CN108373261A - Artificial color changing gem and preparation method thereof - Google Patents
Artificial color changing gem and preparation method thereof Download PDFInfo
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- CN108373261A CN108373261A CN201810040828.8A CN201810040828A CN108373261A CN 108373261 A CN108373261 A CN 108373261A CN 201810040828 A CN201810040828 A CN 201810040828A CN 108373261 A CN108373261 A CN 108373261A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/04—Opacifiers, e.g. fluorides or phosphates; Pigments
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/004—Refining agents
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/04—Compositions for glass with special properties for photosensitive glass
- C03C4/06—Compositions for glass with special properties for photosensitive glass for phototropic or photochromic glass
- C03C4/065—Compositions for glass with special properties for photosensitive glass for phototropic or photochromic glass for silver-halide free photochromic glass
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Geochemistry & Mineralogy (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
The invention belongs to synthetic cut stone technical fields, and in particular to artificial color changing gem and preparation method thereof.Artificial color changing gem includes SiO2、K2O、Nd2O3、CaCO3、Pr6O11、Na2O、ZnO、As2O3, fluxing agent, fining agent.Preparation method includes the following steps：(1) each raw material is mixed in proportion, is stirred evenly, obtain mixture A；(2) mixture A is heated to 1,350 1500 DEG C, is kept for 20 hours so that mixture A is completely melt, obtains molten mass B；(3) molten mass B is cooled to 1,200 1250 DEG C, pours into mold after being kept for 4 hours, obtains stone C；(4) stone C is annealed.The artificial color changing gem of the present invention can generate broader color and tone, and there is the distincter green color changeable effect of purple, preparation method can significantly improve mass output rate and environmental protection under different light.
Description
Technical field
The invention belongs to synthetic cut stone technical fields, and in particular to artificial color changing gem and preparation method thereof.
Background technology
Alexandria alexandrite (ALEXANDRITE) is also known as the green alexandrite of gold, is one of five big rare jewels, belongs to chrysoberyl
Change colour kind.Under daylight or daylight type light, its color typically exhibits grayish green, yellowish green to blue-green；But in incandescence
Under source, it usually looks like brown red or aubergine.It is commonly called as " emerald in the daytime, the ruby at night ".Influence alexandrite price
Factor be mainly alexandrite color changeable effect, size, transparency and flaw how much.It is, in general, that color changeable effect is more apparent, it is such as white
It is in emerald green, is at night cerise, then price is higher.But the jewel under normal circumstances, having color changeable effect apparent in this way is few,
Usually daytime be in dirty-green, at night be in bronzing, i.e. daytime as Brazilian emerald, at night as garnet.
The yield of alexandrite is extremely rare at present, and most important source is Brazil and Sri Lanka, and others have Burma, smooth
Sani Asia and Zimbabwe, cause its price excessively expensive, therefore jewel fan one after another analyzes Alexandria alexandrite, mould
It is imitative, it is intended to develop a kind of identical artificial stone of Alexandria alexandrite performance.
Patent 85108154A discloses a kind of synthetic cut stone, and rare earth element nd 3+ is added in niobates, uses czochralski method
Monocrystal is grown into, the jewel is at rose under incandescent lamp, and at pale red under sunlight, lower in daylight etc. is in pale purple
Color, the jewel cannot show grandmother's green, and lift law technology and only have 1/4 raw material that can be drawn as the available crystalline substance of color and luster
Body, and czochralski method equipment is complicated, technology require it is high, it is low for output/output-input ratio for producing such civilian jewel, be unfavorable for batch
Amount production.
Patent 201110154049.9 discloses a kind of color-changing crystal, and silver halide, the halogenation of 2-4% are added in crystal
Titanium, caddy, copper chloride or rare earth compound, for the crystal to discoloration, needing could be real in the case where fluorescent lamp lives ultraviolet light
It is existing, be not suitable for wearing.
Patent 200810122029.1 discloses a kind of preparation method of beryllium aluminate crystal substrate color changing gem,
In BeAl2O4 monocrystalline, mixed with tri- kinds of dopants of Cr2O3, Fe2O3, Ti2O3 or NiO, using vertical static temperature gradients method
Color changing gem is prepared, which can only realize the red variation with green, and color and luster is not fine.
