Inorganic non-metallic and the combination of plastics and preparation method thereof
Technical field
The present invention relates to combination technical field, a kind of combination more particularly, to inorganic non-metallic and plastics and
Preparation method.
Background technique
With the fast development of the electronic products such as mobile phone, tablet computer, user proposes shell, the component of electronic product
Higher requirement.Shell should also have the requirement such as specious, exquisite in texture while meeting no signal shielding.
Currently, the shell of electronic product mostly uses the combination of nonmetallic materials and plastics.For example, by ceramics, sapphire
Either the inorganic non-metallic materials such as glass are combined by the modes such as bonding or mechanical engaging.But these combinations have centainly
Defect.
By the way of bonding, on the one hand, inorganic non-metallic material and plastics pass through bonding agent meeting during compound
There is excessive glue, in conjunction with the problems such as bad, influences the stability of combination;On the other hand, the mode of bonding factor affected by environment
Greatly, temperature and the qualification of operator have different degrees of influence.
In addition it can which by way of machinery engaging, inorganic non-metallic part and plastics are fastened on one with specific modality
It rises.But the mode of this combination is only applicable to the simple inorganic non-metallic part of structure and plastics, and the two bond strength is low, in conjunction with
There are gaps at place, influence product beauty.
Summary of the invention
It is an object of the present invention to provide the new solutions of a kind of inorganic non-metallic and the combination of plastics.
According to the first aspect of the invention, the combination of a kind of inorganic non-metallic and plastics is provided, comprising: inorganic non-gold
Belong to part, plastics and multicomponent oxide nitride layer, the inorganic non-metallic part has first surface, and the multicomponent oxide nitride layer is by forging
The mode of burning is formed on the first surface, and the multicomponent oxide nitride layer is made of silica and basic anhydride;It is described
Multicomponent oxide nitride layer has one of cellular micropore, mesoporous, macropore or a variety of cavernous structures, and the plastics are incorporated in institute
In the cavernous structure for stating multicomponent oxide nitride layer.
Optionally, the basic anhydride are at least one of sodium oxide molybdena or potassium oxide.
Optionally, further includes: regulator, the regulator are zirconium oxide, titanium oxide or aluminium oxide.
Optionally, the multicomponent oxide nitride layer with a thickness of 10nm-100 μm.
Optionally, the plastics include material of main part and modified material,
Wherein, the material of main part is polyethylene terephthalate plastics, polyphenylene sulfide plastics, gathers to benzene two
At least one of formic acid butanediol fat plastics, Maranyl;
The modified material be glass fibre, carbon fiber, sheet glass, calcium carbonate, magnesium carbonate, silica, in talcum
Any one, the modified material addition is in the material of main part.
Optionally, the diameter of the cavernous structure is 1nm-10 μm, and depth is 1-100 μm.
Optionally, the material of the inorganic non-metallic part is olivine, spinelle, sapphire, glass or ceramics.
According to the second aspect of the invention, a kind of preparation method of the combination of inorganic non-metallic and plastics is provided, including
Following steps:
A kind of inorganic non-metallic part is provided, the inorganic non-metallic part has first surface;
Precursor layer is prepared on the first surface, and the precursor layer is heat-treated, multivariant oxide is obtained
Layer;
The multicomponent oxide nitride layer is surface-treated, the multivariant oxide surface formed cellular micropore,
One of mesoporous, macropore or a variety of cavernous structures;
By plastic injection in the multicomponent oxide nitride layer, combination is formed.
Optionally, before the first surface processing to the inorganic non-metallic part, further includes: surface preparation, it is described
Surface preparation is used to remove the grease on the first surface.
Optionally, the preparation of the precursor layer is using any one or more in coating, dipping, spraying process.
Optionally, the temperature of the heat treatment is 500-1200 DEG C.
Optionally, the surface treatment is alkaline etching processing, and the temperature of alkaline etching processing is 50-100 DEG C, and the processing time is
10min-2h。
It optionally, further include borehole cleaning processing after alkaline etching processing, the borehole cleaning processing is for removing the poroid knot
Powdered granule in structure.
Optionally, during the moulding is moulded in the multicomponent oxide nitride layer, the temperature of injection mold is
100-280 DEG C, injection pressure 30-80Mpa, injection speed 10-20mm/s.
