WO2016101704A1 - Composite d'alliage de nickel-titane hyperélastique et d'une résine élastique, substrat en alliage de nickel-titane hyperélastique, son procédé de préparation et boîtier de produit électronique - Google Patents

Composite d'alliage de nickel-titane hyperélastique et d'une résine élastique, substrat en alliage de nickel-titane hyperélastique, son procédé de préparation et boîtier de produit électronique 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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WIPO (PCT)
Prior art keywords
titanium alloy
elastic resin
superelastic nickel
substrate
nickel
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PCT/CN2015/093244
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English (en)
Chinese (zh)
Inventor
章晓
陶乐天
孙剑
陈梁
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比亚迪股份有限公司
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Publication of WO2016101704A1 publication Critical patent/WO2016101704A1/fr

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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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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

La présente invention concerne un composite d'alliage de nickel-titane hyperélastique et d'une résine élastique et un procédé de préparation. Le composite comprend un substrat en alliage de nickel-titane hyperélastique et une couche de résine élastique collée à au moins une partie d'une surface du substrat, la surface du substrat collée à la couche de résine élastique étant couverte d'évidements et ces évidements étant remplis d'une partie de la résine de la couche de résine élastique. L'invention concerne également un alliage de nickel-titane hyperélastique traité en surface ainsi que son procédé de préparation et le procédé comprend l'attaque de l'alliage de nickel-titane hyperélastique avec un acide et une base de manière séquentielle. L'invention concerne en outre un boîtier de produit électronique. En utilisant le procédé de la présente invention pour réaliser un traitement superficiel de l'alliage de nickel-titane hyperélastique, des évidements répartis de manière dense peuvent être formés sur la surface de l'alliage de nickel-titane hyperélastique, de telle sorte qu'une force de liaison plus importante existe entre la couche de résine et le substrat en alliage de nickel-titane hyperélastique dans le composite de l'alliage de nickel-titane hyperélastique préparé et la résine élastique convenant aux boîtiers de divers produits électroniques.
PCT/CN2015/093244 2014-12-25 2015-10-29 Composite d'alliage de nickel-titane hyperélastique et d'une résine élastique, substrat en alliage de nickel-titane hyperélastique, son procédé de préparation et boîtier de produit électronique WO2016101704A1 (fr)

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WO2018129996A1 (fr) * 2017-01-10 2018-07-19 广东长盈精密技术有限公司 Procédé de traitement de surface de matériau, produit de matériau et matériau composite
CN106965374A (zh) * 2017-03-20 2017-07-21 歌尔股份有限公司 一种不锈钢和塑料的结合件及其加工方法
CN109130069A (zh) * 2017-06-15 2019-01-04 优尔工业材料（廊坊）有限公司 钛合金-塑胶复合体的制造方法
CN112203444A (zh) * 2019-07-08 2021-01-08 苹果公司 具有蚀刻表面的钛部件
US11511519B2 (en) 2019-07-08 2022-11-29 Apple Inc. Titanium part having an etched surface

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