
将步骤(1)得到的超弹性镍钛合金片置于500mL蚀刻液中于35℃浸泡90分钟后，将超弹性镍钛合金片取出，用去离子水洗涤3次。其中，蚀刻液为浓度为15重量％的盐酸。
(2.2)第二蚀刻步骤
将步骤(2.1)得到的超弹性镍钛合金片置于500mL蚀刻液中于35℃浸泡90分钟后，将超弹性镍钛合金片取出，用去离子水洗涤3次。然后放入烘箱中于65℃烘干，得到经表面处理的超弹性镍钛合金片。其中，蚀刻液为氢氧化钠和碳酸钠的混合水溶液，氢氧化钠的浓度为6mol/L，碳酸钠的浓度为0.2mol/L。
采用金相显微镜对经表面处理的超弹性镍钛合金片的表面进行观察，确定得到的经表面处理的超弹性镍钛合金片表面形成有密集分布的凹坑，所述凹坑的宽度各自在300-30000nm的范围内，深度各自在100-3000nm的范围内。采用扫描电镜对该经表面处理的超弹性镍钛合金片的表面进行能谱分析，测定各元素含量并确定氧元素含量，结果见表1。
(3)采用与实施例1步骤(1)相同的方法向步骤(2)得到的经表面处理的超弹性镍钛合金片的表面注塑含聚酰胺弹性树脂和玻璃纤维的组合物并进行成型，以得到超弹性镍钛合金-弹性树脂复合体，其中，超弹性镍钛合金基材与弹性树脂层之间的平均剪切强度在表2中列出。
实施例4
(1)采用与实施例1步骤(1)相同的方法进行前处理。
(2)表面处理
(2.1)采用与实施例1步骤(2.1)相同的方法对步骤(1)得到的超弹性镍钛合金片进行蚀刻。
(2.2)采用与实施例1步骤(2.2)相同的方法对步骤(2.1)得到的经盐酸蚀刻的超弹性镍钛合金片进行蚀刻，不同的是，蚀刻液为氢氧化钠水溶液，氢氧化钠的浓度为7mol/L。
采用金相显微镜对经表面处理的超弹性镍钛合金片的表面进行观察，确定得到的经表面处理的超弹性镍钛合金片表面形成有密集分布的凹坑，所述凹坑的宽度各自在10-100000nm 的范围内，深度各自在10-5000nm的范围内。采用扫描电镜对该经表面处理的超弹性镍钛合金片的表面进行能谱分析，测定各元素含量并确定氧元素含量，结果见表1。
(3)采用与实施例1步骤(1)相同的方法向步骤(2)得到的经表面处理的超弹性镍钛合金片的表面注塑含聚酰胺弹性树脂和玻璃纤维的组合物并进行成型，以得到超弹性镍钛合金-弹性树脂复合体，其中，超弹性镍钛合金基材与弹性树脂层之间的平均剪切强度在表2中列出。
实施例5
(1)采用与实施例1步骤(1)相同的方法进行前处理。
(2)采用与实施例1步骤(2)相同的方法对步骤(1)得到的超弹性镍钛合金片进行表面处理，不同的是，步骤(2.2)中，蚀刻液的温度为45℃，浸泡时间为40分钟。
采用金相显微镜对经表面处理的超弹性镍钛合金片的表面进行观察，确定得到的经表面处理的超弹性镍钛合金片表面形成有密集分布的凹坑，所述凹坑的宽度各自在300-30000nm的范围内，深度各自在100-3000nm的范围内。采用扫描电镜对该经表面处理的超弹性镍钛合金片的表面进行能谱分析，测定各元素含量并确定氧元素含量，结果见表1。
(3)采用与实施例1步骤(1)相同的方法向步骤(2)得到的经表面处理的超弹性镍钛合金片的表面注塑含聚酰胺弹性树脂和玻璃纤维的组合物并进行成型，以得到超弹性镍钛合金-弹性树脂复合体，其中，超弹性镍钛合金基材与弹性树脂层之间的平均剪切强度在表2中列出。
表1
Figure PCTCN2015093244-appb-000001
表2
编号 平均剪切强度/MPa
实施例1 17.65
