CN103950147A - Metal wetting agent and preparation method of composite material - Google Patents
Metal wetting agent and preparation method of composite material Download PDFInfo
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- CN103950147A CN103950147A CN201410181395.XA CN201410181395A CN103950147A CN 103950147 A CN103950147 A CN 103950147A CN 201410181395 A CN201410181395 A CN 201410181395A CN 103950147 A CN103950147 A CN 103950147A
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
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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
- B29C2045/1486—Details, accessories and auxiliary operations
- B29C2045/14868—Pretreatment of the insert, e.g. etching, cleaning
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- ing And Chemical Polishing (AREA)
- Laser Beam Processing (AREA)
Abstract
The invention discloses a preparation method of a composite material and a metal wetting agent. The method comprises the following steps: (1) carrying out surface laser treatment on a metal substrate so as to form fine holes; (2) carrying out surface treatment on the metal substrate with the fine holes by virtue of the metal wetting agent; (3) carrying out injection molding on plastic and the metal substrate processed by virtue of the metal wetting agent so as to form the composite material integrating metal and the plastic. The metal wetting agent contains an organic acid agent for improving the difference of surface tension coefficients of the metal substrate and the plastic. By virtue of the metal wetting agent, the bonding strength of the metal and the plastic can be effectively improved.
Description
Technical field
The present invention relates to the preparation method of a kind of wetting metal agent and complex material.
Background technology
By chemical pretreatment solution, metallic substrate surface is processed, can be made metallic substrate surface form irregular hole, and then carry out integrated molding with plastics and be prepared into complex material.Because chemical pretreatment solution generally all contains the chemical reagent of strong acid and strong base and other compositions, its waste liquid has increased processing cost to a great extent, and the processing of waste liquid exists many difficulty.
Existing by FIB, etching carried out in metal surface and form nanopore array, then the method for carrying out integrated combination with resin.Because FIB is to utilize the mode focusing on that heat is focused on to working position to melt metal, this can cause the position of its periphery to produce larger heat affected area, and metal part easily occurs and burns phenomenon, is unfavorable for following process processing.According to prior art, directly by plastic injection-moulded, to be combined with metallic substrate surface, bond strength is more limited, is difficult to desirable degree.
Summary of the invention
One object of the present invention is to overcome the deficiencies in the prior art, and a kind of preparation method of complex material is provided, and realizes the high-strength combination of metal and plastics.
Another object is to provide a kind of wetting metal agent, can effectively improve the bond strength of metal and plastics for described preparation method.
For achieving the above object, the present invention is by the following technical solutions:
A preparation method for complex material, comprises the following steps:
1) metal base is carried out to surface laser processing, to form fine hole;
2) with wetting metal agent, to thering is the metal base of fine hole, carry out surface treatment;
3) metal base and plastics after wetting metal agent is processed are carried out to injection mo(u)lding, obtain the integrated complex material of metal and plastics;
Wherein, in described wetting metal agent, contain the organic acid agent that is useful on the surface tension coefficient difference of improving described metal base and plastics.
In further technical scheme:
Described wetting metal agent adopts following formula:
The water of 1000 parts or organic solvent, be at least furnished with organic acid agent 50-400 part, and described organic acid agent is one or more organic acids or organic acid derivatives or its combination.
Described organic acid agent is selected from one or more in following composition: terephthalic acid (TPA), maleic acid, citric acid, ethylenediamine tetra-acetic acid, tartaric acid, p-nitrophenyl sulfonic acid, acetic acid, malic acid, trifluoroacetic acid, 1,3-malonic acid, paranitrobenzoic acid, trinitrobenzoic acid and water soluble amino acids, or their organic derivative.
Described wetting metal agent is also furnished with inorganic acid 60-250 part, and described inorganic acid is selected from one or more in hydrochloric acid, sulfuric acid, hydrobromic acid, nitric acid, phosphoric acid.
