CN107573061B - The manufacturing method and its application of honeycomb blind hole toughened zirconium oxide ceramic shell - Google Patents
The manufacturing method and its application of honeycomb blind hole toughened zirconium oxide ceramic shell Download PDFInfo
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- CN107573061B CN107573061B CN201710740132.1A CN201710740132A CN107573061B CN 107573061 B CN107573061 B CN 107573061B CN 201710740132 A CN201710740132 A CN 201710740132A CN 107573061 B CN107573061 B CN 107573061B
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Abstract
The invention discloses the manufacturing methods and its application of a kind of honeycomb blind hole toughened zirconium oxide ceramic shell.By green body, sintering at a temperature of being lower than ceramic firing makes particle residual adhesion have some strength to this method, density is only 85%~95% biscuit of theoretical density, densified sintering product again is carved after positive multiform blind hole or blind round hole with carving machine, then filling has cured the organic polymers plastic material such as epoxy resin or silica gel in blind hole.The program is used below firing temperature sintering processing, there is better machinability than injection molding green body, higher processing efficiency and cost advantage are machined with than firing part, organic polymer plastic material absorbs the impact energy fallen part in collision falling process in blind hole, to improve the fracture toughness of ceramic shell.The weight of shell can be effectively reduced in the another aspect program, conducive to the lightening of electronic product, can be used for preparing the consumer electronics shell such as Watchcase, phone housing, panel housings.
Description
Technical field
The present invention relates to structural member preparation fields, and in particular to consumer electronics back board structure part preparation field, in particular to
The manufacturing method and its application of honeycomb blind hole toughened zirconium oxide ceramic shell.
Background technique
With the fast development of consumer electronics, the structural members such as shell (backboard) of consumer electronics achieve significantly into
Step.Conventional metals are due to its included shield effectiveness when especially the structures such as 5G epoch consumer electronics shell design, to antenna
Design brings huge challenge, and plastics its inborn low-intensity disadvantages limits it and answers in large scale screen, ultra-thin field
With in addition as consumers' aesthetic needs to improve, traditional metal shell and plastic shell will be difficult to move consumer.
Since ZrO2 ceramics have high obdurability, good hardness, high-wearing feature, it is widely used in structural ceramics
With function ceramics field.Have been reported that partially stabilized zirconia (TZP) can prepare the hand of corrosion resistant by powder metallurgy process
Table watchcase, table part and Other Instruments part.Therefore in recent years, it is applied to large-sized phone housing also more and more quilt
Researcher is attempted.Such as application No. is in 201510309285.1 patent use zirconium oxide main phase in add aluminium oxide,
The additives such as titanium oxide prepare phone housing by the way of curtain coating.In another example application No. is in 201510940002.3 patent
Using the stable zirconia ceramics powder of yttrium and organic matter mixing extrusion shaping mobile phone shell.It is reported that thanking to " the structure of will roc work
Ceramics " the best ZrO of book introduction toughening performance commercial at present2Ceramic fracture toughness is also only 8~12MPa.m1/2, commercial
There are still problems: zirconia ceramics and metal and plastics ratio, fracture toughness is still bad, and anti-dropping capability is poor, this certainty
Its application is limited, another aspect zirconia ceramics backboard is in order to reach the same anti-dropping capability of other materials, necessarily using thicker
Ceramics manufacture, notably thickness is more than 1mm for some, and zirconia ceramics density is up to 6.1g/cm3, this necessarily causes zirconium oxide to be made pottery
Porcelain backing is heavy, is not inconsistent with the lightening development path of electronic product.
Summary of the invention
In view of this, in view of the deficiencies of the prior art, the present invention aims to provide a kind of honeycomb blind holes
The manufacturing method and its application of toughened zirconium oxide ceramic shell.This method is the interior of honeycomb blind hole toughened zirconium oxide ceramic shell
The multiple regular polygon blind holes of surface engraving or blind round hole, it is organic high that the interior filling of this blind hole has cured epoxy resin or silica gel etc.
Molecule plastic material, organic polymer plastic material absorbs the impact energy that part is fallen to mention in collision falling process
High fracture toughness.
To achieve the above object, the present invention is using following technical solution: a kind of honeycomb blind hole toughened zirconium oxide ceramic
The manufacturing method of shell, comprising the following steps:
A) by surface modifier, inorganic nano Zirconium powder, paraffin and high-molecular organic material in mixer high temperature
Negative pressure mixing obtains feeding；
B) step a) is obtained into feeding and injects shell molds green body under mould cavity negative pressure；
C) that shell green body that step a) is obtained is accounted for theoretical density in high temperature kiln roasting actual density is greater than 70% and small
In 85% biscuit of ceramics；
D) the regular polygon blind hole more than one in the first cam plane engraving of biscuit of ceramics；
E) by the processed biscuit of ceramics of step d) after 1350 DEG C~1450 DEG C normal pressure heat-insulatings are sintered 2h~4h reheating etc.