The present invention provides the technical solution of a kind of inorganic non-metallic and the combination of plastics, which is by nothing
Machine nonmetal parts surface forms multicomponent oxide nitride layer, and forms in multicomponent oxide nitride layer cellular micropore, in mesoporous, macropore
One or more cavernous structures, then by way of injection molding, by plastics in conjunction with multicomponent oxide nitride layer.The porous knot
Structure can not only improve the binding force between plastics and inorganic non-metallic part, and not will cause to the structure of inorganic non-metallic part
Damage, will not have an impact the mechanical property of inorganic non-metallic material.The plastics being molded in cellular structures, increase
Bonded area between plastics and multicomponent oxide nitride layer, the two are combined closely by way of mechanical snap, significantly improve nothing
Binding force between machine nonmetal parts and plastics.
By referring to the drawings to the detailed description of exemplary embodiment of the present invention, other feature of the invention and its
Advantage will become apparent.
Detailed description of the invention
It is combined in the description and the attached drawing for constituting part of specification shows the embodiment of the present invention, and even
With its explanation together principle for explaining the present invention.
Fig. 1 is the structural schematic diagram of the combination of inorganic non-metallic and plastics provided in an embodiment of the present invention;
Fig. 2 is the scanning electron microscope schematic diagram of the combination of inorganic non-metallic and plastics provided in an embodiment of the present invention;
Fig. 3 is the flow chart of the preparation method of the combination of inorganic non-metallic and plastics provided in an embodiment of the present invention.
Specific embodiment
Carry out the various exemplary embodiments of detailed description of the present invention now with reference to attached drawing.It should also be noted that unless in addition having
Body explanation, the unlimited system of component and the positioned opposite of step, numerical expression and the numerical value otherwise illustrated in these embodiments is originally
The range of invention.
Be to the description only actually of at least one exemplary embodiment below it is illustrative, never as to the present invention
And its application or any restrictions used.
Technology, method and apparatus known to person of ordinary skill in the relevant may be not discussed in detail, but suitable
In the case of, the technology, method and apparatus should be considered as part of specification.
It is shown here and discuss all examples in, any occurrence should be construed as merely illustratively, without
It is as limitation.Therefore, other examples of exemplary embodiment can have different values.
It should also be noted that similar label and letter indicate similar terms in following attached drawing, therefore, once a certain Xiang Yi
It is defined in a attached drawing, then in subsequent attached drawing does not need that it is further discussed.
The present invention provides a kind of combination, can be used for the shell or components of electronic product.The combination can satisfy nothing
Intensity requirement of the machine nonmetal parts in conjunction with plastics, while the surface of inorganic non-metallic part will not be caused to damage, it influences inorganic
The mechanical property of nonmetal parts.Fig. 1 shows the structural schematic diagram of the combination of inorganic non-metallic and plastics, and Fig. 2 shows inorganic
The nonmetallic scanning electron microscope schematic diagram with the combination of plastics, Fig. 3 is the preparation method of the combination of inorganic non-metallic and plastics
Flow chart.Now by taking Fig. 1 to Fig. 3 as an example, structure feature of combination of the invention, principle and preparation method thereof etc. are retouched
It states.
The present invention provides the combination of a kind of inorganic non-metallic and plastics, which includes: inorganic non-metallic part, plastics
And multicomponent oxide nitride layer.Inorganic non-metallic part is the workpiece made of inorganic non-metallic material, inorganic non-metallic material by
Various industries are widely used in having high-melting-point, high intensity, corrosion resistance and good inoxidizability.In practical application
In, it is often necessary to by inorganic non-metallic part in conjunction with plastics.
As shown in Figure 1, the inorganic non-metallic part 10 has first surface 31, the first surface 31 is to be used for and plastics
20 be combined with each other.Compact multicomponent oxide nitride layer 30, the multicomponent oxide nitride layer are formed on the first surface 31
30 are formed on the first surface 31 by way of calcining, and the multicomponent oxide nitride layer 30 is by silica and alkaline oxygen
Compound is made.By the way that film forming slurry is made by silica and the mixing of a variety of basic anhydride, in the certain processing of process, if
It sets on the first surface 31 of inorganic non-metallic part 10.
