CN108608615B - Preparation method of direct combination of composite material and resin - Google Patents
Preparation method of direct combination of composite material and resin Download PDFInfo
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- CN108608615B CN108608615B CN201810345067.7A CN201810345067A CN108608615B CN 108608615 B CN108608615 B CN 108608615B CN 201810345067 A CN201810345067 A CN 201810345067A CN 108608615 B CN108608615 B CN 108608615B
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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
- B29C45/14778—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 the article consisting of a material with particular properties, e.g. porous, brittle
- B29C45/14795—Porous or permeable material, e.g. foam
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
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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
- B29C45/14778—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 the article consisting of a material with particular properties, e.g. porous, brittle
- B29C45/14795—Porous or permeable material, e.g. foam
- B29C2045/14803—Porous or permeable material, e.g. foam the injected material entering minute pores
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
- B29K2105/041—Microporous
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- Chemical Kinetics & Catalysis (AREA)
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- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Chemically Coating (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
Abstract
The invention belongs to the technical field of materials, and particularly relates to a preparation method of a direct combination of a composite material and resin, which comprises the steps of pretreatment, direct nickel electroplating, micropore nickel electrodeposition, adsorption, injection molding and the like.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a preparation method of a direct combination of a composite material and resin.
Background
In the fields of mobile phone communication equipment, electronic and electrical equipment, automobile machinery and the like, in order to achieve the purposes of reducing the weight of products, increasing the bonding strength and the like, the metal and resin integrated molding technology is widely developed and sufficiently applied, a plurality of patents related to the nano injection molding integrated molding technology of various materials have emerged at present, however, most products are subjected to nano treatment by single metal and then injection molding so as to achieve the purpose of integrated molding, along with the change of aesthetic sense of people and the improvement of the performance of electronic products, a single metal framework is urgently needed to be replaced by composite materials meeting the requirements of various performances, such as stainless steel and aluminum composite parts which have the mechanical strength and the processing performance, stainless steel and copper composite parts which have the electromagnetic performance and the mechanical strength, stainless steel and ceramic composite parts which have the communication performance and the mechanical performance and the like, if patent CN204498163U links together stainless steel inner panel and aluminum alloy shell, carries out the nanometer and moulds plastics, and combined material's design has improved product outward appearance and feel greatly, has reduced the risk that the screen was broken through structural reinforcement, has reduced the thickness of cell-phone and has improved cell-phone bulk strength simultaneously.
However, in the market at present, only a single material can be subjected to integrated molding after nano treatment, and particularly, the composite material is subjected to nano treatment and then nano injection molding at the same time, and the waterproof and dustproof performance is considered to be less and less. In patent CN105599219A, the outer frame and the middle plate made of different materials on the composite material are respectively processed, respectively surface-treated, and then placed under the same mold for simultaneous injection molding, so as to achieve nano injection molding of different materials, however, the process is complicated because different materials are respectively treated; in patent CN105098439A, when the nano injection molding treatment is performed on four composite materials, i.e., stainless steel and titanium alloy, aluminum alloy and copper alloy, the aluminum alloy and copper alloy are first shielded, the stainless steel and titanium alloy are treated, then the aluminum alloy and copper alloy are subjected to nano treatment, and finally the four composite materials and resin are integrated by high-strength bonding through aminosilane adsorption, and then the materials of different types are still subjected to separate treatment during the treatment. The reason for this is that the properties of different materials in the composite material are too different, and the traditional surface nano-treatment method is a chemical or electrochemical corrosion method for forming holes, which is based on the holes generated on the base material itself, but the properties of different base materials are different, so that suitable nano-holes cannot be simultaneously generated to perform nano-injection molding integrated molding of the composite material, which results in the disadvantages of complex process, small range of selectable materials, and the like.