Static pressure sintering, 1100 DEG C~1200 DEG C of HIP sintering temperature, pressure 50MPa~100MPa, soaking time is 30min~1h
Obtain backboard blank；
F) using the regular polygon blind hole of surface improver processing backboard blank；
G) injection liquid-state epoxy resin or liquid-state silicon in the regular polygon blind hole of the backboard blank by step f) processing
In 60 DEG C~180 DEG C temperature-curable 5min~120min after glue.
Preferably, sintering temperature is 1200 DEG C~1280 DEG C in step c), and soaking time is 1h~2h.
Preferably, the hole depth of positive shape changeable blind hole is 0.1mm~0.9mm, the side of the regular polygon of regular polygon blind hole
A length of 0.5mm~10mm, the wall thickness of two neighboring regular polygon blind hole are 0.5mm~3mm.
Preferably, regular polygon blind hole is equilateral triangle blind hole, square blind hole, regular pentagon blind hole, regular hexagon
It is a kind of in blind hole and round blind hole.
Preferably, in step a) high-molecular organic material be one of polyethylene, polypropylene, polyphenylene sulfide, it is inorganic to receive
Rice Zirconium powder is that yttrium stablizes nano zircite, and D50 is 30nm~200nm.
Preferably, the mass percent of step a) surface modifier is 0.5%~0.8%, inorganic nano Zirconium powder
Mass percent be 85.2%~92.5%, the mass percent that paraffin is is 4%~9%, organic macromolecule quality hundred
Divide than being 3%~5%.
Preferably, step a) and f) in surface modifier be stearic acid, ammonium stearate, it is a kind of in silane coupling agent or two
Kind combination.
Preferably, silane coupling agent is γ-aminopropyl triethoxysilane (KH550), γ-glycidyl ether oxygen propyl
Trimethoxy silane (KH560) and γ-(methacryloxypropyl) propyl trimethoxy silicane (KH570).
Preferably, smelting temperature is 120~150 DEG C in step a), and negative pressure is -0.05MPa~-0.08MPa, mixing time
For 1~4h；Injecting forming temperature is 130~155 DEG C in step b), and negative pressure is -0.07MPa~-0.09MPa.
A kind of phone housing uses the manufacture of honeycomb blind hole toughened zirconium oxide ceramic shell described in above-mentioned technical proposal
Method is prepared.
Beneficial effects of the present invention: the invention discloses a kind of manufacturing methods of honeycomb blind hole toughened zirconium oxide ceramic
And its application.This method, which will be molded green body sintering at a temperature of being lower than ceramic firing, makes particle residual adhesion have some strength,
After its density is only 70%~85% biscuit of ceramics of theoretical density, burnt again after carving multiple positive multiform blind holes or blind round hole
Knot is fine and close, and then filling has cured the organic polymers plastic material such as epoxy resin or silica gel in blind hole.The program uses
It is sintered and machines lower than firing temperature, directly have better machinability than injection molding green body, be machined with higher add than firing part
Work efficiency rate and cost advantage, organic polymer plastic material absorbs the impact fallen part in collision falling process in blind hole
Energy, to improve the fracture toughness of ceramic shell.On the other hand since the shell is ceramic and organic matter composite shell, together
The weight that shell can be effectively reduced under equal strength is conducive to the lightening development of electronic product.
Detailed description of the invention
Fig. 1 is the manufacturing method schematic diagram of honeycomb blind hole toughened zirconium oxide ceramic shell.
Fig. 2 is the schematic diagram of cured epoxy resin gain of heat zirconia ceramics phone housing in honeycomb regular hexagon blind hole.
Specific embodiment
Present invention is further described in detail below, wherein used raw material and equipment be it is commercially available, be not important to
It asks.It is understood that specific embodiment described herein is only used for explaining related invention, rather than the restriction to the invention.
A kind of manufacturing method of honeycomb blind hole toughened zirconium oxide ceramic shell, prepares according to the following steps:
A) by surface modifier, inorganic nano Zirconium powder, paraffin and high-molecular organic material in mixer high temperature
Negative pressure mixing obtains feeding.Wherein high-molecular organic material is common polyethylene, polypropylene, polycarbonate, liquid crystal polymer
Equal organic matters, in this example preferred high-molecular organic material be polyethylene, polypropylene, it is a kind of in polyphenylene sulfide, it is inorganic to receive
Rice Zirconium powder is that yttrium stablizes nano zircite, and D50 is 30nm~200nm.Surface modifier is stearic acid, stearic acid
One or two kinds of combinations in salt, silane coupling agent.Wherein, stearate is preferably ammonium stearate, and silane coupling agent is γ-ammonia
Propyl-triethoxysilicane (KH550), γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560) and γ-(metering system
One of acyl-oxygen) propyl trimethoxy silicane (KH570).
