CN108262915A - Composite construction and its manufacturing method with stainless steel material and plastic material - Google Patents
Composite construction and its manufacturing method with stainless steel material and plastic material Download PDFInfo
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- CN108262915A CN108262915A CN201611264456.4A CN201611264456A CN108262915A CN 108262915 A CN108262915 A CN 108262915A CN 201611264456 A CN201611264456 A CN 201611264456A CN 108262915 A CN108262915 A CN 108262915A
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- China
- Prior art keywords
- stainless steel
- piece
- composite construction
- steel work
- manufacturing
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 141
- 239000010935 stainless steel Substances 0.000 title claims abstract description 137
- 239000000463 material Substances 0.000 title claims abstract description 102
- 239000004033 plastic Substances 0.000 title claims abstract description 63
- 229920003023 plastic Polymers 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000010276 construction Methods 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 238000005530 etching Methods 0.000 claims abstract description 38
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003792 electrolyte Substances 0.000 claims abstract description 16
- 238000002048 anodisation reaction Methods 0.000 claims abstract description 15
- 238000003486 chemical etching Methods 0.000 claims abstract description 12
- 238000001746 injection moulding Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims abstract description 9
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims abstract description 9
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 8
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 7
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 8
- 239000000470 constituent Substances 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 4
- -1 polybutylene terephthalate Polymers 0.000 claims description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 3
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- 210000003850 cellular structure Anatomy 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims 1
- 229920000768 polyamine Polymers 0.000 claims 1
- 239000000243 solution Substances 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 15
- 238000012545 processing Methods 0.000 description 13
- 238000001000 micrograph Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 7
- 238000000137 annealing Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000002203 pretreatment Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229910000619 316 stainless steel Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 229920006260 polyaryletherketone Polymers 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- 239000010963 304 stainless steel Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- 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
- B29C45/14336—Coating a portion of the article, e.g. the edge of the article
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/095—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/08—Interconnection of layers by mechanical means
-
- 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
- C23F1/28—Acidic compositions for etching iron group metals
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F1/00—Details not covered by groups G06F3/00 - G06F13/00 and G06F21/00
- G06F1/16—Constructional details or arrangements
- G06F1/1613—Constructional details or arrangements for portable computers
- G06F1/163—Wearable computers, e.g. on a belt
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2009/00—Layered products
- B29L2009/003—Layered products comprising a metal layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
Abstract
The present invention provides a kind of composite construction and its manufacturing method with stainless steel material and plastic material.Manufacturing method includes：Stainless steel work-piece is placed in electrolyte and carries out anodization step so that stainless steel work-piece is formed the first erosional surface by oxidation；Chemical etching step is carried out so that the first erosional surface is etched to form the second erosional surface by being placed in etching solution with the stainless steel work-piece of the first erosional surface；And by injection-moulding step, plastic layer is incorporated on the second erosional surface of stainless steel work-piece to form composite construction.Second erosional surface has size for multiple nanostructureds between 50 to 300 nanometers.Etching solution includes the water of etchant and surplus of the concentration between 50 to 200 g/l, and etchant includes sulfuric acid, the ferric sulfate of 10 to 30 weight % and the ferrous sulfate of 5 to 15 weight % of 60 to 80 weight %.Whereby, the present invention can improve the binding force between stainless steel material and plastic material by the nanostructured on stainless steel work-piece.
Description
Technical field
The present invention relates to a kind of composite construction and its manufacturing methods, have stainless steel material and plastics more particularly to one kind
The composite construction and its manufacturing method of material.
Background technology
In mobile electronic device field, especially in intelligent wearable device field, stainless steel material have many advantages, such as and
One of material for being intended to actively develop and apply as these fields.Specifically, stainless steel material generally can by with plastics material
Material be combined with each other and is formed the component of intelligent wearable device.
In the material of two kinds of different characteristics of stainless steel material and plastic material, the prior art is usually to utilize buckle knot
Two kinds of materials are bonded to each other by the design in the structures such as structure or bolt arrangement.However, thus, it will increase is manufactured into
Sheet and the complexity for improving product structure, and then influence the beauty of product.Therefore, still a need to develop new technology, with
The binding force between different materials is promoted without using under additional fixed structure, being handled by the surface to material, with
Ensure the quality of product.