As depicted in figs. 1 and 2, the multicomponent oxide nitride layer 30 have one of cellular micropore, mesoporous, macropore or
A variety of cavernous structures 32, the different cavernous structure 32 of diameter are distributed in multicomponent oxide nitride layer 30, the cavernous structure 32 it is micro-
Seeing structure is nano-scale or micron-scale.The cavernous structure increases the faying face between plastics and inorganic point of metalwork
Product, plastic injection can make inorganic non-metallic part and plastics in the mistake of combination in the cavernous structure of the multicomponent oxide nitride layer
Mechanical snap is generated in journey, to effectively promote the binding force between inorganic non-metallic part and plastics.Combination provided by the invention
Body is tightly combined between inorganic non-metallic part and plastics, and the inorganic non-metallic part in conjunction with after is able to maintain preferably mechanical property.
Optionally, the basic anhydride are at least one of sodium oxide molybdena or potassium oxide.Basic anhydride facilitate
In end processing sequences, prevent the multicomponent oxide layer being formed on inorganic non-metallic part first surface from cracking.
In addition, in multicomponent oxide nitride layer further include: regulator, regulator are zirconium oxide, titanium oxide or aluminium oxide.Addition
Regulator is conducive to be tightly combined inorganic non-metallic part and multicomponent oxide nitride layer.Present embodiment illustrates several optional adjustings
Agent, but without limitation to the type of regulator, those skilled in the art can be according to the type of inorganic non-metallic part, and it is suitable to select
Regulator.
Specifically, the multicomponent oxide nitride layer with a thickness of 10nm-100 μm.It should be understood that a variety of cavernous structures are shapes
At in multicomponent oxide nitride layer, the multicomponent oxide nitride layer of different-thickness can be correspondingly formed different pore size and depth by processing
Cavernous structure.
The material of inorganic non-metallic part provided in this embodiment is olivine, spinelle, sapphire, glass or ceramics.On
It states material and belongs to inorganic nonmetallic materials, the combination that the inorganic non-metallic material of hard is formed in conjunction with plastics,
It can give full play to that inorganic non-metallic material is specious, does not generate the characteristic of signal shielding, be provided simultaneously with higher hardness, apply
In on electronic product casing or components, it is not likely to produce scratch.
In a kind of optional embodiment, formed in the multicomponent oxide nitride layer of inorganic non-metallic part with cellular micro-
One of hole, mesoporous, macropore or a variety of cavernous structures, the diameter of the cavernous structure are 1nm-10 μm, and depth is 1-100 μ
m.The cellular cavernous structure can be handled by alkaline etching or other surfaces processing mode, forms micro- different with depth of diameter
One or more of hole, mesoporous, macropore, the present embodiment is without limitation.Cellular cavernous structure, increases plastics
With the bond strength of inorganic non-metallic part.
In another optional embodiment, it is formed in the multicomponent oxide nitride layer of inorganic non-metallic part rough
Structure, plastics can be filled in the structure of the convex injustice of multicomponent oxide nitride layer fovea superior, to realize combination.
Further, the plastics include material of main part and modified material, wherein the material of main part is poly- terephthaldehyde
Sour glycol ester plastics, polyphenylene sulfide plastics, polybutylene terephthalate (PBT) plastics, at least one in Maranyl
Kind.Aforementioned body material has preferable electrical insulating property, heat resistance and intensity, easy to process.
In order to further increase the mechanical property and mechanical performance of plastics, the present embodiment is in the plastic also added with modified material
Material.The modified material can be used as filler, be filled in material of main part, to enhance the performance of material of main part, Enlarge the main parts material
Application range.
For example, the modified material is glass fibre, carbon fiber, sheet glass, calcium carbonate, magnesium carbonate, silica, talcum
In any one.The modified material of addition can reduce the thermal expansion coefficient between inorganic non-metallic part and plastics, prevent from moulding
Material shrinks, warpage or falls off;The anti-bending strength that plastics can be promoted simultaneously helps to enhance inorganic non-metallic part and modeling
The combination of material.
The another aspect of the present embodiment also provides a kind of preparation method of combination, is applied to above-mentioned combination, referring to figure
3, this method comprises the following steps:
S1, a kind of inorganic non-metallic part is provided, the inorganic non-metallic part has first surface;
Wherein, the material of inorganic non-metallic part is olivine, spinelle, sapphire, glass or ceramics.To described inorganic
Before the first surface processing of nonmetal parts, further includes: surface preparation, the surface preparation is for removing first table
Grease on face.The first surface of ceramic matrix can be handled using degreaser or degreasing agent during surface preparation
Regular hour, such as: 300s;It is finally putting into and cleans in deionized water and dry completely.