The formula that described wetting metal agent adopts is that the water of 1000 parts or organic solvent are at least furnished with following inorganic acid and organic acid agent:
105 parts of concentrated hydrochloric acids, 120 parts of maleic acids, 80 parts of malic acid; Or
65 parts of concentrated hydrochloric acids, 105 parts of maleic acids, 95 parts of malic acid; Or
248 parts of concentrated hydrochloric acids, 85 parts of maleic acids, 115 parts of malic acid; Or
85 parts of concentrated hydrochloric acids, 10 parts of the concentrated sulfuric acids, 54 parts of terephthalic acid (TPA)s; Or
50 parts of concentrated hydrochloric acids, 25 parts of the concentrated sulfuric acids, 175 parts of terephthalic acid (TPA)s, 25 parts of trifluoroacetic acids; Or
75 parts of concentrated hydrochloric acids, 50 parts of the concentrated sulfuric acids, 385 parts of terephthalic acid (TPA)s, 15 parts of malic acid.
Step 2) in, the metal base with micron order hole is put into described wetting metal agent and carry out surface treatment, treatment temperature is 45-85 ℃, and the processing time is 10-35min.
Step 1) in, metal base is carried out to surperficial Ultra-Violet Laser processing, take and form the micron order hole that opening diameter is 100-350 micron as 10-60 micron, the degree of depth, wherein the wavelength of Ultra-Violet Laser is 190-400nm, power is 3-12W, and the diameter of light beam is 1-50 micron.
Step 3) in, the surperficial injection of plastic to this base material in injection forming mold, injection temperature is controlled between 120-145 ℃.
For described preparation method's a wetting metal agent, described wetting metal agent is containing the organic acid agent that is useful on the surface tension coefficient difference of improving described metal base and plastics.
The formula of described wetting metal agent is:
The water of 1000 parts or organic solvent, be at least furnished with organic acid agent 50-400 part, and described organic acid agent is one or more organic acids or organic acid derivatives or its combination.
Preferably, described wetting metal agent is also furnished with inorganic acid 60-250 part, and described inorganic acid is selected from one or more in hydrochloric acid, sulfuric acid, hydrobromic acid, nitric acid, phosphoric acid.
Preferably, described organic acid agent is selected from one or more in following composition: terephthalic acid (TPA), maleic acid, citric acid, ethylenediamine tetra-acetic acid, tartaric acid, p-nitrophenyl sulfonic acid, acetic acid, malic acid, trifluoroacetic acid, 1,3-malonic acid, paranitrobenzoic acid, trinitrobenzoic acid and water soluble amino acids, or their organic derivative.
Useful technique effect of the present invention:
According to the present invention, using Laser Processing metallic substrate surface to form after fine hole, with wetting metal agent, carry out moistened surface processing, improve the surface tension coefficient difference of metal base and plastics, overcome in prior art metal base and plastics when carrying out injection mo(u)lding, because both exist each other the former of surface tension coefficient difference thereby cause plastics to be difficult for producing the problem of effective combination with metal surface, the adhesion of effectively improving metal base fine hole surface and plastics, realizes the high-strength combination of metal and plastics.And technological operation of the present invention is simple and easy, is particularly suitable for metal base and combines formation compound system with plastics for electronic product structural member, after injection mo(u)lding, be difficult for occurring the loosening of binding site, the serviceability that guarantees structural member, its cost of manufacture is low, effective.In addition, the method of Laser Processing of the present invention metal surface combines the processing of metal wetting agent, but be different from the method that traditional dependence chemical pretreatment solution forms fine hole, the relatively environmental protection of processing processing procedure, and the metallic substrate surface after wetting metal agent is processed does not shade substantially, does not affect the outward appearance of structural member product.
Accompanying drawing explanation
Fig. 1 is the basic flow sheet of the preparation method embodiment of complex material of the present invention.
The specific embodiment
Below in conjunction with accompanying drawing, embodiments of the invention are elaborated.Should be emphasized that, following explanation is only exemplary, rather than in order to limit the scope of the invention and to apply.
When preparing metallo-plastic complex material, metal and plastics surface both coefficient of tension difference are an objective reality easy uncared-for major issues again.Metal and plastics are when carrying out injection mo(u)lding, because both exist the reason of surface tension coefficient difference each other, cause plastics to be difficult for producing effective combination with metal surface, also affect plastics and enter the Expected Results of filling enhancing combination in metal hole simultaneously, the bond strength of prepared like this metallo-plastic complex material is not high, even if also easily there is structural becoming flexible after moulding, this serviceability on structural member produces larger impact.Inventor notices, if can improve in some way metal and plastics surface both coefficient of tension difference, can effectively improve both bond strengths.