Invention content
To solve the above-mentioned problems, the solution that wherein an embodiment is provided of the invention, which is to provide one kind, has
The manufacturing method of the composite construction of stainless steel material and plastic material, it includes：One stainless steel work-piece is placed in an electrolyte
An anodization step is carried out, so that the stainless steel work-piece is formed one first erosional surface by oxidation；To have described the
The stainless steel work-piece of one erosional surface is placed in an etching solution and carries out a chemical etching step, so that first erosional surface
One second erosional surface is etched to form, wherein, it is more between 50 to 300 nanometers that second erosional surface, which has size,
A nanostructured；And by an injection-moulding step, a plastic layer is incorporated in second corruption of the stainless steel work-piece
On erosion face, to form the composite construction.The etching solution include an etchant of the concentration between 50 to 200 g/l with
And the water of surplus, and the etchant includes the ferric sulfate and 5 to 15 weights of the sulfuric acid of 60 to 80 weight %, 10 to 30 weight %
Measure the ferrous sulfate of %.
Preferably, the temperature of the etching solution be between 55 to 70 DEG C, and the time of the chemical etching step be 5
To 20 minutes.
Preferably, the electrolyte includes the water of sulfuric acid and surplus of the concentration between 100 to 200 g/l, and institute
The time for stating anodization step is 5 to 20 minutes.
Preferably, multiple nanostructureds form a cellular structures or a facet level stack structure.
Preferably, the stainless steel work-piece is formed by SUS304 stainless steels or SUS316 stainless steels.
Preferably, the plastic layer be by polybutylene terephthalate, polyphenylene sulfide, polyamide, polyether-ether-ketone and
Thermoplastic polyurethane at least one of formed.
Preferably, the bond strength between the stainless steel work-piece with second erosional surface and the plastic layer is
Between 20 to 40MPa/cm2Between.
Preferably, the injection-moulding step further comprises：A molding tool is heated between 140 to 200 DEG C
Between temperature.
To solve the above-mentioned problems, the solution that an other embodiment of the invention is provided, which is to provide one kind, to be had
The composite construction of stainless steel material and plastic material, the composite construction be as made by manufacturing method as described above, wherein,
Bond strength between the stainless steel work-piece and the plastic layer with second erosional surface is between 20 to 40MPa/
cm2Between.
To solve the above-mentioned problems, the solution that other another embodiment of the invention is provided is to provide a kind of erosion
Constituent is carved, the etching constituent is used for the manufacturing method of above-mentioned composite construction, wherein, the etching constituent includes concentration
The water of an etchant and surplus between 50 to 200 g/l, and the etchant includes the sulphur of 60 to 80 weight %
The ferrous sulfate of acid, the ferric sulfate of 10 to 30 weight % and 5 to 15 weight %.
The beneficial effects of the present invention are provided by the present invention a kind of compound with stainless steel material and plastic material
Structure and its manufacturing method, by the use of the etching solution with specific composition, so that energy on the surface of stainless steel work-piece
Nanostructured is formed, whereby to improve the binding force between stainless steel material and plastic material.
For the enabled feature and technology contents for being further understood that the present invention, please refer to below in connection with the present invention specifically
Bright and attached drawing, however the attached drawing provided is only for reference and description, and is not intended to limit the present invention.
Description of the drawings
The manufacture of a kind of composite construction with stainless steel material and plastic material that Fig. 1 is provided by the embodiment of the present invention
The flow chart of method；
Fig. 2A is the schematic diagram of the stainless steel work-piece used in the embodiment of the present invention；
In the manufacturing method that Fig. 2 B are provided by the embodiment of the present invention, there is the signal of the stainless steel work-piece of the first erosional surface
Figure；
In the manufacturing method that Fig. 2 C are provided by the embodiment of the present invention, there is the signal of the stainless steel work-piece of the second erosional surface
Figure；
Fig. 2 D are shown by a kind of composite construction with stainless steel material and plastic material that the embodiment of the present invention provides
It is intended to；
Fig. 3 A are the micro- photograph in surface of one of which stainless steel work-piece used in the embodiment of the present invention；
The stainless steel work-piece that Fig. 3 B are Fig. 3 A is after the anodization step of 5 minutes is carried out, the first erosional surface for being formed
The micro- photograph in surface；
The stainless steel work-piece that Fig. 3 C are Fig. 3 A is after the anodization step of 10 minutes is carried out, the first erosional surface for being formed
The micro- photograph in surface；
Fig. 3 D are surface micro- photograph of the stainless steel work-piece of Fig. 3 A after the second erosional surface is formed；
Fig. 3 E are the partial enlarged view of Fig. 3 D；
Fig. 4 A are the micro- photograph in surface of another stainless steel work-piece used in the embodiment of the present invention；
Fig. 4 B are surface micro- photograph of the stainless steel work-piece of Fig. 4 A after the second erosional surface is formed；And
Fig. 4 C are the partial enlarged view of Fig. 4 B.