Disclosure of Invention
The invention aims to: aiming at the defects of the prior art, the preparation method of the direct combination of the composite material and the resin is provided, and the combination strength and the sealing property are improved by innovatively increasing the selection range of the materials.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a direct combination of a composite material and resin comprises the following steps:
firstly, carrying out pretreatment and weak activation on the composite material to expose a clean and active substrate;
step two, directly carrying out nickel electroplating on the base material obtained in the step one in a storage tank containing a direct nickel plating solution; depositing a uniform and compact nickel-plated layer on the base material;
step three, the base material obtained in the step two is placed in a storage tank containing the microporous nickel additive for electrodeposition, so that a layer of microporous nickel layer with regularity is deposited on the surface of the base material;
soaking the base material obtained in the step three in a storage tank containing reactive dye with a special structure to enable micropores on the microporous nickel layer to adsorb the reactive dye capable of reacting with the resin;
and step five, combining and molding the resin and the base material treated in the step in an injection molding mode to obtain a direct combination of the composite material and the resin.
As an improvement of the preparation method of the direct combination of the composite material and the resin, the composite material is a composite material of metal and metal or a composite material of metal and nonmetal. The substrate of the present invention may be a single metal, i.e., a composite material of the same metal, such as aluminum, copper, stainless steel, zirconium alloy, titanium alloy, magnesium alloy, etc., or a composite material composed of different metals, such as stainless steel and aluminum, stainless steel and copper, aluminum profile and die-cast aluminum, zirconium alloy and aluminum, titanium alloy and aluminum, etc., or a composite material of metal and nonmetal, such as a composite material of metal and glass, a composite material of metal and plastic, a composite material of metal and ceramic, a composite material of metal and wood and bamboo, etc. Wherein the metal includes stamped, extruded, CNC formed metal, formed metal by forging, die casting, formed metal by powder metallurgy MIM, and the like.
As an improvement of the preparation method of the direct combination of the composite material and the resin, the pretreatment refers to a cleaning process for removing wax ester, dirt, oxide skin and rust; the weak activation refers to a process which only activates the pretreated composite material but does not generate over corrosion.
The direct nickel plating solution is a solution which is obtained by introducing a complexing agent, an auxiliary agent and adjusting plating solution parameters on the basis of watt nickel to realize direct nickel plating on an electroplatable base material, wherein the complexing agent is an organic carboxylic acid complexing agent, the auxiliary agent is an organic matter or an inorganic matter with reducibility, and the electroplatable base material is a base material with certain strength and capable of conductively depositing metal nickel.
As an improvement of the preparation method of the direct combination of the composite material and the resin, the organic carboxylic acid complexing agent is a complexing agent with a multidentate ligand structure, and comprises at least one of tartaric acid, citric acid, malic acid, malonic acid, ethylenediamine tetraacetic acid, nitrilotriacetic acid, diethylenetriamine pentacarboxylic acid, iminodisuccinic acid and salts thereof; the organic or inorganic matter with reducibility comprises at least one of sodium hypophosphite, phosphorous acid, hydrazine hydrate, formaldehyde, sodium borohydride and dimethyl borane.
As an improvement of the preparation method of the direct combination of the composite material and the resin, the microporous nickel layer is provided with micropores, the pore diameter of the micropores is 0.5-5um, and the depth of the micropores is 1-5 um. The micropores have certain regularity, which means that when the concentration of the microporous nickel additive is consistent with the electroplating parameters, the micropores are basically consistent in appearance, similar to the aluminum anodized nanopores which are distributed in an oval shape, the porosity accounts for more than 30%, and the change range of the diameter of the pores is not more than 1um, namely, under certain plating conditions, the diameter of the pores is basically determined to be the change of plus or minus 0.5um of a specific value in 0.5-5um, and the pores are regular micropores rather than a rough surface with a large inclusion range in the traditional sense.
As an improvement of the preparation method of the direct combination of the composite material and the resin, the microporous nickel additive is characterized in that macromolecular crown organic matters and a surfactant are introduced into a conventional nickel plating additive; the conventional nickel plating additive comprises at least one of saccharin sodium, propiolic alcohol, diethyl propiolic amine, sodium propenyl sulfonate, sodium benzene sulfinate, benzyl allyl pyridine inner salt, 2-ethyl hexyl sodium sulfate and succinate sodium salt; the macromolecular coronary organic matter comprises at least one of beta-cyclodextrin, 18-crown-6, dibenzo-18-crown ether-6, dicyclohexyl-18-crown-6, 15-crown-6, dibenzo-15-crown-6, dicyclohexyl-15-crown-6, tetraphenylporphyrin, nickel tetramethoxy phenylporphyrin and nickel phthalocyanine; the surfactant comprises at least one of hexadecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium chloride, dioctadecyl dimethyl ammonium chloride and N-lauroyl sarcosine sodium.