The mass percent of preferred surface modifier is 0.5%~0.8% in this example, inorganic nano zirconia powder
The mass percent of body is 85.2%~92.5%, and the mass percent that paraffin is is 4%~9%, organic macromolecule quality
Percentage is 3%~5%.
In the present embodiment, different according to above-mentioned preferred component, temperature is 120 DEG C~150 in preferred internal mixing pass
DEG C, negative pressure of vacuum is -0.05MPa~-0.08MPa, and the time is 1h~4h.
B) it will be evacuated in the die cavity of mold after negative pressure state and step a) obtained into mixing feeding injection moulding shell green body.?
In this example injecting forming temperature be 130 DEG C~155 DEG C, injection before will be evacuated in mould cavity negative pressure -0.07MPa~-
Within 0.09MPa, to reduce injection pressure, the injection molding green body internal flaw such as trace, stomata is reduced, blank strength is improved.
C) that shell green body that step a) is obtained is accounted for theoretical density in high temperature kiln roasting actual density is greater than 70% and small
In 85% biscuit of ceramics；Preferably its stacking after degreasing, is transferred to sintering furnace in debinding furnace by shell green body in this example
In slowly heating exclude organic polymer framework material after by furnace temperature be warming up to sintering temperature and keep the temperature a period of time.This heat preservation is burnt
Junction temperature is sintered lower than ceramic firing temperature, is made residual adhesion between ceramic particle and particle, is become the pottery not densified completely
Porcelain biscuit, because the hardness of biscuit of ceramics is conducive to machining steps below lower than the ceramic hardness after firing.According in this example
The difference of material and preparation process early period, in order to by blank sintering to being greater than 70% and less than the biscuit of ceramics of 85% consistency,
The sintering temperature of this preferred example is 1200 DEG C~1280 DEG C, and soaking time is 1h~2h.
D) in the multiple regular polygon blind holes of the first cam plane engraving of biscuit of ceramics.Preferred first plane is inner surface of outer cover,
Outer surface is complete ceramic surface, is conducive to beautiful and wear-resisting.Polygonal blind hole can also be carved, is preferably in this example
Regular polygon blind hole, the technique of engraving are CNC engraving or laser engraving.Regular polygon blind hole can be equilateral in this example
It is a kind of in triangle blind hole, square blind hole, regular pentagon blind hole, regular hexagon blind hole and round blind hole, it is also possible to other
Shape has no special requirement limitation.Wherein the hole depth of positive shape changeable blind hole is according to the thickness of shell in 0.1mm~0.9mm
It is preferred that the side length of the regular polygon of preferred regular polygon blind hole is 0.5mm~10mm, phase in order to not influence the intensity of shell
The wall thickness of adjacent two regular polygon blind holes is 0.5mm~3mm.
Step d) e) is carved to the biscuit of ceramics densified sintering product after blind hole.Due to biscuit of ceramics have already passed through it is once sintered,
Partial particulate, which has, grows up and adhesion phenomenon, needs sintering in the case where being higher than 1500 DEG C of normal pressures or at higher temperature could be fine and close
Change.Therefore HIP sintering makes its quick densifying again after preferred elder generation is normal pressure-sintered in this example.Preferred ceramics element
HIP sintering obtains backboard blank, HIP sintering to base again after 1350 DEG C~1450 DEG C normal pressure heat-insulatings are sintered 2h~4h
1100 DEG C~1200 DEG C of temperature, pressure 50MPa~100MPa, soaking time is 30min~1h.
F) using the regular polygon blind hole of surface improver processing backboard blank, make itself and organic polymer plastic material
Bond strength is higher, without using in the process as falling off.It is preferable to use stearic acid, ammonium stearate, silane coupled in this example
The blind hole of one or two kinds of combination modification backboard blanks in agent.
G) injection liquid-state epoxy resin or liquid-state silicon in the regular polygon blind hole of the backboard blank by step f) processing
In 60 DEG C~180 DEG C temperature-curable 5min~120min after glue, liquid resin is set to be cured as organic polymer plastic material, with back
The firm connection of plate blank.It preferably in this example can flash and surplus being added using CNC process equipment by backboard blank
Work is fallen, then by outer surface of outer cover grinding and polishing light processing.