Consult Fig. 1, according to embodiments of the invention, the preparation method of complex material comprises the following steps:
Metal base is carried out to surface laser processing, to form fine hole;
With wetting metal agent, to thering is the metal base of fine hole, carry out surface treatment;
Metal base and plastics after wetting metal agent is processed are carried out to injection mo(u)lding, obtain the integrated complex material of metal and plastics;
Wherein, in described wetting metal agent, contain the organic acid agent that is useful on the surface tension coefficient difference of improving described metal base and plastics.
Implement method of the present invention material used as follows.
1, metal: described metal can be the metal base by machining moulding, can be, but not limited to is a kind of in stainless steel, titanium alloy, aluminium alloy, magnesium alloy and copper alloy.
2, plastics: it is crystalline thermoplastic material that said plastics can be, but not limited to can be for example a kind of in polybutylene terephthalate (PBT), nylon, Merlon, PETG, polyphenylene sulfide and aromatic polyamide resin.Described resin be take polybutylene terephthalate (PBT) or PETG or polyphenylene sulfide as main component, is wherein added with mass content simultaneously and is the glass fibre of 25%-50% as auxiliary element.
3, complex material: metal base and plastics by machining moulding can be by the integrated complex materials that obtains of injection molding technology.This metallic substrate surface can be after Ultra-Violet Laser processing is processed, to form have micron order hole and process through wetting metal agent, makes plastics can enter in metal hole component with wetting agent and reacts and form chemical bond and connecting shaping.In preferred embodiment, the micron order hole of described genus substrate surface, its opening diameter is less than diameter at the bottom of its hole, and its opening diameter is 10-60 micron, and the degree of depth of micropore is 100-350 micron.
4, wetting metal agent:
In the solvents of 1000 parts (can include but not limited to water, ethanol, methyl alcohol, wherein one or more of acetone), can be furnished with the raw material of following weight ratio:
1) inorganic acid 60-250 part
It is one or more in concentrated hydrochloric acid, the concentrated sulfuric acid, hydrobromic acid, red fuming nitric acid (RFNA), SPA that said inorganic acid can be, but not limited to.
The Main Function of inorganic acid is to carry out further etching reaction with metal, improves surperficial roughness, strengthens the bonded area with plastics; Meanwhile, inorganic acid fluid enters in the micron order hole of metal surface, can react with the metal of hole inside, further expands scope and the degree of depth of hole, increases the bonded area of plastics and metal hole.
2) organic acid agent 50-400 part
It is one or more organic acids of following component that said organic acid agent can be, but not limited to: terephthalic acid (TPA), maleic acid, citric acid, ethylenediamine tetra-acetic acid, tartaric acid, p-nitrophenyl sulfonic acid, acetic acid, malic acid, trifluoroacetic acid, 1,3-malonic acid, paranitrobenzoic acid, trinitrobenzoic acid and water soluble amino acids.Organic acid agent of the present invention can also comprise organic acid organic derivative.
The effect of organic acid agent is, can improve on the one hand the surface tension of metal base, improves the wetability of metal surface, on the other hand organic acid from when injection moulding can with the plastics formation chemical bond that reacts, effectively increase the conjugation of plastics and metal.
According to embodiments of the invention, a kind of preparation method of complex material can comprise the following steps:
1) provide by the metal base of machining moulding, can be, but not limited to is a kind of in stainless steel, titanium alloy, aluminium alloy, magnesium alloy and copper alloy.
2) with degreaser, metal base is carried out to electrochemical deoiling processing, to remove the greasy dirt of metal surface; Electrochemical deoiling temperature 50-100 ℃, the oil removing time determines according to concrete deoiling effect.
3) metal base after oil removal treatment is carried out to surperficial Ultra-Violet Laser processing, take and form opening diameter as 10-60 micron, the degree of depth of micropore is the hole of 100-350 micron.
The technological parameter that Ultra-Violet Laser is processed: a) wavelength is 190-400nm; B) power is 3-12W; C) diameter of light beam is 1-50 micron.
