CN103519675B - Non-stick pan of a kind of not fluoride and preparation method thereof - Google Patents
Non-stick pan of a kind of not fluoride and preparation method thereof Download PDFInfo
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- CN103519675B CN103519675B CN201310468291.2A CN201310468291A CN103519675B CN 103519675 B CN103519675 B CN 103519675B CN 201310468291 A CN201310468291 A CN 201310468291A CN 103519675 B CN103519675 B CN 103519675B
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Abstract
The present invention is specifically related to non-stick pan of a kind of not fluoride and preparation method thereof.Its technical scheme is: first at inner surface coating transition zone (2) of aluminum alloy pan substrate (3), and the material of transition zone (2) is aluminium oxide or is aluminium nitride; Then will be coated with aluminum alloy pan substrate (3) ultrasonic cleaning in acetone soln of transition zone (2), then use absolute ethyl alcohol processed, dry; Finally adopt multi sphere ion plating technology, the upper depositing Ti C of transition zone (2) of aluminum alloy pan substrate (3) after the drying, the hard ceramic layer (1) of TiCN or TiN nanostructured, the non-stick pan of obtained not fluoride.The thickness of described transition zone (2) is 10 ~ 50 μm; The scavenging period of described ultrasonic cleaning is 10 ~ 60min.Non-stick pan technique prepared by the present invention is simple, safe preparation process environmental protection, and obtained non-stick pan has the feature of the good and long service life of not fluoride, harmless health, wearability.
Description
Technical field
The invention belongs to non-stick pan technical field.Be specifically related to non-stick pan of a kind of not fluoride and preparation method thereof.
Background technology
In daily life, often there is food with conventional aluminum alloy pot cooking food and glue pot phenomenon.The food be charred not only destroys profile, and it is healthy easily to produce harmful substance harm humans.In addition, also for cooker cleaning adds difficulty.The method of existing solution non-stick pan is at aluminum alloy pan surface coating one deck polytetrafluoroethylene (PTFE).
Though the needs of sticky pot do not occur when can meet people's cooking food existing non-stick pan, polytetrafluorethylecoatings coatings intensity is not high, easily peels off and damages.After top layer hydrophobic substance is worn away, the performance that non-stick pan just loses " not gluing ".And in use whether there is hidden danger also to there is dispute to health for polytetrafluoroethylene (PTFE) non-stick pan, constantly cause controversial issue.
The patent No. is that the utility model patent of ZL95226356.4 discloses a kind of plating of novel non-stick pan by name non-stick pan of one deck amorphous phosphorus-nickel alloy layer, this coating has that wearability is good, coefficient of friction is low and the feature such as self-lubricating property is good, not only overcome short shortcoming in traditional fluorine-containing non-stick pan service life, and not fluoride.But nickel itself is heavy metal, nickel, phosphorus are harmful to the person, and this patented technology does not carry out European Union's food-grade sanitary index test heavy metal transformation amount.
Summary of the invention
The present invention is intended to overcome prior art defect, and object is to provide the preparation method of the non-stick pan of the not fluoride of the simple and safety and environmental protection of a kind of technique, the good and long service life of the non-stick pan wearability prepared by the method.
For achieving the above object, the technical solution used in the present invention is: first at the inner surface coating transition zone of aluminum alloy pan substrate, and the material of transition zone is aluminium oxide or is aluminium nitride; Then will be coated with aluminum alloy pan substrate ultrasonic cleaning in acetone soln of transition zone, then use absolute ethyl alcohol processed, dry; Finally adopt multi sphere ion plating technology, the hard ceramic layer of depositing Ti C, TiCN or TiN nanostructured on the transition zone of aluminum alloy pan substrate after the drying, the non-stick pan of obtained not fluoride.
The chemical constituent of described aluminum alloy pan is: Si is 0.20 ~ 1.70wt%, Fe be 0.003 ~ 1.60 wt%, Cu be 0.05 ~ 7.0 wt%, Mn be 0.01 ~ 1.50 wt%, Zn is 0.03 ~ 6.70 wt%, and surplus is Al and inevitable impurity.
The thickness of described transition zone is 10 ~ 50 μm.
The scavenging period of described ultrasonic cleaning is 10 ~ 60min.