Specific embodiment
Be below illustrated by specific specific example it is presently disclosed in relation to " have stainless steel material and plastics material
The embodiment of the composite construction and its manufacturing method of material ", those skilled in the art can be by contents disclosed in this specification
Solve advantages of the present invention and effect.The present invention can be implemented or be applied by other different specific embodiments, this specification
In every details also can be based on different viewpoints with application, it is without departing from the spirit it is lower carry out it is various modification and change.
In addition, the attached drawing of the present invention is only simple schematically illustrate, not according to the description of actual size, first give chat it is bright.Following embodiment party
The relevant technologies content of the present invention will be explained in further detail in formula, but disclosure of that is not the technology to limit the present invention
Scope.
First, it please refers to Fig.1.Fig. 1 has stainless steel material and plastic material by one kind that the embodiment of the present invention provides
Composite construction manufacturing method flow chart.
As shown in Figure 1, a kind of manufacture of composite construction with stainless steel material and plastic material provided by the present invention
Method includes at least the following steps：Stainless steel work-piece is placed in electrolyte and carries out anodization step, so that stainless steel work
Part is formed the first erosional surface (S100) by oxidation；Change being placed in etching solution with the stainless steel work-piece of the first erosional surface
Etching step is learned, so that the first erosional surface is etched to form the second erosional surface (S102), wherein, the second erosional surface has ruler
Very little multiple nanostructureds between 50 to 300 nanometers；And by injection-moulding step, plastic layer is incorporated in not
It becomes rusty on the second erosional surface of steel workpiece, to form composite construction (S104).
Before the step S100 to S104 is carried out, pre-treatment step can be carried out to stainless steel work-piece 1.For example,
Pre-treatment step can include cleaning stainless steel work-piece 1 or degreasing so that the surface cleaning of stainless steel work-piece 1 without
Oil.
It please coordinate shown in Fig. 3 A and Fig. 4 A.Fig. 3 A and Fig. 4 A different stainless steel works used in the embodiment of the present invention
The micro- photograph in surface of part 1.In an embodiment of the present invention, stainless steel work-piece 1 can use SUS304 or SUS316 series
Stainless steel material is formed.The stainless steel work-piece 1 of Fig. 3 A is and the stainless steel work of Fig. 4 A as made by SUS304 stainless steel materials
Part 1 is formed by SUS316 stainless steel materials.
As shown in Figure 3A and 4A, the surface of SUS304 stainless steel materials and SUS316 stainless steel materials all has sheet
Structure (that is, crystal structure of stainless steel material).In comparison, the crystal structure of SUS316 stainless steel materials is comparatively dense, and
The crystal structure of SUS304 stainless steel materials is more loose.
It, can be by step S100 and S102 as shown in Figure 1 to not in stainless steel work-piece 1 after pre-treatment step
Rust steel workpiece 1 is further processed, and by step S104 by treated stainless steel work-piece 1 and plastic material knot
It closes and forms a kind of composite construction S with stainless steel material and plastic material that the embodiment of the present invention is provided.
Next, it will be described in detail for step S100 to S104.First, referring to Fig. 1, and coordinating Fig. 2A and 2B
It is shown.Fig. 2A is the schematic diagram of the stainless steel work-piece used in the embodiment of the present invention, and Fig. 2 B are carried by the embodiment of the present invention
In the manufacturing method of confession, there is the schematic diagram of the stainless steel work-piece of the first erosional surface.
In the step s 100, stainless steel work-piece 1 is placed in electrolyte and carries out anodization step, so that stainless steel work
Part 1 is formed the first erosional surface S1 by oxidation.Specifically, anodization step can be removed by electrochemical etching method
The Native Oxide membrane structure on 1 surface of stainless steel work-piece, and the metal material in stainless steel work-piece 1 is aoxidized, and then generate first
Erosional surface S1.