4) metal base after Ultra-Violet Laser processing processing with micron order hole is put into wetting metal agent and carry out surface treatment.
Surface-treated technological parameter: a) temperature: 45-85 ℃; B) time: 10-35min.
5) metal base after wetting metal agent is processed is put into integrated injection molding mould, then injection of plastic is carried out in the surface of this base material, obtain the integrated complex material of metal and plastics; During injection moulding, mold temperature is controlled between 120-145 ℃.
Embodiment mono-
Wetting metal agent comprises following component:
In 1000 parts of solvents (wherein water is 700 parts, 300 parts of ethanol), be furnished with the raw material components of following weight ratio:
1) concentrated hydrochloric acid is 105 parts;
2) organic acid is 200 parts, wherein: 120 parts of maleic acids, 80 parts of malic acid.
The preparation method of complex material comprises the following steps:
1) provide by the metal base of machining moulding, relate generally to and comprise a kind of in stainless steel, titanium alloy, aluminium alloy, magnesium alloy and copper alloy.
2) with the degreaser of selling on the market, metal base is carried out to electrochemical deoiling processing, to remove the greasy dirt of metal surface; 85 ℃ of electrochemical deoiling temperature, the oil removing time determines according to concrete deoiling effect.
3) metal base after oil removal treatment is carried out to surperficial Ultra-Violet Laser processing, take and form opening diameter as 10-60 micron, the degree of depth of micropore is the hole of 100-350 micron.
The technological parameter that Ultra-Violet Laser is processed: a) wavelength is 355nm; B) power is 5.5W; C) diameter of light beam is 10 microns.
4) metal base after Ultra-Violet Laser processing processing with micron order hole is put into wetting metal agent and carry out moistened surface processing.
Surface-treated technological parameter: a) temperature: 75 ℃; B) time: 15min.
5) metal base after wetting metal agent is processed is put into integrated injection molding mould, then injection of plastic is carried out in the surface of this base material, obtain the integrated complex material of metal and plastics; During injection moulding, mold temperature is controlled between 130-140 ℃.
Bond strength test: the resulting metal of aforesaid way and plastics complex material are carried out to tensile strength test with electronic universal material testing machine, and the average tensile strength of this complex material reaches 16.3MPa.
Embodiment bis-
Wetting metal agent comprises following component:
In 1000 parts of solvents (wherein water is 700 parts, 300 parts of ethanol), be furnished with the raw material components of following weight ratio:
1) concentrated hydrochloric acid is 65 parts;
2) organic acid is 200 parts, wherein: 105 parts of maleic acids, 95 parts of malic acid.
The preparation method of complex material comprises the following steps:
1) provide by the metal base of machining moulding, relate generally to and comprise a kind of in stainless steel, titanium alloy, aluminium alloy, magnesium alloy and copper alloy.
2) with the degreaser of selling on the market, metal base is carried out to electrochemical deoiling processing, to remove the greasy dirt of metal surface; 85 ℃ of electrochemical deoiling temperature, the oil removing time determines according to concrete deoiling effect.
3) metal base after oil removal treatment is carried out to surperficial Ultra-Violet Laser processing, take and form opening diameter as 10-60 micron, the degree of depth of micropore is the hole of 100-350 micron.
The technological parameter that Ultra-Violet Laser is processed: a) wavelength is 355nm; B) power is 5.5W; C) diameter of light beam is 10 microns.
4) metal base after Ultra-Violet Laser processing processing with micron order hole is put into wetting metal agent and carry out moistened surface processing.
Surface-treated technological parameter: a) temperature: 85 ℃ of b) time: 10min.
5) metal base after wetting metal agent is processed is put into integrated injection molding mould, then injection of plastic is carried out in the surface of this base material, obtain the integrated complex material of metal and plastics; During injection moulding, mold temperature is controlled between 130-140 ℃.
Bond strength test: the resulting metal of aforesaid way and plastics complex material are carried out to tensile strength test with electronic universal material testing machine, and the average tensile strength of this complex material reaches 15.2MPa.
Embodiment tri-
Wetting metal agent comprises following component:
In 1000 parts of solvents (wherein water is 700 parts, 300 parts of ethanol), be furnished with the raw material components of following weight ratio:
1) concentrated hydrochloric acid is 248 parts;
2) organic acid is 200 parts, wherein: 85 parts of maleic acids, 115 parts of malic acid.