S2, precursor layer is prepared on the first surface, the precursor layer is heat-treated, multicomponent oxide is obtained
Nitride layer;
The precursor layer of the multivariant oxide includes zirconia nanopowder ball, zirconium hydroxide, zirconium-n-propylate, dichloro oxidation
Zirconium, butyl titanate, TiOx nano ball, alum, monox nanometer ball, ethyl orthosilicate, normal propyl alcohol, oleic acid, adjacent benzene two
Formic acid dibutyl ester, zirconium oxide, calcium carbonate, potassium carbonate, sodium carbonate, sodium hydroxide, combination a variety of in potassium hydroxide.Above-mentioned substance
After mixing, film forming slurry can be prepared.
Prepared film forming slurry is arranged in described first using one or more of coating, dipping, spraying mode
On surface, precursor layer is formed.
The temperature being heat-treated to the precursor layer is 500-1200 DEG C.
S3, the multicomponent oxide nitride layer is surface-treated, is formed on the multivariant oxide surface cellular micro-
One of hole, mesoporous, macropore or a variety of cavernous structures;
To the multicomponent oxide nitride layer carry out alkaline etching processing temperature at 50-100 DEG C, handle the time in 10min to 2h.
After alkaline etching processing, by the way of ultrasonic wave borehole cleaning, borehole cleaning processing, polynary oxygen are carried out to multicomponent oxide nitride layer
The surface of compound layer has powdered granule and falls off, and being formed has one of cellular micropore, mesoporous, macropore or a variety of poroid
Structure.
S4, by plastic injection in the multicomponent oxide nitride layer, formed combination.
By the way of nanometer injection molding, by plastic injection in the multicomponent oxide nitride layer of inorganic non-metallic material.Injection molding
Temperature is controlled at 100-280 DEG C, with the injection pressure of 30-80Mpa, 10-20mm/s injection speed by plastic injection to polynary
In the cavernous structure of oxide skin(coating).
Wherein, plastics are being added to made of modified material in material of main part.Material of main part is poly- terephthaldehyde
Sour glycol ester plastics, polyphenylene sulfide plastics, polybutylene terephthalate's plastics, at least one in Maranyl
Kind.Material of main part has preferable electrical insulating property, heat resistance and intensity, easy to process.The modified material be glass fibre,
Carbon fiber, sheet glass, calcium carbonate, magnesium carbonate, silica, any one in talcum.The modified material adds as filler
It is added in the material of main part, the thermal expansion coefficient between inorganic non-metallic part and plastics can be reduced, prevent plastics from receiving
Contracting, warpage fall off;The anti-bending strength that plastics can be promoted simultaneously facilitates the knot for enhancing inorganic non-metallic part and plastics
It closes.
Embodiment 1
A kind of inorganic non-metallic part is provided, which is zirconia ceramics piece, the zirconia ceramics piece tool
There is first surface, the first surface is used in conjunction with plastics, to form combination.
Firstly, pre-processing using degreaser or degreasing agent to the first surface, the grease on first surface is removed.
One can be handled to the first surface of ceramic matrix using degreaser or degreasing agent during surface preparation
The fixed time, such as: 300s;It is finally putting into and cleans in deionized water and dry completely.
Secondly, preparing film forming slurry.
50 parts of n-butanol, 5 parts of diethanol amine, 50 parts of butyl titanate, 200 parts of normal propyl alcohol are added in beaker
Zirconium is mixed uniformly by way of stirring;It is micro- to weigh 20 parts of nanometer titanium dioxide micro-sphere, 50 parts of nano silica
Ball is put into 2 parts of potassium hydroxide in ball grinder, 5 parts of calcium carbonate, adds 50 parts of n-butanol, and 2 are added in n-butanol
The silane coupling agent of part, 5 parts of dispersing agent;Finally, the solution in beaker is poured into ball grinder, carried out on horizontal ball mill
Ball-milling treatment 0.5h controls the viscosity of slurry in 500cps or less.
Again, inorganic thin film is prepared.
The slurry prepared is placed in spraying equipment, is then sprayed on the first surface of zirconia ceramics piece
Film controls film thickness at 5-20 μm, and 2h is then dried at 50 DEG C, that is, can be made into the precursor layer of multivariant oxide.
Then, heat setting processing is carried out to inorganic thin film.
High-temperature process is divided into three steps, and the first step needs to carry out heat preservation 3h at 280 DEG C, the organic of low molecular weight is discharged
Object;Second step carries out calcining 5h at 750 DEG C, solidifies to film;Final step is warming up to 1100 DEG C of heat preservation 1h, to protect
Card film is tightly combined with zirconia ceramics piece.