The technological parameter of the hard ceramic layer of described depositing Ti C nano structure is: back bias voltage is 0 ~ 300V; C
2h
2flow is 0.15 ~ 0.25L/min; Ar flow is 0.01 ~ 0.04L/min; Target current is 50 ~ 80A; Depositing temperature is 50 ~ 300 DEG C; Sedimentation time is 30 ~ 90min.
The technological parameter of the hard ceramic layer of described depositing Ti CN nanostructured is: back bias voltage is 0 ~ 300V; N
2flow is 0.15 ~ 0.25L/min; C
2h
2flow is 0.15 ~ 0.25L/min; Ar flow is 0.01 ~ 0.04L/min; Target current is 50 ~ 80A; Depositing temperature is 50 ~ 300 DEG C; Sedimentation time is 30 ~ 90min.
The technological parameter of the hard ceramic layer of the nanostructured of described TiN is: back bias voltage is 0 ~ 300V; N
2flow is 0.15 ~ 0.25L/min; Ar flow is 0.01 ~ 0.04L/min; Target current is 50 ~ 80A; Depositing temperature is 50 ~ 300 DEG C; Sedimentation time is 30 ~ 90min.
Owing to adopting technique scheme, the present invention compared with prior art has following economic effect:
The present invention covers one deck hardness transition zone placed in the middle at the hard ceramic interlayer of the inner surface of the lower aluminum alloy pan substrate of hardness and the very high nanostructured of hardness, adhesion between outer coating and matrix is significantly improved, namely significantly improve the adhesion of the hard ceramic layer of nanostructured and the inner surface of aluminum alloy pan substrate, make the hard ceramic layer of the nanostructured of deposition incrust.
The hard ceramic layer of TiCN, TiC or TiN nanostructured has that hardness is high, good toughness, coefficient of friction are little, chemical stability good and to the advantage such as food is pollution-free.Multi-arc ion coating method is adopted to be coated with inner surface depositing Ti CN, TiC or TiN of aluminum alloy pan substrate of transition zone, obtain the hard ceramic layer of nanoscale rough structure, hard ceramic layer is made to have hydrophobicity, obtained non-stick pan coating layer stable chemical nature under cooking temp, prepared aluminium alloy non-stick pan is tested, by 26 ~ 30 circulations through frying pan spades speeding-up simulation.Compare the non-stick pan of polytetrafluorethylecoatings coatings, not only extend one times service life, and there is not potential safety hazard, can be replaced it and use.In addition, multi sphere ion plating technology is adopted not produce polluter, safety and environmental protection in the process of the hard ceramic layer of depositing nano structure.
Therefore, preparation technology of the present invention is simple, safe preparation process environmental protection, and obtained non-stick pan has the feature of the good and long service life of not fluoride, harmless health, wearability.
Accompanying drawing explanation
Fig. 1 is a kind of structural representation of the present invention.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the invention will be further described, the restriction not to its protection domain.
For avoiding repetition, first by as follows for the technical parameter Unify legislation involved by this detailed description of the invention, repeat no more in embodiment:
The chemical constituent of described aluminum alloy pan substrate 3 is: Si is 0.20 ~ 1.70wt%, Fe be 0.003 ~ 1.60 wt%, Cu be 0.05 ~ 7.0 wt%, Mn be 0.01 ~ 1.50 wt%, Zn is 0.03 ~ 6.70 wt%, and surplus is Al and inevitable impurity.
embodiment 1
Non-stick pan of a kind of not fluoride and preparation method thereof.As shown in Figure 1, first at the inner surface coating transition zone 2 of aluminum alloy pan substrate 3, the material of transition zone 2 is aluminium oxide; Then will be coated with aluminum alloy pan substrate 3 ultrasonic cleaning in acetone soln of transition zone 2, then use absolute ethyl alcohol processed, dry; Finally adopt multi sphere ion plating technology, the hard ceramic layer 1 of depositing Ti C nano structure on the transition zone 2 of aluminum alloy pan substrate 3 after the drying, the non-stick pan of obtained not fluoride.
The thickness of described transition zone 2 is 10 ~ 30 μm.
The scavenging period of described ultrasonic cleaning is 10 ~ 40min.