The preparation method of complex material comprises the following steps:
1) provide by the metal base of machining moulding, relate generally to and comprise a kind of in stainless steel, titanium alloy, aluminium alloy, magnesium alloy and copper alloy.
2) with the degreaser of selling on the market, metal base is carried out to electrochemical deoiling processing, to remove the greasy dirt of metal surface; 85 ℃ of electrochemical deoiling temperature, the oil removing time determines according to concrete deoiling effect.
3) metal base after oil removal treatment is carried out to surperficial Ultra-Violet Laser processing, take and form opening diameter as 10-60 micron, the degree of depth of micropore is the hole of 100-350 micron.
The technological parameter that Ultra-Violet Laser is processed: a) wavelength is 355nm; B) power is 5.5W; C) diameter of light beam is 10 microns.
4) metal base after Ultra-Violet Laser processing processing with micron order hole is put into wetting metal agent and carry out moistened surface processing.
Surface-treated technological parameter: a) temperature: 70 ℃; B) time: 20min.
5) metal base after wetting metal agent is processed is put into integrated injection molding mould, then injection of plastic is carried out in the surface of this base material, obtain the integrated complex material of metal and plastics; During injection moulding, mold temperature is controlled between 130-140 ℃.
Bond strength test: the resulting metal of aforesaid way and plastics complex material are carried out to tensile strength test with electronic universal material testing machine, and the average tensile strength of this complex material reaches 17.0MPa.
Embodiment tetra-
Wetting metal agent comprises following component:
In 1000 parts of solvents (wherein 550 parts, water, 300 parts of ethanol, 150 parts of methyl alcohol), the raw material of being furnished with following weight ratio forms:
1) inorganic acid is 95 parts, wherein, and 85 parts of concentrated hydrochloric acids, 10 parts of the concentrated sulfuric acids;
2) organic acid is 54 parts, wherein: 54 parts of terephthalic acid (TPA)s.
The preparation method of complex material comprises the following steps:
1) provide by the metal base of machining moulding, relate generally to and comprise a kind of in stainless steel, titanium alloy, aluminium alloy, magnesium alloy and copper alloy.
2) with the degreaser of selling on the market, metal base is carried out to electrochemical deoiling processing, to remove the greasy dirt of metal surface; 85 ℃ of electrochemical deoiling temperature, the oil removing time determines according to concrete deoiling effect.
3) metal base after oil removal treatment is carried out to surperficial Ultra-Violet Laser processing, take and form opening diameter as 10-60 micron, the degree of depth of micropore is the hole of 100-350 micron.
The technological parameter that Ultra-Violet Laser is processed: a) wavelength is 355nm; B) power is 5.5W; C) diameter of light beam is 10 microns.
4) metal base after Ultra-Violet Laser processing processing with micron order hole is put into wetting metal agent and carry out moistened surface processing.
The technological parameter that moistened surface is processed: a) temperature: 85 ℃; B) time: 10min.
5) metal base after wetting metal agent is processed is put into integrated injection molding mould, then injection of plastic is carried out in the surface of this base material, obtain the integrated complex material of metal and plastics; During injection moulding, mold temperature is controlled between 125-135 ℃.
Bond strength test: the resulting metal of aforesaid way and plastics complex material are carried out to tensile strength test with electronic universal material testing machine, and the average tensile strength of this complex material reaches 15.4MPa.
Embodiment five
Wetting metal agent comprises following component:
In 1000 parts of solvents (wherein 550 parts, water, 300 parts of ethanol, 150 parts of methyl alcohol), be furnished with the raw material components of following weight ratio:
1) inorganic acid is 75 parts, wherein, and 50 parts of concentrated hydrochloric acids, 25 parts of the concentrated sulfuric acids;
2) organic acid is 200 parts, wherein: 175 parts of terephthalic acid (TPA)s, 25 parts of trifluoroacetic acids.
The preparation method of complex material comprises the following steps:
1) provide by the metal base of machining moulding, relate generally to and comprise a kind of in stainless steel, titanium alloy, aluminium alloy, magnesium alloy and copper alloy.