对比例1 /*
对比例2 1.19
对比例3 /*
对比例4 1.68
实施例2 16.72
实施例3 16.24
实施例4 15.06
实施例5 16.39
*：脱模时，弹性树脂层从超弹性镍钛合金表面脱落。
从表2的结果可以看出，根据本发明的超弹性镍钛合金-弹性树脂复合体中，超弹性镍钛合金基材与弹性树脂层之间的平均剪切强度高，表明超弹性镍钛合金基材与弹性树脂层之间具有较高的结合强度，因而本发明的超弹性镍钛合金-弹性树脂复合体的结构稳定性好。

Claims (33)

  1. 一种超弹性镍钛合金-弹性树脂复合体，该复合体包括超弹性镍钛合金基材以及附着于所述基材的至少部分表面上的弹性树脂层，附着有所述弹性树脂层的基材表面分布有凹坑，所述弹性树脂层中的部分树脂向下延伸并填充于所述凹坑中。
  2. 根据权利要求1所述的复合体，其中，所述凹坑的宽度为10-100000nm，优选为300-30000nm；所述凹坑的深度为10-5000nm，优选为100-3000nm。
  3. 根据权利要求1或2所述的复合体，其中，所述超弹性镍钛合金基材表层氧元素的含量为1-10重量％，优选为1-6重量％，更优选为2-5重量份，进一步优选为3-4重量％。
  4. 根据权利要求1所述的复合体，其中，所述弹性树脂层中的树脂为至少一种橡胶和/或至少一种弹性体。
  5. 一种超弹性镍钛合金基材表面处理方法，该方法包括第一蚀刻步骤和第二蚀刻步骤：
    在第一蚀刻步骤中，将超弹性镍钛合金基材浸泡于第一蚀刻液中，所述第一蚀刻液为盐酸；
    在第二蚀刻步骤中，将经第一蚀刻的超弹性镍钛合金基材浸泡于第二蚀刻液中，得到经表面处理的超弹性镍钛合金基材，所述第二蚀刻液含有至少一种碱金属氢氧化物。
  6. 根据权利要求5所述的方法，其中，所述盐酸的浓度为1-30重量％，优选为5-20重量％。
  7. 根据权利要求5或6所述的方法，其中，所述第一蚀刻液的温度为15-50℃，优选为15-40℃。
  8. 根据权利要求7所述的方法，其中，第一蚀刻步骤中，在第一蚀刻液中的浸泡时间为5-300分钟。
  9. 根据权利要求5所述的方法，其中，所述碱金属氢氧化物为氢氧化钠和/或氢氧化钾。
  10. 根据权利要求6或9所述的方法，其中，所述第二蚀刻液中，碱金属氢氧化物的浓度为1-10mol/L，优选为5-8mol/L。
  11. 根据权利要求6、9和10中任意一项所述的方法，其中，所述第二蚀刻液还含有至少一种缓冲剂，所述缓冲剂能够稳定第二蚀刻液中氢氧根离子的浓度。
  12. 根据权利要求11所述的方法，其中，所述缓冲剂为选自硼酸、硼酸钠、碳酸钠、碳酸二氢钠、磷酸三钠、磷酸氢二钠和柠檬酸钠中的一种或两种以上。
  13. 根据权利要求11或12所述的方法，其中，所述缓冲剂的浓度为0.1-1.5mol/L。
  14. 根据权利要求9-13中任意一项所述的方法，其中，所述第二蚀刻液的温度为15-70℃。
  15. 根据权利要求14所述的方法，其中，第二蚀刻步骤中，在第二蚀刻液中的浸泡时间为0.5-24小时。
  16. 根据权利要求5-15中任意一项所述的方法，其中，经过第一蚀刻步骤和第二蚀刻步骤后形成的经表面处理的超弹性镍钛合金基材表面形成有凹坑，所述凹坑的宽度为10-100000nm，优选为300-30000nm；所述凹坑的深度为10-5000nm，优选为100-3000nm。