The technological parameter of the hard ceramic layer 1 of described depositing Ti C nano structure is: back bias voltage is 0V; C
2h
2flow is 0.15 ~ 0.18L/min; Ar flow is 0.02 ~ 0.03L/min; Target current is 60 ~ 70A; Depositing temperature is 50 ~ 130 DEG C; Sedimentation time is 50 ~ 70min.
The non-stick pan of the not fluoride prepared by the present embodiment carries out the test of frying pan spades speeding-up simulation, by 26 ~ 27 circulations.
embodiment 2
Non-stick pan of a kind of not fluoride and preparation method thereof.As shown in Figure 1, be first coated with transition zone 2 at the inner surface of aluminum alloy pan substrate 3, the material of transition zone 2 is aluminium nitride; Then will be coated with aluminum alloy pan substrate 3 ultrasonic cleaning in acetone soln of transition zone 2, then use absolute ethyl alcohol processed, dry; Finally adopt multi sphere ion plating technology, the hard ceramic layer 1 of depositing Ti C nano structure on the transition zone 2 of aluminum alloy pan substrate 3 after the drying, the non-stick pan of obtained not fluoride.
The thickness of described transition zone 2 is 20 ~ 40 μm.
The scavenging period of described ultrasonic cleaning is 20 ~ 50min.
The technological parameter of the hard ceramic layer 1 of described depositing Ti C nano structure is: back bias voltage is 1 ~ 150V; C
2h
2flow is 0.18 ~ 0.22L/min; Ar flow is 0.03 ~ 0.04L/min; Target current is 70 ~ 80A; Depositing temperature is 130 ~ 210 DEG C; Sedimentation time is 70 ~ 90min.
The non-stick pan of the not fluoride prepared by the present embodiment is tested, by 26 ~ 27 circulations through frying pan spades speeding-up simulation.
embodiment 3
Non-stick pan of a kind of not fluoride and preparation method thereof.As shown in Figure 1, first at the inner surface coating transition zone 2 of aluminum alloy pan substrate 3, the material of transition zone 2 is aluminium oxide; Then will be coated with aluminum alloy pan substrate 3 ultrasonic cleaning in acetone soln of transition zone 2, then use absolute ethyl alcohol processed, dry; Finally adopt multi sphere ion plating technology, the hard ceramic layer 1 of depositing Ti C nano structure on the transition zone 2 of aluminum alloy pan substrate 3 after the drying, the non-stick pan of obtained not fluoride.
The thickness of described transition zone 2 is 30 ~ 50 μm.
The scavenging period of described ultrasonic cleaning is 30 ~ 60min.
The technological parameter of the hard ceramic layer 1 of described depositing Ti C nano structure is: back bias voltage is 150 ~ 300V; C
2h
2flow is 0.22 ~ 0.25L/min; Ar flow is 0.01 ~ 0.02L/min; Target current is 50 ~ 60A; Depositing temperature is 210 ~ 300 DEG C; Sedimentation time is 30 ~ 50min.
The non-stick pan of the not fluoride prepared by the present embodiment is tested, by 29 ~ 30 circulations through frying pan spades speeding-up simulation.
embodiment 4
Non-stick pan of a kind of not fluoride and preparation method thereof.As shown in Figure 1, first at the inner surface coating transition zone 2 of aluminum alloy pan substrate 3, the material of transition zone 2 is aluminium oxide; Then will be coated with aluminum alloy pan substrate 3 ultrasonic cleaning in acetone soln of transition zone 2, then use absolute ethyl alcohol processed, dry; Finally adopt multi sphere ion plating technology, the hard ceramic layer 1 of depositing Ti CN nanostructured on the transition zone 2 of aluminum alloy pan substrate 3 after the drying, the non-stick pan of obtained not fluoride.
The thickness of described transition zone 2 is 10 ~ 30 μm.
The scavenging period of described ultrasonic cleaning is 10 ~ 40min.
The technological parameter of the hard ceramic layer 1 of described depositing Ti CN nanostructured is: back bias voltage is 0V; N
2flow is 0.15 ~ 0.18L/min; C
2h
2flow is 0.22 ~ 0.25L/min; Ar flow is 0.01 ~ 0.02L/min; Target current is 50 ~ 60A; Depositing temperature is 50 ~ 130 DEG C; Sedimentation time is 30 ~ 50min.