2) with the degreaser of selling on the market, metal base is carried out to electrochemical deoiling processing, to remove the greasy dirt of metal surface; 85 ℃ of electrochemical deoiling temperature, the oil removing time determines according to concrete deoiling effect.
3) metal base after oil removal treatment is carried out to surperficial Ultra-Violet Laser processing, take and form opening diameter as 10-60 micron, the degree of depth of micropore is the hole of 100-350 micron.
The technological parameter that Ultra-Violet Laser is processed: a) wavelength is 355nm; B) power is 5.5W; C) diameter of light beam is 10 microns.
4) metal base after Ultra-Violet Laser processing processing with micron order hole is put into wetting metal agent and carry out moistened surface processing.
The technological parameter that moistened surface is processed: a) temperature: 75 ℃; B) time: 15min.
5) metal base after wetting metal agent is processed is put into integrated injection molding mould, then injection of plastic is carried out in the surface of this base material, obtain the integrated complex material of metal and plastics; During injection moulding, mold temperature is controlled between 125-135 ℃.
Bond strength test: the resulting metal of aforesaid way and plastics complex material are carried out to tensile strength test with electronic universal material testing machine, and the average tensile strength of this complex material reaches 16.4MPa.
Embodiment six:
Wetting metal agent comprises following component:
In 1000 parts of solvents (wherein 550 parts, water, 300 parts of ethanol, 150 parts of methyl alcohol), the raw material of being furnished with following weight ratio forms:
1) inorganic acid is 125 parts, wherein, and 75 parts of concentrated hydrochloric acids, 50 parts of the concentrated sulfuric acids;
2) organic acid is 400 parts, wherein, and 385 parts of terephthalic acid (TPA)s, 15 parts of malic acid.
The preparation method of complex material comprises the following steps:
1) provide by the metal base of machining moulding, relate generally to and comprise a kind of in stainless steel, titanium alloy, aluminium alloy, magnesium alloy and copper alloy.
2) with the degreaser of selling on the market, metal base is carried out to electrochemical deoiling processing, to remove the greasy dirt of metal surface; 85 ℃ of electrochemical deoiling temperature, the oil removing time determines according to concrete deoiling effect.
3) metal base after oil removal treatment is carried out to surperficial Ultra-Violet Laser processing, take and form opening diameter as 10-60 micron, the degree of depth of micropore is the hole of 100-350 micron.
The technological parameter that Ultra-Violet Laser is processed: a) wavelength is 355nm; B) power is 5.5W; C) diameter of light beam is 10 microns.
4) metal base after Ultra-Violet Laser processing processing with micron order hole is put into wetting metal agent and carry out moistened surface processing.
The technological parameter that moistened surface is processed: a) temperature: 70 ℃; B) time: 20min.
5) metal base after wetting metal agent is processed is put into integrated injection molding mould, then injection of plastic is carried out in the surface of this base material, obtain the integrated complex material of metal and plastics; During injection moulding, mold temperature is controlled between 125-135 ℃.
Bond strength test: the resulting metal of aforesaid way and plastics complex material are carried out to tensile strength test with electronic universal material testing machine, and the average tensile strength of this complex material reaches 17.2MPa
The contrast of table 1 embodiment and comparative example (processing without wetting agent) gained complex average tensile strength test data
Above content is in conjunction with concrete preferred embodiment further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (10)
1. a preparation method for complex material, is characterized in that, comprises the following steps:
1) metal base is carried out to surface laser processing, to form fine hole;
2) with wetting metal agent, to thering is the metal base of fine hole, carry out surface treatment;
3) metal base and plastics after wetting metal agent is processed are carried out to injection mo(u)lding, obtain the integrated complex material of metal and plastics;
Wherein, in described wetting metal agent, contain the organic acid agent that is useful on the surface tension coefficient difference of improving described metal base and plastics.
2. the preparation method of complex material as claimed in claim 1, is characterized in that, described wetting metal agent adopts following formula:
The water of 1000 parts or organic solvent, be at least furnished with organic acid agent 50-400 part, and described organic acid agent is one or more organic acids or organic acid derivatives or its combination.