Invention content
In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide a kind of artificial discoloration is precious
Stone can show amber, aubergine, the green three kinds of colors of grandmother, artificial color changing gem face of the invention under different light
Color is vivid, and discoloration is achieved that under daylight and incandescent light, is suitble to wear, and using SiO2 as base material, and material is easy to obtain, and
Cost is relatively low, can meet the needs of public；Another object of the present invention is to provide a kind of preparation method of artificial color changing gem,
This method is conducive to the large-scale production of high-quality jewel and preparation process is environmentally friendly, does not generate poisonous and harmful substance.
The purpose of the invention is achieved by the following technical solution：Artificial color changing gem includes the raw material of following parts by weight：
The artificial color changing gem of the present invention passes through in SiO2Middle addition K2O,Nd2O3,CaCO3,Pr6O11,Na2O,ZnO,
As2O3,B2O3So that jewel can generate more wide color and tone, and have has distincter purple green under different light
Color changeable effect.
Further, the artificial color changing gem includes the raw material of following parts by weight：
Further, the artificial color changing gem includes the raw material of following parts by weight：
Preferably, the fluxing agent is B2O3、K2CO3And Na2CO3At least one of.
B2O3It can help to reduce viscosity of glass metal, accelerate clarifying process, B2O3The formation reaction of silicate is converted to lower
Temperature region, while formation, surface tension and the viscosity etc. for reducing eutectic finally makes speed of melting promote 15%-
16%, production efficiency greatly improves；K2CO3The tendency towards devitrification that glass can be reduced increases transparency and gloss of glass etc.；
Na2CO3Thermal stability, chemical stability and mechanical strength can be reduced；Make the easy melting of glass.
More preferably, B2O3、K2CO3And Na2CO3Ratio be 1：1-3：1-5.
Preferably, the fining agent is Sb2O3And CaF2One or two.
Sb2O3It can release O after pyrolytic2, CaF2It can release F after pyrolytic2, reaction process is released
Minute bubbles become emersion metal level after air pocket so that glass clarifying.
More preferably, Sb2O3And CaF2Ratio be 1：1-3.
A kind of preparation method of artificial color changing gem, includes the following steps：
(1) each raw material is mixed in proportion, is stirred evenly, obtain mixture A；
(2) mixture A is heated to 1350-1500 DEG C, is kept for 20 hours so that mixture A is completely melt, is melted
Body B；
(3) molten mass B is cooled to 1200-1250 DEG C, pours into mold after being kept for 4 hours, obtains stone C；
(4) stone C is annealed, obtains artificial color changing gem.
Further, in the step (2), mixture A is put into electric melting furnace or pot furnace and is heated.
Preferably, in the step (2), mixture A is put into pot furnace and is heated.
Pot furnace is simple in structure, low cost, builds soon, fast and easy puts into production, and melting system is easy to control adjusting, right
Technique it is adaptable, can reload at any time；With among cullet feeding crucible, this charging process can increase raw material simultaneously
The heating surface area of raw material, strengthened glass melting process make the unreacted grains of sand that will not sink in glass metal, and it is solid to eliminate glass
Phenomenon obtains the finished product of better quality.
Further, it is heated to 1450 DEG C in the step (2), is kept for 20 hours so that mixture A is completely melt, is obtained
To molten mass B, be cooled in the step (3) 1250 DEG C kept for 4 hours after pour into mold, obtain stone C.
After crucible are added in raw material by the present invention, 1450 DEG C are constantly warming up to, raw material is put into crucible and is fused into melt,
After period melt-blended material will spend 20 hours, 1250 DEG C are cooled to, can effectively exclude the bubble in glass melts and striped,
So that the jewel prepared is more glittering and translucent.
Further, annealing includes such as the next stage in the step (4)：
(a) stone C is warming up to 500-530 DEG C by the heating period；
(b) temperature of holding stage, holding stage is 480-510 DEG C, keeps the temperature 20-24 hours；
(c) slow cooling stage, slow cooling stage are cooled to the strain point of glass with the cooling rate of 5-15 DEG C/min；
(d) rapid cooling stage, rapid cooling stage are cooled to room temperature with the cooling rate of 20-40 DEG C/min from the strain point of glass.