The non-stick pan of the not fluoride prepared by the present embodiment is tested, by 27 ~ 28 circulations through frying pan spades speeding-up simulation.
embodiment 5
Non-stick pan of a kind of not fluoride and preparation method thereof.As shown in Figure 1, first at the inner surface coating transition zone 2 of aluminum alloy pan substrate 3, the material of transition zone 2 is aluminium nitride; Then will be coated with aluminum alloy pan substrate 3 ultrasonic cleaning in acetone soln of transition zone 2, then use absolute ethyl alcohol processed, dry; Finally adopt multi sphere ion plating technology, the hard ceramic layer 1 of depositing Ti CN nanostructured on the transition zone 2 of aluminum alloy pan substrate 3 after the drying, the non-stick pan of obtained not fluoride.
The thickness of described transition zone 2 is 20 ~ 40 μm.
The scavenging period of described ultrasonic cleaning is 20 ~ 50min.
The technological parameter of the hard ceramic layer 1 of described depositing Ti CN nanostructured is: back bias voltage is 1 ~ 150V; N
2flow is 0.18 ~ 0.22L/min; C
2h
2flow is 0.15 ~ 0.18L/min; Ar flow is 0.02 ~ 0.03L/min; Target current is 60 ~ 70A; Depositing temperature is 130 ~ 210 DEG C; Sedimentation time is 50 ~ 70min.
The non-stick pan of the not fluoride prepared by the present embodiment is tested, by 29 ~ 30 circulations through frying pan spades speeding-up simulation.
embodiment 6
Non-stick pan of a kind of not fluoride and preparation method thereof.As shown in Figure 1, first at the inner surface coating transition zone 2 of aluminum alloy pan substrate 3, the material of transition zone 2 is aluminium oxide; Then will be coated with aluminum alloy pan substrate 3 ultrasonic cleaning in acetone soln of transition zone 2, then use absolute ethyl alcohol processed, dry; Finally adopt multi sphere ion plating technology, the hard ceramic layer 1 of depositing Ti CN nanostructured on the transition zone 2 of the aluminum alloy pan substrate 3 after drying up, the non-stick pan of obtained not fluoride.
The thickness of described transition zone 2 is 30 ~ 50 μm.
The scavenging period of described ultrasonic cleaning is 30 ~ 60min.
The technological parameter of the hard ceramic layer 1 of described depositing Ti CN nanostructured is: back bias voltage is 150 ~ 300V; N
2flow is 0.22 ~ 0.25L/min; C
2h
2flow is 0.18 ~ 0.22L/min; Ar flow is 0.03 ~ 0.04L/min; Target current is 70 ~ 80A; Depositing temperature is 210 ~ 300 DEG C; Sedimentation time is 70 ~ 90min.
The non-stick pan of the not fluoride prepared by the present embodiment is tested, by 29 ~ 30 circulations through frying pan spades speeding-up simulation.
embodiment 7
Non-stick pan of a kind of not fluoride and preparation method thereof.As shown in Figure 1, first at the inner surface coating transition zone 2 of aluminum alloy pan substrate 3, the material of transition zone 2 is aluminium oxide; Then will be coated with aluminum alloy pan substrate 3 ultrasonic cleaning in acetone soln of transition zone 2, then use absolute ethyl alcohol processed, dry; Finally adopt multi sphere ion plating technology, the hard ceramic layer 1 of depositing TiN nanostructured on the transition zone 2 of aluminum alloy pan substrate 3 after the drying, the non-stick pan of obtained not fluoride.
The thickness of described transition zone 2 is 10 ~ 30 μm.
The scavenging period of described ultrasonic cleaning is 10 ~ 40min.
The technological parameter of the hard ceramic layer 1 of the nanostructured of described depositing TiN is: back bias voltage is 0V; N
2flow is 0.15 ~ 0.18L/min; Ar flow is 0.01 ~ 0.02L/min; Target current is 50 ~ 60A; Depositing temperature is 50 ~ 130 DEG C; Sedimentation time is 30 ~ 50min.