Phone housing, watchcase, panel housings are manufactured by the preparation method technical solution of zirconia ceramics shell described above
Equal electronic shells structural member.
The following are specific embodiments of the present invention:
Embodiment 1
Weigh the 3Y-TZP ceramic powder that γ-(methacryloxypropyl) propyl trimethoxy silicane 14g, D50 are 30nm
Weighed organic matter is added in the mixer of 3L and is warming up to 130 DEG C by the polypropylene of 1.706kg, No. 58 paraffin 180g and 100g
Make its thawing, then divide 3 times and mixing is added in ceramic powder, after ceramic powder addition after the completion of, by mixer take out negative pressure to-
0.05MPa obtains feeding in 135 DEG C of mixing 3h.Feeding is packed into the hopper of injection molding machine, by 2.15 inches of Watchcase molds
Die cavity is packed into injection molding machine, and 2.15 inches of Watchcase mould cavities are evacuated to -0.08MPa, set injection molding machine barrel temperature as 145
DEG C, injection pressure is 180MPa injection molding, and pressure maintaining 4s in the feeding high speed injection die cavity of melting is made to obtain Watchcase backboard biscuit.
Watchcase biscuit stacking is put into debinding furnace and is to slowly warm up to 170 DEG C with the rate of 0.2 DEG C/min, heat preservation
Cell phone back laminin base stacking is put into sintering furnace by 1 DEG C/min by furnace cooling after 20h, is warming up to 430 DEG C and is kept the temperature two hours,
Then 1 DEG C/min is warming up to 650 DEG C, is cooled to after being then warming up to 1200 DEG C of heat preservation 2h with 5 DEG C/min rate by 5 DEG C/min
1050 DEG C of furnace coolings obtain the phone housing biscuit of ceramics that consistency is 70.2%.
Watchcase biscuit of ceramics is put into high speed CNC process equipment and is accommodated with fixture, with 0.1mm feed velocity whole
A inner surface fluting processing equilateral triangle blind hole, wherein the blind hole side length 5mm for the equilateral triangle processed, blind hole depth 0.1mm, blind hole
The wall thickness 2mm between blind hole is dried in an oven after rinsing it with clear water after completion of processing.
The Watchcase biscuit of ceramics of drying is placed after being warming up to 1350 DEG C of heat preservation 4h in sintering furnace with 5 DEG C/min rate
1050 DEG C of furnace coolings are cooled to by 5 DEG C/min, are then placed in hot isostatic pressure stove, are heated up with the rate of 10 DEG C/min
To 1100 DEG C, under 100MPa pressure, soaking time is cold with furnace to be cooled to 1050 DEG C of furnace coolings by 5 DEG C/min after 30min
But Watchcase blank is obtained.
It weighs γ-aminopropyl triethoxysilane (KH550) 50g and 2kg deionized water and 2kg alcohol mixed solution is added
In, Watchcase blank is put into after wherein impregnating 2h and is put into oven drying, then coats liquid-state epoxy resin to blind hole
60 DEG C of solidification 120min in an oven are scraped off after extra liquid-state epoxy resin, then backboard blank uses CNC process equipment will
Flash and surplus machine away, and are then handled using ceramic grinding polishing machine and obtain the honeycomb blind hole toughened zirconium oxide ceramic mobile phone
Backboard.
It is repeatedly sampled by the sample requirement of three-point bending method test bending strength and Single edge notch beam test fracture toughness
Test is averaged, and test result is that the bending strength of the ceramics is 1213MPa, fracture toughness 15.8MPa.m1/2, and according to thanking
The bending strength of " structural ceramics " book introduction that will roc writes Y-TZP commercial at present is usually 800~1200MPa, is broken tough
Property be 8~12MPa.m1/2.With commercial Y-TZP ceramic phase ratio, fracture toughness is significantly improved, it is particularly suited for phone housing
(backboard).
Embodiment 2
Weigh 3Y-TZP ceramic powder 1.704kg, 180g56 paraffin and 100g that ammonium stearate 16g, D50 are 30nm
Weighed organic matter is added in the mixer of 3L and is warming up to 115 DEG C and makes its thawing by polyethylene, then divide 3 times by ceramic powder
Mixing is added, after the completion of ceramic powder addition, mixer is taken out into negative pressure to -0.05MPa, obtains feeding in 120 DEG C of mixing 4h.
Feeding is packed into the hopper of injection molding machine, injection molding machine will be packed into a thickness of 5 inches of phone mould die cavitys, by 5 inches of phone moulds
Die cavity is evacuated to -0.09MPa, sets injection molding machine barrel temperature as 130 DEG C, injection pressure is 250MPa injection molding, makes the feeding of melting
Pressure maintaining 3s obtains cell phone back laminin base in high speed injection die cavity.