As an improvement of the preparation method of the direct combination of the composite material and the resin, the reactive dye containing the special structure is prepared by adding rare earth metal salt into azo acid dye containing sulfydryl, sulfonic group and amino group and mixing;
the azo acid dye containing sulfydryl, sulfonic group and amino can be represented by the following structural general formula (1),
wherein R is1、R2Is at least one of sulfydryl, hydroxyl, amido and amido, R3、R4Is at least one of alkyl, phenyl, amino, aldehyde group, sulfonyl and carboxyl amino, R5、R6At least one of them is a sulfonic acid group;
the rare earth metal salt is cerium salt or lanthanum salt, and specifically is at least one of lanthanum nitrate, lanthanum sulfate, lanthanum chloride, ammonium ceric nitrate and ammonium ceric sulfate.
The surface of the base material is electrodeposited with a microporous nickel layer, the microporous nickel layer with certain pore size and porosity adsorbs active dye through electrostatic attraction and Van der Waals force, and during molding and injection molding, active groups on dye anions and resin electron-deficient groups such as a- [ S ] -group on polyphenylene sulfide resin, a- [ NHCO ] -group on polyamide resin, a- [ COO ] -group on polybutylene terephthalate, a- [ O ] -group on polyaryletherketone, a- [ CO ] -group and the like are subjected to ionic bonding, so that the resin further penetrates into the microporous nickel layer, and the waterproof and dustproof performance of firm combination of the resin and the microporous nickel layer is improved. The rare earth metal salt is introduced into the reactive dye, because the rare earth element has equivalent chemical activity and has strong tendency of generating a complex with the dye, the rare earth element has good passivation and corrosion resistance and can form a corresponding acid salt structure with active nickel, thereby achieving the purposes of passivating the microporous nickel layer, improving the strength of the microporous nickel layer, promoting the further adsorption of the dye on the microporous nickel layer and creating more favorable conditions for the reaction with resin during subsequent molding and injection molding.
As an improvement of the preparation method of the direct combination of the composite material and the resin, the reactive dye containing the special structure also comprises organic acid.
As an improvement of the preparation method of the direct combination of the composite material and the resin, the resin comprises at least one of PBT resin, PPS resin, PA resin, PPA resin, PAEK resin, PEEK resin and PPSU resin. The injection molding method of the invention is to make the needed resin into various shapes by adopting a plastic molding die and adopting a pressurizing extrusion mode through an injection molding machine, in order to ensure that the melted resin can completely enter the micropores, the invention generally adopts a high-speed high-pressure injection method, in addition, the resin adopted by the invention is engineering resin with certain mechanical strength, most of the resin is crystalline engineering resin with delayed cooling, and part of the resin is amorphous resin, and the resin also has better bonding strength and waterproof and dustproof performance to the amorphous resin due to the uniformity of the micropores.
Compared with the prior art, the invention at least has the following beneficial effects: the invention simplifies the technical problem that the composite material composed of different base materials can not be subjected to nano-micropore treatment simultaneously through direct nickel treatment, and the dye adsorbed on the micropore nickel layer reacts with the resin to be injected through innovatively soaking the dye tank solution with a special structure, so that the high-strength bonding and waterproof and dustproof functions between the composite material and the resin are achieved, and the limit range of the conventional nano injection molding on engineering resin is greatly expanded.
Drawings
FIG. 1 is a photograph of the composite substrate of example 1, which was observed by scanning electron microscope with SU-70 thermal field emission at magnification of 5K times before it was treated to active adsorption and molded.
FIG. 2 is a picture observed by scanning electron microscope (2K times) of SU-70 thermal field emission before the composite substrate is treated to active adsorption and molded and injected in example 1.
FIG. 3 is a picture observed by scanning electron microscope magnification of SU-70 thermal field emission before processing to active adsorption, molding and injection molding of the composite substrate in example 1.