  17. 根据权利要求5-16中任意一项所述的方法，其中，经过第一蚀刻步骤和第二蚀刻 步骤后形成的经表面处理的超弹性镍钛合金基材表层氧元素的含量为1-10重量％，优选为1-6重量％，更优选为2-5重量份，进一步优选为3-4重量％。
  18. 一种经表面处理的超弹性镍钛合金基材，该超弹性镍钛合金基材的至少部分表面为采用权利要求5-17中任意一项所述的方法进行蚀刻而形成的表面。
  19. 一种超弹性镍钛合金-弹性树脂复合体的制备方法，该方法包括向权利要求18所述超弹性镍钛合金基材的经处理的表面注入一种含弹性树脂的组合物并使部分组合物填充于所述凹坑中，成型后形成弹性树脂层。
  20. 根据权利要求19所述的方法，其中，所述弹性树脂为至少一种橡胶和/或至少一种弹性体。
  21. 一种由权利要求19或20所述的方法制备的超弹性镍钛合金-弹性树脂复合体。
  22. 一种电子产品外壳，该外壳包括金属壳本体以及附着于所述金属壳本体的至少部分内表面和/或至少部分外表面的至少一个树脂件，所述金属壳本体的材质为超弹性镍钛合金，所述树脂件的材质为弹性树脂，其特征在于，附着有所述树脂件的金属壳本体表面分布有凹坑，所述树脂件中的部分树脂向下延伸并填充于所述凹坑中。
  23. 根据权利要求22所述的电子产品外壳，其中，所述凹坑的宽度为10-100000nm，优选为300-30000nm；所述凹坑的深度为10-5000nm，优选为100-3000nm。
  24. 根据权利要求22或23所述的电子产品外壳，其中，附着有所述树脂件的金属壳本体的表层氧元素的含量为1-10重量％，优选为1-6重量％，更优选为2-5重量份，进一步优选为3-4重量％。
  25. 根据权利要求22-24中任意一项所述的电子产品外壳，其中，所述金属壳本体上设置有至少一个开口。
  26. 根据权利要求25所述的电子产品外壳，其中，至少部分开口的位置对应于发射和/或接受信号的元件的安装位置。
  27. 根据权利要求25或26所述的电子产品外壳，其中，所述开口位置设置有树脂件，所述树脂件中的部分树脂填充于所述开口中。
  28. 根据权利要求22-27中任意一项所述的电子产品外壳，其中，所述金属壳本体包括相互断开的至少两个部分，相邻两部分的拼接位置设置有所述树脂件，该树脂件分别与相邻两部分搭接并覆盖所述拼接位置。
  29. 根据权利要求22-28中任意一项所述的电子产品外壳，其中，所述金属壳本体的至少部分外表面附着有树脂件，所述树脂件在金属壳本体的外表面形成图案。
  30. 根据权利要求22-29中任意一项所述的电子产品外壳，其中，所述树脂件附着于所述金属壳本体的整个内表面。
  31. 根据权利要求30所述的电子产品外壳，其中，附着于所述金属壳本体的树脂件为一体结构。
  32. 根据权利要求22-31中任意一项所述的电子产品外壳，其中，所述电子产品为移动终端或者可穿戴电子设备。
  33. 根据权利要求22-31中任意一项所述的电子产品外壳，其中，所述电子产品为移动电话、便携式电脑、智能表或者智能手环。
PCT/CN2015/093244 2014-12-25 2015-10-29 超弹性镍钛合金-弹性树脂复合体和超弹性镍钛合金基材及其制备方法以及电子产品外壳 Ceased WO2016101704A1 (zh)

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