Cell phone back laminin base stacking, which is put into debinding furnace, is to slowly warm up to 170 DEG C with the rate of 0.2 DEG C/min, keeps the temperature 20h
Cell phone back laminin base stacking is put into sintering furnace by 1 DEG C/min by furnace cooling afterwards, is warming up to 400 DEG C and is kept the temperature two hours, then
1 DEG C/min is warming up to 650 DEG C, is cooled to 1050 DEG C by 5 DEG C/min after being then warming up to 1280 DEG C of heat preservation 1h with 5 DEG C/min rate
Furnace cooling obtains the mobile phone backboard biscuit of ceramics that relative density is 84.7%.
Mobile phone backboard biscuit of ceramics biscuit of ceramics is put into high speed CNC process equipment and is accommodated with fixture, with 0.1mm feed
Speed slots in entire inner surface and processes square blind hole, wherein the blind hole side length 0.5mm for the square processed, blind hole are deep
0.1mm, wall thickness 0.5mm between blind hole and blind hole are dried in an oven after rinsing it with clear water after completion of processing.
The Watchcase biscuit of ceramics of drying is placed after being warming up to 1450 DEG C of heat preservation 2h in sintering furnace with 5 DEG C/min rate
1050 DEG C of furnace coolings are cooled to by 5 DEG C/min, are then placed in hot isostatic pressure stove, are heated up with the rate of 10 DEG C/min
To 1200 DEG C, in pressure 50MPa, soaking time is cooled to 1050 DEG C of furnace cooling furnace coolings by 5 DEG C/min after being 1h and obtains
Phone housing blank.
Weigh γ-aminopropyl triethoxysilane 30g and γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560)
20g is added in 2kg deionized water and 2kg alcohol mixed solution, is then put into phone housing blank after wherein impregnating 2h and is put into
Then oven drying coats liquid-state silicon gel to scraping off 180 DEG C of solidifications in an oven after extra liquid-state silicon gel resin in blind hole
5min, then backboard blank is machined away flash and surplus using CNC process equipment, is then using the processing of ceramic grinding polishing machine
Obtain the honeycomb blind hole toughened zirconium oxide ceramic mobile phone backboard.
It is repeatedly sampled by the sample requirement of three-point bending method test bending strength and Single edge notch beam test fracture toughness
Test is averaged, and test result is that the bending strength of the ceramics is 1143MPa, fracture toughness 14.0MPa.m1/2。
Embodiment 3
Weigh the polyphenyl of 3Y-TZP ceramic powder 1.85kg, 80g58 paraffin and 60g that stearic acid 10g, D50 are 200nm
Thioether makes its thawing for being warming up to 120 DEG C in the mixer of weighed organic matter addition 3L, then divides 3 times and add ceramic powder
Enter mixing, after the completion of ceramic powder addition, mixer is taken out into negative pressure to -0.08MPa, obtains feeding in 150 DEG C of mixing 1h.It will
Feeding is packed into the hopper of injection molding machine, will be packed into injection molding machine with a thickness of 8 inch flat panel die cavitys, 8 inch flat panel mould cavities are taken out
To -0.07MPa, injection molding machine barrel temperature is set as 155 DEG C, injection pressure is 200MPa injection molding, infuses the feeding high speed of melting
Enter pressure maintaining 5s in die cavity and obtains panel housings biscuit.
Panel housings biscuit stacking, which is put into debinding furnace, is to slowly warm up to 170 DEG C with the rate of 0.2 DEG C/min, keeps the temperature 20h
Plate backboard biscuit stacking is put into sintering furnace by 1 DEG C/min by furnace cooling afterwards, is warming up to 450 DEG C and is kept the temperature two hours, then
1 DEG C/min is warming up to 650 DEG C, is cooled to 1050 DEG C by 5 DEG C/min after being then warming up to 1250 DEG C of heat preservation 2h with 5 DEG C/min rate
Furnace cooling obtains the panel housings biscuit of ceramics that relative density is 80.5%.
Panel housings biscuit of ceramics is put into high speed CNC process equipment and is accommodated with fixture, with 0.3mm depth of cut whole
A inner surface opens milling regular pentagon blind hole, wherein the blind hole side length 10mm of the regular pentagon milled, blind hole depth 0.9mm, blind hole with it is blind
Wall thickness 3mm between hole is dried in an oven after rinsing it with clear water after completion of processing.