Detailed Description
The present invention will be described in further detail with reference to the following detailed description and the accompanying drawings, but the embodiments of the invention are not limited thereto.
Example 1
A method of making a composite and resin combination comprising the steps of:
firstly, carrying out pretreatment and weak activation on the composite material to expose a clean and active substrate;
step two, directly carrying out nickel electroplating on the base material obtained in the step one in a storage tank containing a direct nickel plating solution; depositing a uniform and compact nickel-plated layer on the base material;
step three, the base material obtained in the step two is placed in a storage tank containing the microporous nickel additive for electrodeposition, so that a layer of microporous nickel layer with regularity is deposited on the surface of the base material;
soaking the base material obtained in the step three in a storage tank containing reactive dye with a special structure to enable micropores on the microporous nickel layer to adsorb the reactive dye capable of reacting with the resin;
and step five, combining and molding the resin and the base material treated in the step in an injection molding mode to obtain a direct combination of the composite material and the resin.
Specifically, (1) pretreatment: randomly taking ten special composite material test pieces (the outer frame is made of stainless steel, the middle plate is made of die-cast aluminum, and a position special for measuring shearing force and air tightness is reserved), and firmly hanging the test pieces on a stainless steel hanger wrapped by electroplating glue; then soaking the mixture in a commercially available neutral degreasing agent (CW-6007 produced by Hui Ling technology) for 300 seconds, and washing with water at 60 ℃; soaking in 65g/l sodium hydroxide water solution for 40 seconds, and washing with water at 65 deg.C; soaking the aluminum die casting powder in a dust remover for 40 seconds, washing the aluminum die casting powder with water, and keeping the aluminum die casting powder at normal temperature; then placing the mixture into an activation tank, soaking for 30 seconds, and then soaking at a speed of 5A/dm2The cathode current flash plating is carried out for 30 seconds, the activation tank is 200ml/L hydrochloric acid and 200g/L nickel chloride, the temperature is set to be normal temperature, and the anode is a nickel block arranged in a titanium basket.
(2) Direct nickel electroplating: placing the test piece treated in the step (1) in a direct nickel bath at a ratio of 3A/dm2The cathode electrogalvanic deposition is carried out for 120 seconds, and then the cathode electrogalvanic deposition is washed clean, wherein the direct nickel plating solution consists of the following components: 100g/L of nickel sulfate, 20g/L of boric acid, 100g/L of potassium citrate, 15g/L of sodium hypophosphite, 2g/L of sodium fluoride, 10mg/L of propiolic alcohol, 10mg/L of sodium propenyl sulfonate and 5mg/L of benzyl allyl pyridine inner salt, wherein the temperature is set to be 45 ℃, the pH value is adjusted to be 6.0, and the anode is a nickel block arranged in a titanium basket.
(3) And (3) electrodeposition of a microporous nickel layer: placing the test piece treated in the step (2) in a storage tank containing a micropore nickel plating solution with the cathode current density of 3A/dm2The current electrodeposition time of 300 seconds, wherein the microporous nickel plating solution consists of the following components: 240g/L of nickel sulfate, 36g/L of nickel chloride, 36g/L of boric acid, 10mg/L of propiolic alcohol, 10mg/L of sodium propenyl sulfonate and 1g/L, N g/L of tetraphenylporphyrin-200 mg/L of sodium lauroyl sarcosinate, the temperature is set to be 50 ℃, the pH value is adjusted to be 4.3, and the anode is a nickel block filled in a titanium basket.
(4) Adsorption: soaking the test piece treated in the step (3) in a storage tank containing reactive dye with a special structure for 10 minutes, wherein the reactive dye with the special structure consists of the following components: the direct black 22 was 1g/L, propionic acid was 20ml/L, glycolic acid was 10ml/L, and cerium ammonium nitrate was 2g/L, the temperature was 50 ℃ and the pH was adjusted to 2.0. The surface-treated test piece was observed by using an SU-70 thermal field emission scanning electron microscope, and micropores with a pore size of 3 μm were uniformly distributed on the surface, as shown in FIGS. 1, 2, and 3.