For example, the electrolyte used in step S100 includes concentration between 100 to 200 g/l of sulfuric acid
(H2SO4) and surplus water.The voltage for being applied to electrolyte is fixed voltage, and voltage range is between 3 to 5 volts.Anodic oxygen
The time for changing step is between 5 to 20 minutes.In a preferred embodiment, it is using the sulfuric acid for including a concentration of 200 g/l
Solution is as electrolyte, and to 3 volts of voltage of electrolyte application, and processing time is 5 to 10 minutes.In preferred embodiment
In, processing time is 10 minutes.
It please refers to shown in Fig. 3 B and Fig. 3 C.The stainless steel work-piece that Fig. 3 B are Fig. 3 A is carrying out the anodic oxidation step of 5 minutes
After rapid, the micro- photograph in the surface of the first erosional surface that is formed, and the stainless steel work-piece that Fig. 3 C are Fig. 3 A is carrying out 10 minutes
After anodization step, the micro- photograph in the surface of the first erosional surface that is formed.In other words, Fig. 3 B and Fig. 3 C are equally used
SUS304 stainless steel materials form stainless steel work-piece 1, and the time for only carrying out anodization step is different.
It can be seen that by the comparison of Fig. 3 B and Fig. 3 C, when the time of anodization step is 5 minutes (Fig. 3 B), although stainless steel
The first erosional surface S1 that 1 surface of workpiece is formed has had apparent groove structure, still it can be seen that stainless steel material sheet
The crystal distribution trend of body, therefore, the structure shown in Fig. 3 B can speculate the corrosion institute between mainly stainless steel material crystal
It is formed.And the time of anodization step be 10 minutes when (Fig. 3 C), on the first erosional surface S1 on 1 surface of stainless steel work-piece
Groove structure and the difference shown in Fig. 3 B, it can be seen that corrosive effect evenly, therefore can be with the structure shown in inference Fig. 3 C
Include the corrosiveness on entire 1 surface of stainless steel work-piece.The comparison result of B and Fig. 3 C according to fig. 3, in the embodiment of the present invention
In, most preferred anodization step processing time is 10 minutes.
Next, referring to Fig. 1.In step S102, the stainless steel work-piece 1 with the first erosional surface S1 is placed in erosion
It carves in liquid and carries out chemical etching step, so that the first erosional surface S1 is etched to form the second erosional surface S2.Second erosional surface
S2 has size for multiple nanostructureds between 50 to 300 nanometers.
Specifically, it is with comprising specific by the stainless steel work-piece 1 with the first erosional surface S1 that step S100 is formed
The etching solution of composition carries out chemical etching so that the first erosional surface S1, which is etched to form, to be had and the first erosional surface S1 difference knots
Second erosional surface of structure.Etching solution includes the water of etchant and surplus of the concentration between 50 to 200 g/l.Etchant
Include the sulfuric acid (H of 60 to 80 weight %2SO4), the ferric sulfate (Fe of 10 to 30 weight %2(SO4)3) and 5 to 15 weight %
Ferrous sulfate (FeSO4).In an embodiment of the present invention, the temperature of etching solution is and the chemical etching between 55 to 70 DEG C
The time of step is 5 to 20 minutes.
In a preferred embodiment, using DH730 etching solutions as carrying out the etching solution of chemical etching.
Sulfuric acid that the Contents of Main Components of DH730 etching solutions is 70%, 20% ferric sulfate is with 10% ferric sulfate and the water of surplus.
Using DH730 etching solutions to there is the details of the stainless steel work-piece 1 of the first erosional surface S1 progress chemical etching and effect later
Narration.
The stainless steel work-piece 1 with the second erosional surface S2 formed by step S102, based on the second erosional surface S2's
There can be good binding force between structure feature and follow-up used plastic material.As previously mentioned, the second erosional surface S2
It is multiple nanostructureds between 50 to 300 nanometers with size.The nanostructured of second erosional surface S2 is complicated and not
Rule, the structures such as nano-pore, hole, hole or bumps can be included.In other words, by step S102, there is the first corrosion
The stainless steel work-piece 1 of face S1 is handled by nanometer pore-forming, and then forms the second erosional surface S2.
Please refer to Fig. 3 D, 3E, 4B and 4C.Fig. 3 D are that surface of the stainless steel work-piece of Fig. 3 A after the second erosional surface is formed is shown
Microfacies piece, Fig. 3 E are the partial enlarged view of Fig. 3 D, and Fig. 4 B are surface of the stainless steel work-piece of Fig. 4 A after the second erosional surface is formed
Micro- photograph, and the partial enlarged view that Fig. 4 C are Fig. 4 B.