The panel housings biscuit of ceramics of drying is placed after being warming up to 1400 DEG C of heat preservation 3h in sintering furnace with 5 DEG C/min rate
1050 DEG C of furnace coolings are cooled to by 5 DEG C/min, are then placed in hot isostatic pressure stove, are heated up with the rate of 10 DEG C/min
To 1150 DEG C, in pressure 100MPa, soaking time is cooled to 1050 DEG C of furnace cooling furnace coolings by 5 DEG C/min after being 1h and obtains
Panel housings blank.
It weighs γ-(methacryloxypropyl) propyl trimethoxy silicane 50g and 2kg deionized water and the mixing of 2kg ethyl alcohol is added
In solution, then panel housings blank is put into after wherein impregnating 2h and is put into oven drying, then coat liquid-state silicon gel to blind
180 DEG C of solidification 10min in an oven are scraped off after extra liquid-state silicon gel in hole, then panel housings blank is set using CNC processing
It is standby to machine away flash and surplus, it is then handled using ceramic grinding polishing machine and obtains the honeycomb blind hole toughened zirconium oxide ceramic
Panel housings.
It is repeatedly sampled by the sample requirement of three-point bending method test bending strength and Single edge notch beam test fracture toughness
Test is averaged, and test result is that the bending strength of the ceramics is 1077MPa, fracture toughness 14.5MPa.m1/2。
Embodiment 4
Weighing γ-aminopropyl triethoxysilane 12g, D50 is the 8Ce-TZP ceramic powder 1.708kg of 50nm, No. 58
The polypropylene of paraffin 180g and 100g make its thawing for being warming up to 130 DEG C in the mixer of weighed organic matter addition 3L, then
Divide 3 times and mixing is added in ceramic powder, after the completion of ceramic powder addition, mixer is taken out into negative pressure to -0.07MPa, at 140 DEG C
Mixing 3h obtains feeding.Feeding is packed into the hopper of injection molding machine, will be packed into a thickness of the 6 of 0.6mm inches of phone mould die cavitys
6 inches of phone mould die cavitys are taken out negative pressure to -0.08MPa by injection molding machine, set injection molding machine barrel temperature as 150 DEG C, injection pressure
For 190MPa injection molding, pressure maintaining 4s in the feeding high speed injection die cavity of melting is made to obtain 6 cun of phone housing biscuits.
Phone housing biscuit stacking, which is put into debinding furnace, is to slowly warm up to 170 DEG C with the rate of 0.2 DEG C/min, keeps the temperature 20h
Phone housing biscuit stacking is put into sintering furnace by 1 DEG C/min by furnace cooling afterwards, is warming up to 420 DEG C and is kept the temperature two hours, then
1 DEG C/min is warming up to 650 DEG C, is cooled to 1050 DEG C by 5 DEG C/min after being then warming up to 1270 DEG C of heat preservation 1h with 5 DEG C/min rate
Furnace cooling obtains the phone housing biscuit of ceramics that relative density is 83.2%.
Phone housing biscuit of ceramics is put into high speed CNC process equipment and is accommodated with fixture, with 0.3mm depth of cut whole
A inner surface mills regular hexagon blind hole, wherein the blind hole side length 3mm of the regular hexagon milled, blind hole depth 0.3mm, blind hole and blind hole it
Between wall thickness 2mm, dried in an oven after rinsing it with clear water after completion of processing.
The panel housings biscuit of ceramics of drying is placed in sintering furnace, 1400 DEG C of heat preservation 2.5h are warming up to 5 DEG C/min rate
1050 DEG C of furnace coolings are cooled to by 5 DEG C/min afterwards, are then placed in hot isostatic pressure stove, with the rate liter of 10 DEG C/min
Temperature is to 1150 DEG C, and in pressure 50MPa, soaking time is cooled to 1050 DEG C of furnace cooling furnace coolings by 5 DEG C/min after being 1h and obtains
To mobile phone outer sleeve blank.
It weighs and is uniformly mixed in stearic acid 50g addition 3kg ethanol solution, then mobile phone backboard blank is put into and is wherein impregnated
It is put into oven drying after 3h, then coats liquid-state epoxy resin to scraping off in blind hole after extra liquid-state epoxy resin in baking oven
In 80 DEG C of solidification 40min, then backboard blank is machined away flash and surplus using CNC process equipment, then use ceramic grinding
Polishing machine processing obtains the honeycomb blind hole toughened zirconium oxide ceramic phone housing, as shown in Figure 2.