(5) Injection molding: 1kg of mixed resin mixture (containing 65% of polyamide and 35% of glass fiber) is taken, and the resin mixture is injected on the test piece with the surface treatment by an injection molding machine at the injection pressure of 100MPa and the injection speed of 180mm/s, wherein the polyamide resin is purchased special nylon resin for commercial nano injection molding and is pretreated completely according to the physical property parameter table thereof, and ten groups of direct composites and resin combinations of the embodiment are obtained.
(6) And (3) baking the ten groups of direct combined bodies of the composite materials and the resin obtained in the step (5) for 1 hour at 150 ℃, measuring the average bonding strength of the ten groups of direct combined bodies of the composite materials and the resin to be 43Mpa by using a universal test tensile stripping machine, and measuring the air leakage of the ten groups of combined bodies to be lower than 0.2SCCM within 30min by using the ten groups of direct combined bodies of the composite materials and the resin to be tested under the air pressure of 2 Kpa.
Example 2
The difference from example 1 is: in this embodiment, ten composite material test pieces (the outer frame is an aluminum profile, the middle plate is stainless steel, a copper material is embedded in a small block, and a position special for measuring shearing force and air tightness is reserved) are randomly taken and firmly hung on a stainless steel hanger wrapped by electroplating glue, the subsequent processing method is the same as that of embodiment 1, ten groups of direct composites and resin combinations of the embodiment are obtained, the average bonding strength is measured to be 45Mpa, the ten groups of direct composites and resin combinations are tested under the air pressure of 2Kpa, and the air leakage of the ten groups of combinations is measured to be lower than 0.2SCCM within 30 min.
Example 3
The difference from example 1 is: the resin of this example is a commercially available polyaryletherketone resin PAEK dedicated for nano injection molding, the molding parameters are performed according to the physical property parameter table, the other processing procedures are the same as those of example 1, ten sets of direct composites and resin combinations of this example are obtained, the average bonding strength is measured to be 40Mpa, and the air leakage of the ten sets of combinations is measured to be lower than 0.2SCCM within 30min when the ten sets of direct composites and resin combinations are tested at the air pressure of 2 Kpa.
Example 4
The difference from example 1 is: in this embodiment, the outer frame of the composite material test piece is an aluminum profile, the middle plate is die-cast aluminum, that is, an all-aluminum base material, and a position special for measuring the shearing force and the air tightness is reserved, in addition, the resin of this embodiment is commercially available polybutylene terephthalate special for nano injection molding, the other steps are the same as those of embodiment 1, ten groups of direct composites and resin combinations of this embodiment are obtained, the average bonding strength is measured to be 44Mpa, the ten groups of direct composites and resin combinations are tested under the air pressure of 2Kpa, and the air leakage of the ten groups of combinations is measured to be lower than 0.2SCCM within 30 min.
Example 5
Different from the embodiment 1: the outer frame of the composite material test piece is made of stainless steel, the middle plate is made of powder metallurgy MIM molding stainless steel partially and made of conductive ceramic partially, a position special for measuring shearing force and air tightness is reserved, and ten pieces of the composite material test piece are randomly and firmly hung on a stainless steel hanger wrapped by electroplating glue; then soaking the product in a commercially available neutral degreasing agent for 300 seconds, and then washing the product with water at the temperature of 60 ℃; then soaking the raw materials in 100g/L ammonium bifluoride for 10 minutes at normal temperature, and washing the raw materials with water; then soaking in a gelling solution for 5min, specifically 30g/L of stannous chloride, 10ml/L of hydrochloric acid and 0.3g/L of palladium chloride, and setting the temperature to be normal temperature; then placing the mixture into an activation tank, soaking for 60 seconds, and then soaking at a speed of 5A/dm2The cathode current flash plating is carried out for 30 seconds, the activation tank is 200ml/L hydrochloric acid and 200g/L nickel chloride, the temperature is set to be normal temperature, and the anode is a nickel block arranged in a titanium basket;
(2) direct nickel electroplating: placing the test piece treated in the step (1) in a storage tank containing direct nickel plating solution at a speed of 3A/dm2The cathode electrowinning is carried out for 120 seconds, and then the cathode electrowinning is washed clean, wherein the direct nickel plating solution consists of the following components: 100g/L of nickel sulfate, 20g/L of boric acid, 50g/L of potassium citrate, 50g/L of potassium sodium tartrate, 15g/L of phosphorous acid, 3g/L of sodium chloride, 20mg/L of saccharin sodium, 10mg/L of sodium propenyl sulfonate and 5mg/L of 2-ethylhexyl sodium sulfate, the temperature is set to be 45 ℃, the pH value is adjusted to be 6.0, and the anode is a nickel block filled in a titanium basket.