3. the preparation method of complex material as claimed in claim 2, it is characterized in that, described organic acid agent is selected from one or more in following composition: terephthalic acid (TPA), maleic acid, citric acid, ethylenediamine tetra-acetic acid, tartaric acid, p-nitrophenyl sulfonic acid, acetic acid, malic acid, trifluoroacetic acid, 1,3-malonic acid, paranitrobenzoic acid, trinitrobenzoic acid and water soluble amino acids, or their organic derivative.
4. the preparation method of complex material as claimed in claim 2, is characterized in that, is also furnished with inorganic acid 60-250 part, and described inorganic acid is selected from one or more in hydrochloric acid, sulfuric acid, hydrobromic acid, nitric acid, phosphoric acid.
5. the preparation method of complex material as claimed in claim 4, is characterized in that, the formula that described wetting metal agent adopts is that the water of 1000 parts or organic solvent are at least furnished with following inorganic acid and organic acid agent:
105 parts of concentrated hydrochloric acids, 120 parts of maleic acids, 80 parts of malic acid; Or
65 parts of concentrated hydrochloric acids, 105 parts of maleic acids, 95 parts of malic acid; Or
248 parts of concentrated hydrochloric acids, 85 parts of maleic acids, 115 parts of malic acid; Or
85 parts of concentrated hydrochloric acids, 10 parts of the concentrated sulfuric acids, 54 parts of terephthalic acid (TPA)s; Or
50 parts of concentrated hydrochloric acids, 25 parts of the concentrated sulfuric acids, 175 parts of terephthalic acid (TPA)s, 25 parts of trifluoroacetic acids; Or
75 parts of concentrated hydrochloric acids, 50 parts of the concentrated sulfuric acids, 385 parts of terephthalic acid (TPA)s, 15 parts of malic acid.
6. the preparation method of the complex material as described in claim 1 to 4 any one, it is characterized in that step 2) in, the metal base with micron order hole is put into described wetting metal agent and carry out surface treatment, treatment temperature is 45-85 ℃, and the processing time is 10-35min.
7. the preparation method of the complex material as described in claim 1 to 4 any one, it is characterized in that, step 1) in, metal base is carried out to surperficial Ultra-Violet Laser processing, take and form the micron order hole that opening diameter is 100-350 micron as 10-60 micron, the degree of depth, wherein the wavelength of Ultra-Violet Laser is 190-400nm, and power is 3-12W, and the diameter of light beam is 1-50 micron.
8. the preparation method of the complex material as described in claim 1 to 4 any one, is characterized in that step 3) in, the surperficial injection of plastic to this base material in injection forming mold, injection temperature is controlled between 120-145 ℃.
9. for the wetting metal agent of the preparation method described in claim 1 to 8 any one, it is characterized in that, described wetting metal agent is containing the organic acid agent that is useful on the surface tension coefficient difference of improving described metal base and plastics.
10. the preparation method of complex material as claimed in claim 1, is characterized in that, the formula of described wetting metal agent is:
The water of 1000 parts or organic solvent, at least is furnished with organic acid agent 50-400 part, described organic acid agent is one or more organic acids or organic acid derivatives or its combination, preferably, also is furnished with inorganic acid 60-250 part, described inorganic acid is selected from hydrochloric acid, sulfuric acid, hydrobromic acid, nitric acid, one or more in phosphoric acid, preferably, described organic acid agent is selected from one or more in following composition: terephthalic acid (TPA), maleic acid, citric acid, ethylenediamine tetra-acetic acid, tartaric acid, p-nitrophenyl sulfonic acid, acetic acid, malic acid, trifluoroacetic acid, 1, 3-malonic acid, paranitrobenzoic acid, trinitrobenzoic acid and water soluble amino acids, or their organic derivative.
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| CN103950147B (en) | 2017-01-25 |
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Address after: 523878 Changan City, Guangdong Province town on the corner management area Co-patentee after: Dongguan Hua Jing powder metallurgy company limited Patentee after: Guangdong wins smart group Limited by Share Ltd Address before: 523878 Changan City, Guangdong Province town on the corner management area Co-patentee before: Dongguan Hua Jing powder metallurgy company limited Patentee before: Dongguan Janus Precision Components Co., Ltd. |
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