Then, nano-porous structure is prepared.
The mixed solution for first preparing a certain amount of sodium hydroxide, potassium chloride etc. is heated to 90 DEG C, then by zirconia ceramics
1h is impregnated in piece placement in the solution, and zirconia ceramics piece is then placed in 5min in supersonic wave cleaning machine, in multicomponent oxide nitride layer
It has powdered granule to fall off, is formed with porous structure, zirconia ceramics piece is cleaned and dried with deionized water.
Finally, nanometer injection molding.
The zirconia ceramics piece for being formed with porous structure is placed in injection forming mold, is contained in the plastic raw materials of injection molding
Polybutylene terephthalate (PBT) (PBT) resin combination of 20% glass fibre, by the test of zirconia ceramics piece and plastics
Piece is fixed on progress product extension test on universal testing machine, tests 6 groups of testing pieces, testing piece average bonding strength respectively
About 30MPa, test result is as follows shown in table 1.
After testing piece is broken, more plastics are remained in multicomponent oxide nitride layer, illustrate pore-forming in the multicomponent oxide nitride layer of surface
Effect is preferable, and plastics are embedded into the porous structure of multicomponent oxide nitride layer, and firmly anchor bolt is in the inorganic of multicomponent oxide nitride layer
In nonmetal parts.
Embodiment 2
A kind of inorganic non-metallic part is provided, which is sheet glass, and the sheet glass has first surface, institute
It states first surface to be used in conjunction with plastics, to form combination.
Firstly, pre-processing using degreaser or degreasing agent to the first surface, the grease on first surface is removed.
One can be handled to the first surface of ceramic matrix using degreaser or degreasing agent during surface preparation
The fixed time, such as: 300s;It is finally putting into and cleans in deionized water and dry completely.
Secondly, preparing film forming slurry.
50 parts of n-butanol, 5 parts of diethanol amine, 50 parts of butyl titanate, 200 parts of normal propyl alcohol are added in beaker
Zirconium is mixed uniformly by way of stirring;It is micro- to weigh 20 parts of nano silica microsphere, 50 parts of nano silica
Ball is put into ball grinder, is subsequently added into 50 parts of n-butanol, and 2 parts of silane coupling agent is added in n-butanol, is then added
5 parts of dispersing agent;Solution in beaker is poured into ball grinder, ball-milling treatment 0.5h, control slurry are carried out on horizontal ball mill
The viscosity of material is in 500cps or less.
Again, inorganic thin film is prepared.
Sheet glass is immersed in the slurry prepared, 2h is then dried at 50 DEG C, that is, can be made into multivariant oxide
Precursor layer.
Then, heat setting processing is carried out to inorganic thin film.
High-temperature process is divided into three steps, and the first step needs to carry out heat preservation 3h at 280 DEG C, the organic of low molecular weight is discharged
Object, second step carry out calcining 5h at 750 DEG C, solidify to film, and final step is warming up to 1000 DEG C of heat preservation 1h, to guarantee
Film is tightly combined with sheet glass.
Then, nano-porous structure is prepared.
The mixed solution for first preparing a certain amount of potassium hydroxide, potassium chloride is heated to 90 DEG C, is then placed on sheet glass
1h is impregnated in solution, is then cleaned with deionized water, is dried for standby.
Finally, nanometer injection molding.
The sheet glass for being formed with porous structure is placed in injection forming mold, 20% glass is contained in the plastic raw materials of injection molding
Polybutylene terephthalate (PBT) (PBT) resin combination of glass fiber, the testing piece of sheet glass and plastics is fixed on omnipotent
Product extension test is carried out in Material Testing Machine, tests 6 groups of testing pieces respectively, and testing piece average bonding strength is about 30MPa, is surveyed
Test result is as shown in table 2 below.
After testing piece is broken, more plastics are remained in multicomponent oxide nitride layer, illustrate the polynary oxide layer pore-forming
Effect is preferable, and plastics are embedded into the porous structure of multicomponent oxide nitride layer, and firmly anchor bolt is in the substrate in multicomponent oxide nitride layer
It is interior.
Although some specific embodiments of the invention are described in detail by example, the skill of this field
Art personnel it should be understood that example above merely to being illustrated, the range being not intended to be limiting of the invention.The skill of this field
Art personnel are it should be understood that can without departing from the scope and spirit of the present invention modify to above embodiments.This hair
Bright range is defined by the following claims.