(3) And (3) electrodeposition of a microporous nickel layer: placing the test piece treated in the step (2) in a storage tank containing a micropore nickel plating solution with the cathode current density of 3A/dm2The current electrodeposition is carried out for 300 seconds, wherein the microporous nickel plating solution consists of 240g/L of nickel sulfate, 36g/L of nickel chloride, 36g/L of boric acid, 10mg/L of diethyl propynylamine, 10mg/L of sodium propenyl sulfonate, 1g/L of β -cyclodextrin, 0.5g/L of dicyclohexyl-18-crown-6, 200mg/L of hexadecyl trimethyl ammonium chloride, the temperature is set to be 50 ℃, the pH value is adjusted to be 4.3, and the anode is a nickel block arranged in a titanium basket.
(4) Adsorption: soaking the test piece treated in the step (3) in a reactive dye storage tank containing a special structure for 10 minutes, wherein the reactive dye storage tank comprises the following components in parts by weight: the direct suntan 19 is 1g/L, the glacial acetic acid is 20ml/L, the sodium acetate is 5g/L, the lanthanum sulfate is 2g/L, the methanesulfonic acid is 2g/L, the temperature is set to be 50 ℃, and the pH is adjusted to be 2.0.
(5) Injection molding: 1kg of mixed resin mixture (containing 80% of polyphenyl thioether and 20% of glass fiber) is taken, the resin mixture is injected on the test piece with the surface treatment by an injection molding machine at the injection pressure of 100MPa and the injection speed of 180mm/s, the polyphenyl thioether resin is the purchased special polyphenyl thioether resin for commercial nano injection molding, and the pretreatment is carried out completely according to the physical property parameter table, so as to obtain ten groups of direct combinations of the composite material and the resin in the embodiment.
(6) And baking the obtained ten groups of direct combined bodies of the composite materials and the resin for 1 hour at 170 ℃, and testing the average bonding strength of the ten groups of direct combined bodies of the composite materials and the resin by a universal testing tensile stripping machine to be 46Mpa, wherein the air leakage of the ten groups of combined bodies in 30min is lower than 0.2SCCM when the ten groups of direct combined bodies of the composite materials and the resin are tested under the air pressure of 2 Kpa.
Example 6
The difference from example 5 is: the outer frame of the composite material of the embodiment is zirconium alloy, most of the middle plate is stainless steel formed by powder metallurgy, a small part of the middle plate is inlaid into sapphire and glass, and a position special for measuring shearing force and air tightness is reserved, other processing procedures are the same as those of the embodiment 5, ten groups of direct composites of the composite material and resin of the embodiment are obtained, the average bonding strength is measured to be 41MPa, the ten groups of direct composites of the composite material and resin are tested under the air pressure of 2Kpa, and the air leakage of the ten groups of composites is measured to be lower than 0.2SCCM within 30 min.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. A preparation method of a direct combination of a composite material and resin is characterized by comprising the following steps:
firstly, carrying out pretreatment and weak activation on the composite material to expose a clean and active substrate;
step two, directly carrying out nickel electroplating on the base material obtained in the step one in a storage tank containing a direct nickel plating solution; depositing a uniform and compact nickel-plated layer on the base material;
step three, the base material obtained in the step two is placed in a storage tank containing the microporous nickel additive for electrodeposition, so that a layer of microporous nickel layer with regularity is deposited on the surface of the base material;
soaking the base material obtained in the step three in a storage tank containing reactive dye with a special structure to enable micropores on the microporous nickel layer to adsorb the reactive dye capable of reacting with the resin;
step five, combining and molding the resin and the base material treated in the step in an injection molding manner to obtain a direct combination of the composite material and the resin;
the reactive dye with a special structure is prepared by adding rare earth metal salt into azo acid dye containing sulfydryl, sulfonic group and amino group and mixing;
the rare earth metal salt is cerium salt or lanthanum salt, and specifically is at least one of lanthanum nitrate, lanthanum sulfate, lanthanum chloride, ammonium ceric nitrate and ammonium ceric sulfate.