Specifically, Fig. 3 D and 3E are shown by the stainless steel work-piece that SUS304 stainless steel materials are formed by preceding processing
The micro- photograph in surface after step, step S100 and step S102, and Fig. 4 B and 4C are shown by SUS316 stainless steel materials institute
The stainless steel work-piece of formation is passing through the micro- photograph in surface after pre-treatment step, step S100 and step S102.Such as Fig. 3 D
Shown, in the case where using SUS304 stainless steel materials, the second erosional surface S2 of stainless steel work-piece 1 is with cellular porous
Structure.As shown in FIGURE 3 E, porous structure has nano aperture of the range between 50 to 200 nanometers.In addition, such as Fig. 4 B institutes
Show, in the case where using SUS316 stainless steel materials, the second erosional surface S2 of stainless steel work-piece 1 is laminated with polyhedra packing
The pit structure that structure and thus structure are formed.As shown in Figure 4 C, the size of pit structure is 50 to 200 nanometers.Change sentence
It talks about, in the case of forming stainless steel work-piece 1 selecting SUS304 and SUS316 stainless steel materials, is implemented by the present invention
Step S100 and step S102 in example can generate nanostructured on the surface of stainless steel work-piece 1.
Next, before step S104 is carried out, first the stainless steel work-piece 1 with the second erosional surface S2 can also be passed through
It fully washes and dries.The temperature of baking can be between 70 to 100 DEG C, and baking time can be 10 to 30 minutes.
However, in the present invention, as long as can so that stainless steel work-piece 1 is fully dried, the temperature of baking and time are not subject to the limits
System.Stainless steel work-piece 1 by drying, which can pass through, to pack and stores.
Please Fig. 1 is referred to secondary.In step S104, by injection-moulding step, plastic layer 2 is incorporated in stainless steel work-piece
On 1 the second erosional surface S2, to form composite construction S.Step S104 is will pass through processing by injection molding forming method
Stainless steel work-piece 1 be combined with each other with plastic layer 2 (plastic material).In an embodiment of the present invention, plastic layer 2 can be by gathering
Butylene terephthalate (PBT), polyphenylene sulfide (PPS), polyamide (PA), polyaryletherketone (PAEK) thermoplastic poly amido first
Acid esters (TPU) at least one of formed.However, in the present invention, form the material system not subject to the limits of plastic layer 2.
The selection of material based on plastic layer 2 when carrying out injection-moulding step, is needed used injection mold quilt
It is heated to specific temperature.For example, when carrying out embedded injection-moulding step, injection mold can be heated to 140 DEG C
Above temperature.When using the plastic layer 2 formed by PAEK, injection mold must be heated to 180 DEG C or more of temperature.It removes
Except this, before embedded injection-moulding step is carried out, it is also necessary in advance by injection mold be preheated between 140 to 160 DEG C it
Between temperature.
After the completion of the step of injection molding, composite construction S can be made annealing treatment.Annealing temperature is between 135-
Between 165 DEG C, such as 150 DEG C, and annealing time is 1 to 2 hour.
Next, by according to different embodiment examples and comparative example, provided to further illustrate the present invention embodiment
A kind of composite construction with stainless steel material and plastic material manufacturing method content.
(1) parameter of anodization step and chemical etching step confirms
All it is that use size be the stainless steel material testing cushion of 44*18*1.5mm as stainless in each embodiment example
Steel workpiece 1.The material of stainless steel work-piece 1 is SUS304 stainless steel materials or SUS316 stainless steel materials.Carrying out step
Before S100, stainless steel work-piece 1 is all washed and washed and cleaned, degreasing, alkali cleaning, nitric acid neutralization by pre-treatment step.Preceding place
Manage the details of step as previously described, and can be carried out in existing method.
Next, step S100, step S102 and step S104 are carried out to stainless steel work-piece 1.To all embodiments
Example and comparative example, step S100 are to use sulfuric acid as electrolyte, and all apply the voltage of 3V to electrolyte.In step
In S100, concentration and processing time of the variable parameter for sulfuric acid electrolyte.Then, in step s 102, all it is with DH
730 etching solutions carry out chemical etching, and the temperature of etching solution maintains about 65 DEG C.Variable element in step S102 is etching solution
Chemical composition, etchant concentration and processing time.