The non-stick pan of the not fluoride prepared by the present embodiment is tested, by 28 ~ 29 circulations through frying pan spades speeding-up simulation.
embodiment 8
Non-stick pan of a kind of not fluoride and preparation method thereof.As shown in Figure 1, first at the inner surface coating transition zone 2 of aluminum alloy pan substrate 3, the material of transition zone 2 is aluminium nitride; Then will be coated with aluminum alloy pan substrate 3 ultrasonic cleaning in acetone soln of transition zone 2, then use absolute ethyl alcohol processed, dry; Finally adopt multi sphere ion plating technology, the hard ceramic layer 1 of depositing TiN nanostructured on the transition zone 2 of aluminum alloy pan substrate 3 after the drying, the non-stick pan of obtained not fluoride.
The thickness of described transition zone 2 is 20 ~ 40 μm.
The scavenging period of described ultrasonic cleaning is 20 ~ 50min.
The technological parameter of the hard ceramic layer 1 of the nanostructured of described depositing TiN is: back bias voltage is 1 ~ 150V; N
2flow is 0.18 ~ 0.22L/min; Ar flow is 0.02 ~ 0.03L/min; Target current is 60 ~ 70A; Depositing temperature is 210 ~ 300 DEG C; Sedimentation time is 70 ~ 90min.
The non-stick pan of the not fluoride prepared by the present embodiment is tested, by 29 ~ 30 circulations through frying pan spades speeding-up simulation.
embodiment 9
Non-stick pan of a kind of not fluoride and preparation method thereof.As shown in Figure 1, first at the inner surface coating transition zone 2 of aluminum alloy pan substrate 3, the material of transition zone 2 is aluminium oxide; Then will be coated with aluminum alloy pan substrate 3 ultrasonic cleaning in acetone soln of transition zone 2, then use absolute ethyl alcohol processed, dry; Finally adopt multi sphere ion plating technology, the hard ceramic layer 1 of depositing TiN nanostructured on the transition zone 2 of aluminum alloy pan substrate 3 after the drying, the non-stick pan of obtained not fluoride.
The thickness of described transition zone 2 is 30 ~ 50 μm.
The scavenging period of described ultrasonic cleaning is 30 ~ 60min.
The technological parameter of the hard ceramic layer 1 of the nanostructured of described depositing TiN is: back bias voltage is 15 ~ 300V; N
2flow is 0.22 ~ 0.25L/min; Ar flow is 0.03 ~ 0.04L/min; Target current is 70 ~ 80A; Depositing temperature is 130 ~ 210 DEG C; Sedimentation time is 50 ~ 70min.
The non-stick pan of the not fluoride prepared by the present embodiment is tested, by 27 ~ 28 circulations through frying pan spades speeding-up simulation.
This detailed description of the invention compared with prior art has following economic effect:
This detailed description of the invention covers one deck hardness transition zone placed in the middle 2 between the hard ceramic layer 1 of the inner surface of the lower aluminum alloy pan substrate 3 of hardness and the very high nanostructured of hardness, adhesion between outer coating and matrix is significantly improved, namely significantly improve the hard ceramic layer 1 of nanostructured and the adhesion of the inner surface of aluminum alloy pan substrate 3, make the hard ceramic layer 1 of the nanostructured of deposition incrust.
The hard ceramic layer 1 of TiCN, TiC or TiN nanostructured has that hardness is high, good toughness, coefficient of friction are little, chemical stability good and to the advantage such as food is pollution-free.Multi-arc ion coating method is adopted to be coated with inner surface depositing Ti CN, TiC or TiN of aluminum alloy pan substrate 3 of transition zone 2, obtain the hard ceramic layer of nanoscale rough structure, hard ceramic layer is made to have hydrophobicity, obtained non-stick pan coating layer stable chemical nature under cooking temp, the non-stick pan of the not fluoride prepared by this detailed description of the invention is tested, by 26 ~ 30 circulations through frying pan spades speeding-up simulation.Compare the non-stick pan of polytetrafluorethylecoatings coatings, not only extend one times service life, and there is not potential safety hazard, can be replaced it and use.In addition, multi sphere ion plating technology is adopted not produce polluter, safety and environmental protection in the process of the hard ceramic layer 1 of depositing nano structure.