2. The method for preparing a direct combination of a composite material and a resin according to claim 1, wherein: the composite material is a composite material of metal and metal or a composite material of metal and nonmetal.
3. The method for preparing a direct combination of a composite material and a resin according to claim 1, wherein: the pretreatment refers to a cleaning process for removing wax ester, dirt, oxide skin and rust; the weak activation refers to a process which only activates the pretreated composite material but does not generate over corrosion.
4. The method for preparing a direct combination of a composite material and a resin according to claim 1, wherein: the direct nickel plating solution is a solution which is realized by introducing a complexing agent and an auxiliary agent on the basis of watt nickel and adjusting parameters of a plating solution to directly plate nickel on an electroplatable base material, wherein the complexing agent is an organic carboxylic acid complexing agent, the auxiliary agent is an organic matter or an inorganic matter with reducibility, and the electroplatable base material is a base material with certain strength and capable of conductively depositing metal nickel.
5. The method for preparing a direct combination of a composite material and a resin as claimed in claim 4, wherein: the organic carboxylic acid complexing agent is a complexing agent with a polydentate ligand structure and comprises at least one of tartaric acid, citric acid, malic acid, malonic acid, ethylenediamine tetraacetic acid, nitrilotriacetic acid, diethylenetriamine pentacarboxylic acid, iminodisuccinic acid and salts thereof; the organic or inorganic matter with reducibility comprises at least one of sodium hypophosphite, phosphorous acid, hydrazine hydrate, formaldehyde, sodium borohydride and dimethyl borane.
6. The method for preparing a direct combination of a composite material and a resin according to claim 1, wherein: the micropore nickel layer is provided with micropores, the pore diameter of each micropore is 0.5-5um, and the depth of each micropore is 1-5 um.
7. The method for preparing a direct combination of a composite material and a resin according to claim 1, wherein: the microporous nickel additive is characterized in that macromolecular crown organic matters and a surfactant are introduced into a conventional nickel plating additive; the conventional nickel plating additive comprises at least one of saccharin sodium, propiolic alcohol, diethyl propiolic amine, sodium propenyl sulfonate, sodium benzene sulfinate, benzyl allyl pyridine inner salt, 2-ethyl hexyl sodium sulfate and succinate sodium salt; the macromolecular coronary organic matter comprises at least one of beta-cyclodextrin, 18-crown-6, dibenzo-18-crown ether-6, dicyclohexyl-18-crown-6, 15-crown-6, dibenzo-15-crown-6, dicyclohexyl-15-crown-6, tetraphenylporphyrin, nickel tetramethoxy phenylporphyrin and nickel phthalocyanine; the surfactant comprises at least one of hexadecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium chloride, dioctadecyl dimethyl ammonium chloride and N-lauroyl sarcosine sodium.
8. The method for preparing a direct combination of a composite material and a resin according to claim 1, wherein:
the azo acid dye containing sulfydryl, sulfonic group and amino can be represented by the following structural general formula (1),
wherein R is1、R2Is at least one of sulfydryl, hydroxyl, amido and amido, R3、R4Is at least one of alkyl, phenyl, amino, aldehyde group, sulfonyl and carboxyl amino, R5、R6At least one of them is a sulfonic acid group.
9. The method for preparing a direct combination of a composite material and a resin as claimed in claim 8, wherein: the reactive dye containing the special structure also comprises organic acid.
10. The method for preparing a direct combination of a composite material and a resin according to claim 1, wherein: the resin includes at least one of PBT resin, PPS resin, PA resin, PPA resin, PAEK resin, PEEK resin, and PPSU resin.
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