For step S104, the stainless steel work with the second erosional surface S2 handled by step S100 and step S102
Part 1 all first passes through adequately washing and baking step, and the temperature of baking step is the baking time between 70 to 100 DEG C
For between 10 to 30 minutes.Then, stainless steel work-piece 1 is placed in injection mold to be molded, makes it mutual with plastic layer 2
With reference to form composite construction S.Composite construction S is made annealing treatment with the annealing conditions of 150 DEG C of temperature, 1 hour time.Multiple
Structure S is closed after being fully cooled, is combined power (pulling capacity) test, and then the binding force for obtaining 10 composite construction S is put down
Mean value.In step S104, variable element is the plastic material type of plastic layer 2.
Details in relation to variable element in step S100, S102 and S104 is please referred to shown in following table 1 and table 2.Separately
Outside, the binding force test result of each embodiment is also found in table 1 and table 2.In table 1, stainless steel work-piece 1 be by SUS 304 not
It becomes rusty made by Steel material, and in table 2, stainless steel work-piece 1 is as made by 316 stainless steel materials of SUS.
Table 1
Table 2
According to the content of table 1 and table 2, can be confirmed in the step s 100, using the time of 5 to 20 minutes as during processing
Between, using the sulfuric acid of 100 to 200g/l concentration as electrolyte, stainless steel work-piece 1 can be made to be averaged with 2 binding force of plastic layer
Value reaches 20MPa/cm2More than.In addition, in step s 102, the concentration of etching solution is in the range of 100 to 200g/l, processing
Time is in 5 to 20 minutes, and stainless steel work-piece 1 can equally be caused to have excellent binding force average value with plastic layer 2.
(2) the composition test of etching solution
In following comparative example, step S102 is carried out using existing etching solution, this case use is included 60 to 80
The effect that the etchant of the ferrous sulfate of the sulfuric acid of weight %, the ferric sulfate of 10 to 30 weight % and 5 to 15 weight % is obtained
Fruit is compared.It is that iron chloride (FeCl is respectively adopted in following 4 comparative examples3) aqueous solution and hydrochloric acid (HCl) and sulfuric acid
Mixed liquor as etching solution.
In following comparative example, step S100 is the sulfuric acid using concentration 200g/l as electrolyte, voltage 3V, sun
The time of pole oxidation step is 10 minutes.In step S104, all it is using the parameter identical with preceding embodiment example, only moulds
The material category of the bed of material 2 is variant.Details in relation to step S102 is described in each comparative example.
Comparative example 1
By the stainless steel work-piece 1 (SUS 304) handled by step S100 after fully washing, merging is a concentration of
100g/l, temperature are between 5 to 20 minutes to carry out step S102, processing time in 65 DEG C of ferric chloride in aqueous solution.It adopts
By the use of 1101 plastic materials of Toray PBT as plastic layer 3.The binding force that 10 composite construction S are obtained after combined power test is put down
Mean value is as shown in table 3.
Table 3
Comparative example 2
By the stainless steel work-piece 1 handled by step S100 (SUS 316L) after fully washing, merging is a concentration of
100g/l, temperature are between 5 to 20 minutes to carry out step S102, processing time in 65 DEG C of ferric chloride in aqueous solution.It adopts
By the use of 2107 plastic materials of Toray PBT as plastic layer 3.The binding force that 10 composite construction S are obtained after combined power test is put down
Mean value is as shown in table 4.
Table 4
Comparative example 3
By the stainless steel work-piece 1 (SUS 304) handled by step S100 after fully washing, merging is a concentration of
100g/l, temperature are between 5 to 20 minutes to carry out step S102, processing time in 65 DEG C of etching solution.Etching solution packet
The sulfuric acid of hydrochloric acid and 100g/l and the water of surplus containing 50g/l.Using 1101 plastic materials of Toray PBT as plastic layer
3.The binding force average value that 10 composite construction S are obtained after combined power test is as shown in table 5.
Table 5
Comparative example 4
By the stainless steel work-piece 1 handled by step S100 (SUS 316L) after fully washing, merging is a concentration of
100g/l, temperature are between 5 to 20 minutes to carry out step S102, processing time in 65 DEG C of etching solution.Etching solution packet
The sulfuric acid of hydrochloric acid and 100g/l and the water of surplus containing 50g/l.Using 2107 plastic materials of Toray PBT as plastic layer
3.The binding force average value that 10 composite construction S are obtained after combined power test is as shown in table 6.