It is repeatedly sampled by the sample requirement of three-point bending method test bending strength and Single edge notch beam test fracture toughness
Test is averaged, and test result is that the bending strength of the ceramics is 1095MPa, fracture toughness 14.9MPa.m1/2。
Embodiment 5
Weigh γ-glycidyl ether oxygen propyl trimethoxy silicane 8g, γ-(methacryloxypropyl) propyl trimethoxy silicon
Alkane 6g, D50 are the polyphenylene sulfide of the 3Y-TZP ceramic powder 1.766kg of 30nm, No. 56 paraffin 140g and 80g, are had weighed
Being warming up to 145 DEG C in the mixer of machine object addition 3L makes its thawing, then divides 3 times ceramic powder mixing is added, to ceramic powder
After the completion of body is added, mixer is taken out into negative pressure to -0.06MPa, obtains feeding in 150 DEG C of mixing 2h.Feeding is packed into injection molding machine
Hopper in, 5.7 inches of phone mould die cavitys are packed into injection molding machines, 5.7 inches of phone mould die cavitys are evacuated to -0.08MPa, if
Determining injection molding machine barrel temperature is 155 DEG C, and injection pressure is 190MPa injection molding, makes pressure maintaining 4s in the feeding high speed injection die cavity of melting
Obtain phone housing biscuit.
Phone housing biscuit stacking, which is put into debinding furnace, is to slowly warm up to 170 DEG C with the rate of 0.2 DEG C/min, keeps the temperature 20h
Cell phone back laminin base stacking is put into sintering furnace by 1 DEG C/min by furnace cooling afterwards, is warming up to 450 DEG C and is kept the temperature two hours, then
1 DEG C/min is warming up to 650 DEG C, is cooled to 1050 DEG C by 5 DEG C/min after being then warming up to 1230 DEG C of heat preservation 1h with 5 DEG C/min rate
Furnace cooling obtains the mobile phone backboard blank that relative density is 76.6%.
Phone housing biscuit of ceramics is put into high speed CNC process equipment and is accommodated with fixture, with 0.2mm depth of cut whole
A inner surface processes blind round hole, wherein the blind round hole diameter processed is 7mm, blind hole depth 0.2mm, the partition of blind hole and blind hole
Thick 1.5mm is dried in an oven after rinsing it with clear water after completion of processing.
The phone housing biscuit of ceramics of drying is placed after being warming up to 1380 DEG C of heat preservation 3h in sintering furnace with 5 DEG C/min rate
1050 DEG C of furnace coolings are cooled to by 5 DEG C/min, are then placed in hot isostatic pressure stove, are heated up with the rate of 10 DEG C/min
To 1150 DEG C, in pressure 100MPa, soaking time by 5 DEG C/min is cooled to 1050 DEG C of furnace cooling furnace coolings after being 30min
Obtain phone housing blank.
It weighs and is uniformly mixed in ammonium stearate 50g addition 3kg ethanol solution, then mobile phone backboard blank is put into and is wherein soaked
It is put into oven drying after stain 3h, then liquid-state epoxy resin is coated to after scraping off extra liquid-state epoxy resin in blind hole and is being dried
70 DEG C of solidification 60min in case, then backboard blank is machined away flash and surplus using CNC milling cutter, then using ceramic grinding and polishing
Light processing obtains the honeycomb blind hole toughened zirconium oxide ceramic mobile phone backboard.
It is repeatedly sampled by the sample requirement of three-point bending method test bending strength and Single edge notch beam test fracture toughness
Test is averaged, and test result is that the bending strength of the ceramics is 1219MPa, fracture toughness 15.6MPa.m1/2。
Above description is only the preferred embodiment of the application and the explanation to institute's application technology principle.Those skilled in the art
Member is it should be appreciated that invention scope involved in the application, however it is not limited to technology made of the specific combination of above-mentioned technical characteristic
Scheme, while should also cover in the case where not departing from the inventive concept, it is carried out by above-mentioned technical characteristic or its equivalent feature
Any combination and the other technical solutions formed.Such as features described above has similar function with (but being not limited to) disclosed herein
Can technical characteristic replaced mutually and the technical solution that is formed.
Claims (10)
1. the manufacturing method of honeycomb blind hole toughened zirconium oxide ceramic shell, which comprises the following steps:
A) by surface modifier, inorganic nano Zirconium powder, paraffin and high-molecular organic material in mixer high temperature negative pressure
Mixing obtains feeding；
B) step a) is obtained into feeding and injects shell molds green body under mould cavity negative pressure；
C) the shell green body that step b) is obtained is accounted for into theoretical density greater than 70% in high temperature kiln roasting actual density and be less than
85% biscuit of ceramics；
D) in the more than one periodic regular polygon blind hole of the first cam plane engraving of biscuit of ceramics；
E) by the processed biscuit of ceramics of step d) after 1350 DEG C~1450 DEG C normal pressure heat-insulatings are sintered 2h~4h hot isostatic pressing again
Sintering, 1100 DEG C~1200 DEG C of HIP sintering temperature, pressure 50MPa~100MPa, soaking time is that 30min~1h is obtained
Backboard blank；
F) using the periodical regular polygon blind hole of surface improver processing backboard blank；
G) injection liquid-state epoxy resin or liquid in the periodical regular polygon blind hole of the backboard blank by step f) processing
In 60 DEG C~180 DEG C temperature-curable 5min~120min after silica gel.