Therefore, this detailed description of the invention preparation technology is simple, safe preparation process environmental protection, and obtained non-stick pan has the feature of the good and long service life of not fluoride, harmless health, wearability.
Claims (8)
1. a preparation method for the not non-stick pan of fluoride, is characterized in that first at inner surface coating transition zone (2) of aluminum alloy pan substrate (3), and the material of transition zone (2) is aluminium oxide or is aluminium nitride; Then will be coated with aluminum alloy pan substrate (3) ultrasonic cleaning in acetone soln of transition zone (2), then use absolute ethyl alcohol processed, dry; Finally adopt multi sphere ion plating technology, the upper depositing Ti C of transition zone (2) of aluminum alloy pan substrate (3) after the drying, the hard ceramic layer (1) of TiCN or TiN nanostructured, the non-stick pan of obtained not fluoride.
2. the preparation method of the non-stick pan of not fluoride according to claim 1, it is characterized in that the chemical constituent of described aluminum alloy pan substrate (3) is: Si is 0.20 ~ 1.70wt%, Fe is 0.003 ~ 1.60 wt%, Cu is 0.05 ~ 7.0 wt%, Mn is 0.01 ~ 1.50 wt%, Zn is 0.03 ~ 6.70 wt%, and surplus is Al and inevitable impurity.
3. the preparation method of the non-stick pan of not fluoride according to claim 1, is characterized in that the thickness of described transition zone (2) is 10 ~ 50 μm.
4. the preparation method of the non-stick pan of not fluoride according to claim 1, is characterized in that the scavenging period of described ultrasonic cleaning is 10 ~ 60min.
5. the preparation method of the non-stick pan of not fluoride according to claim 1, is characterized in that the technological parameter of the hard ceramic layer (1) of described depositing Ti C nano structure is: back bias voltage is 0 ~ 300V; C
2h
2flow is 0.15 ~ 0.25L/min; Ar flow is 0.01 ~ 0.04L/min; Target current is 50 ~ 80A; Depositing temperature is 50 ~ 300 DEG C; Sedimentation time is 30 ~ 90min.
6. the preparation method of the non-stick pan of not fluoride according to claim 1, is characterized in that the technological parameter of the hard ceramic layer (1) of described depositing Ti CN nanostructured is: back bias voltage is 0 ~ 300V; N
2flow is 0.15 ~ 0.25L/min; C
2h
2flow is 0.15 ~ 0.25L/min; Ar flow is 0.01 ~ 0.04L/min; Target current is 50 ~ 80A; Depositing temperature is 50 ~ 300 DEG C; Sedimentation time is 30 ~ 90min.
7. the preparation method of the non-stick pan of not fluoride according to claim 1, is characterized in that the technological parameter of the hard ceramic layer (1) of the nanostructured of described TiN is: back bias voltage is 0 ~ 300V; N
2flow is 0.15 ~ 0.25L/min; Ar flow is 0.01 ~ 0.04L/min; Target current is 50 ~ 80A; Depositing temperature is 50 ~ 300 DEG C; Sedimentation time is 30 ~ 90min.
8. a non-stick pan for not fluoride, is characterized in that described non-stick pan is the non-stick pan of the not fluoride prepared by preparation method of the non-stick pan of not fluoride according to any one of claim 1 ~ 7.
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KR101510444B1 (en) * | 2014-11-12 | 2015-04-10 | (주) 더몰론코리아 | Heating cookware having excellent durability |
CN107815683A (en) * | 2016-04-22 | 2018-03-20 | 宁波高新区夏远科技有限公司 | A kind of non-stick pan and preparation method thereof |
CN106321494A (en) * | 2016-10-25 | 2017-01-11 | 郑州航空工业管理学院 | Anti-erosion and friction-resistant film for fan blades of aeto-turbofan engine and preparation method of anti-erosion and friction-resistant film |
CN110584496A (en) * | 2019-09-12 | 2019-12-20 | 宁波钛灏新材料科技有限公司 | Non-stick pan and preparation method thereof |
CN115261802A (en) * | 2022-07-11 | 2022-11-01 | 武汉汇九厨具科技有限公司 | Photoetching high-temperature-resistant non-stick metal kitchen ware and preparation process thereof |
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