Table 6
Implemented it can be seen from the result of comparative example 1 to comparative example 4 using existing etching solution compared to using the present invention
It is poor to carry out the binding force average value of composite construction S that step S102 is formed for etching solution used in example.For example, exist
Under the parameter of identical step S100, this case embodiment 5 use 304 stainless steel materials of SUS as stainless steel work-piece 1 and
For 1101 plastic materials of Toray PBT as plastic layer 3, the average binding force obtained is 29MPa/cm2, it is above comparative example 1
And 17 and 22MPa/cm of comparative example 32.For using embodiment of the SUS 316L stainless steel materials as stainless steel work-piece 1
Example and comparative example also show similar result.
The beneficial effects of the present invention are provided by the present invention a kind of compound with stainless steel material and plastic material
Structure and its manufacturing method, by the use of the etching solution with specific composition, so that energy on the surface of stainless steel work-piece
Nanostructured is formed, whereby to improve the binding force between stainless steel material and plastic material.
Content disclosed above is only the preferred possible embodiments of the present invention, and the right for not thereby limiting to the present invention will
The protection domain asked, so every equivalence techniques variation done with description of the invention and accompanying drawing content, is both contained in this
In the scope of the claims of invention.
Claims (10)
- A kind of 1. manufacturing method of the composite construction with stainless steel material and plastic material, which is characterized in that the manufacturer Method includes：One stainless steel work-piece is placed in an electrolyte and carries out an anodization step, so that the stainless steel work-piece is aoxidized And form one first erosional surface；A chemical etching step is carried out by being placed in an etching solution with the stainless steel work-piece of first erosional surface, so that It obtains first erosional surface and is etched to form one second erosional surface, wherein, it is between 50 that second erosional surface, which has size, Multiple nanostructureds between to 300 nanometers；AndBy an injection-moulding step, a plastic layer is incorporated on second erosional surface of the stainless steel work-piece, with shape Into the composite construction；Wherein, the etching solution includes the water of an etchant and surplus of the concentration between 50 to 200 g/l, and described Etchant includes sulfuric acid, the ferric sulfate of 10 to 30 weight % and the ferrous sulfate of 5 to 15 weight % of 60 to 80 weight %.
- 2. the manufacturing method of the composite construction according to claim 1 with stainless steel material and plastic material, feature Be, the temperature for stating etching solution be between 55 to 70 DEG C, and the time of the chemical etching step be 5 to 20 minutes.
- 3. the manufacturing method of the composite construction according to claim 1 with stainless steel material and plastic material, feature It is, the electrolyte includes the water of sulfuric acid and surplus of the concentration between 100 to 200 g/l, and the anodic oxidation The time of step is 5 to 20 minutes.
- 4. the manufacturing method of the composite construction according to claim 1 with stainless steel material and plastic material, feature It is, multiple nanostructureds form a cellular structures or a facet level stack structure.
- 5. the manufacturing method of the composite construction according to claim 1 with stainless steel material and plastic material, feature It is, the stainless steel work-piece is formed by SUS304 stainless steels or SUS316 stainless steels.
- 6. the manufacturing method of the composite construction according to claim 1 with stainless steel material and plastic material, feature It is, the plastic layer is by polybutylene terephthalate, polyphenylene sulfide, polyamide, polyether-ether-ketone and thermoplasticity polyamine Carbamate at least one of formed.
- 7. the manufacturing method of the composite construction according to claim 1 with stainless steel material and plastic material, feature Be, have second erosional surface the stainless steel work-piece and the plastic layer between bond strength be between 20 to 40MPa/cm2Between.
- 8. the manufacturing method of the composite construction according to claim 1 with stainless steel material and plastic material, feature It is, the injection-moulding step further comprises：Temperature a molding tool being heated between 140 to 200 DEG C.
- 9. a kind of composite construction with stainless steel material and plastic material, the composite construction is according to claim 1 Manufacturing method made by, which is characterized in that have second erosional surface the stainless steel work-piece and the plastic layer it Between bond strength be between 20 to 40MPa/cm2Between.
- 10. a kind of etching constituent, the etching constituent is for the manufacturer of composite construction according to claim 9 In method, which is characterized in that the etching constituent includes the etchant and surplus concentration between 50 to 200 g/l Water, and the etchant includes the sulfuric acid of 60 to 80 weight %, the ferric sulfate of 10 to 30 weight % and 5 to 15 weight % Ferrous sulfate.
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