2. the manufacturing method of honeycomb blind hole toughened zirconium oxide ceramic shell according to claim 1, it is characterised in that: step
It is rapid c) in sintering temperature be 1200 DEG C~1280 DEG C, soaking time be 1h~2h.
3. the manufacturing method of honeycomb blind hole toughened zirconium oxide ceramic shell according to claim 2, it is characterised in that: just
The hole depth of shape changeable blind hole is 0.1mm~0.9mm, and the side length of the regular polygon of regular polygon blind hole is 0.5mm~10mm, phase
The wall thickness of adjacent two regular polygon blind holes is 0.5mm~3mm.
4. the manufacturing method of honeycomb blind hole toughened zirconium oxide ceramic shell according to claim 3, it is characterised in that: just
Polygonal blind hole is one in equilateral triangle blind hole, square blind hole, regular pentagon blind hole, regular hexagon blind hole and round blind hole
Kind.
5. the manufacturing method of honeycomb blind hole toughened zirconium oxide ceramic shell according to claim 4, it is characterised in that: step
It is rapid a) in high-molecular organic material be one of polyethylene, polypropylene, polyphenylene sulfide, inorganic nano Zirconium powder be yttrium it is steady
Determine nano zircite, D50 is 30nm~200nm.
6. the manufacturing method of honeycomb blind hole toughened zirconium oxide ceramic shell according to claim 5, it is characterised in that: step
It is rapid a) in the mass percent of surface modifier be 0.5%~0.8%, the mass percent of inorganic nano Zirconium powder is
85.2%~92.5%, the mass percent of paraffin is 4%~9%, and organic macromolecule mass percent is 3%~5%.
7. the manufacturing method of honeycomb blind hole toughened zirconium oxide ceramic shell according to claim 6, it is characterised in that: step
It is rapid a) and f) in surface modifier be stearic acid, ammonium stearate, silane coupling agent one or two kinds of combinations.
8. the manufacturing method of honeycomb blind hole toughened zirconium oxide ceramic shell according to claim 7, it is characterised in that: silicon
Alkane coupling agent is γ-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane and γ-(methyl-prop
One of alkene acyl-oxygen) propyl trimethoxy silicane.
9. the manufacturing method of honeycomb blind hole toughened zirconium oxide ceramic shell according to claim 8, it is characterised in that: step
It is rapid a) in smelting temperature be 120 DEG C~150 DEG C, negative pressure be -0.05MPa~-0.08MPa, mixing time be 1~4h；Step b)
Middle injecting forming temperature is 130 DEG C~155 DEG C, and negative pressure is -0.07MPa~-0.09MPa.
10. a kind of phone housing, it is characterised in that use manufacturer's legal system described in any one of claim 1~9 claim
It is standby to obtain.
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| CN108650344A (en) * | 2018-04-24 | 2018-10-12 | 深圳初上科技有限公司 | A kind of intelligent temp.-sensitive controlled color-change ceramic mobile phone shell |
| CN110655401A (en) * | 2018-06-28 | 2020-01-07 | 东莞信柏结构陶瓷股份有限公司 | Zirconia ceramic material, zirconia ceramic structural member and preparation method thereof |
| CN110323383B (en) * | 2019-06-24 | 2022-03-15 | Oppo广东移动通信有限公司 | Battery cover, preparation method thereof and mobile terminal |
| CN111136999A (en) * | 2019-12-24 | 2020-05-12 | 南京工程学院 | High-toughness shell brick mud structure-imitated ceramic matrix composite material and preparation method thereof |
| CN112589955A (en) * | 2020-12-23 | 2021-04-02 | 深圳艾利佳材料科技有限公司 | Powder injection molding method of ultra-thin wall honeycomb-shaped product |
| CN113105234B (en) * | 2021-04-16 | 2022-08-16 | 深圳陶陶科技有限公司 | Zirconia composite material, ceramic product, preparation method and application thereof |
| CN113225941B (en) * | 2021-05-12 | 2023-02-07 | 四川锐宏电子科技有限公司 | Preparation process of blind hole multilayer high-density circuit board |
| CN113277875A (en) * | 2021-05-27 | 2021-08-20 | 深圳市精而美精密陶瓷科技有限公司 | Bicolor ceramic electronic appearance structural component, preparation method and application thereof |
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