Heating period can effectively eliminate jewel thermal stress；After the upper limit for determining annealing temperature during heating, by temperature
It is reduced to holding temperature, keeps the temperature 20-24 hours so that heat uniformly transfers in jewel, can effectively eliminate stress；The slow cooling stage
Stress can be caused to subside inconsistent and cause jewel crack or material uneven, to influence treasured to avoid too fast due to cooling down
The quality of stone；The rapid cooling stage is carried out after being cooled to jewel strain point or less, the rapid cooling stage can accelerate cooling velocity to shorten
Entire annealing process reduces fuel consumption, improves productivity.
Further, the heating period in the step (a) is warming up to 500-530 with the heating rate of 20-30 DEG C/min
℃。
During heating, gemstone surface will produce compression and jewel caused to deform, therefore keep rate of heat addition phase
To fast so that heat quickly transmits, and reduces deformation extent, and the heating rate of 20-30 DEG C/min is kept to can effectively avoid heating rank
Jewel caused by section deforms.
The beneficial effects of the present invention are：The artificial color changing gem of the present invention can generate more wide color and tone,
There is the distincter green color changeable effect of purple under different light；The preparation method can significantly improve mass output rate, be conducive to high-quality
The large-scale production of jewel, in addition preparation method environmental protection, preparation process will not adversely affect ambient enviroment, will not more produce
Raw poisonous and harmful substance, while meeting the export standard of external cameo glass.
Specific implementation mode
For the ease of the understanding of those skilled in the art, with reference to embodiment, the present invention is further illustrated, real
The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1,
Artificial color changing gem includes the raw material of following parts by weight：
The fluxing agent is B2O3, the fining agent is Sb2O3。
A kind of preparation method of artificial color changing gem, it is characterised in that：Include the following steps：
(1) each raw material is mixed in proportion, is stirred evenly, obtain mixture A；
(2) mixture A is heated to 1350 DEG C, is kept for 20 hours so that mixture A is completely melt, obtains molten mass B；
(3) molten mass B is cooled to 1200 DEG C, pours into mold after being kept for 4 hours, obtains stone C；
(4) stone C is annealed, obtains artificial color changing gem.
Further, mixture A is put into electric melting furnace in the step (2) and is heated.
Further, annealing includes such as the next stage in the step (4)：
(a) stone C is warming up to 500 DEG C by the heating period；
(b) temperature of holding stage, holding stage is 480 DEG C, keeps the temperature 24 hours；
(c) slow cooling stage, slow cooling stage are cooled to the strain point of glass with the cooling rate of 5 DEG C/min；
(d) rapid cooling stage, rapid cooling stage are cooled to room temperature with the cooling rate of 20 DEG C/min from the strain point of glass.
In the present embodiment, the strain point of cameo glass is 430-480 DEG C.
Further, the heating period in the step (a) is warming up to 500 DEG C with the heating rate of 20 DEG C/min.
The present invention preparation method can significantly improve mass output rate, it is simple using equipment, overcome due to machine driving with shake
The harmful effects such as the dynamic abrasion generated to jewel and bubble deformation, are conducive to the large-scale production of high-quality jewel.The preparation method
It is very environmentally friendly, poisonous and harmful substance is not generated, ambient enviroment will not be adversely affected, while meeting external jewel glass
The export standard of glass.
Embodiment 2
Difference lies in the artificial color changing gem includes the raw material of following parts by weight to embodiment 2 with embodiment 1：
The fluxing agent is K2CO3, the fining agent is Sb2O3。
Embodiment 3
Difference lies in the artificial color changing gem includes the raw material of following parts by weight to embodiment 3 with embodiment 1：
The fluxing agent is by B2O3、K2CO3And Na2CO3According to weight ratio 1：1：1 mixes, and the fining agent is Sb2O3。
Embodiment 4
Difference lies in the artificial color changing gem includes the raw material of following parts by weight to embodiment 4 with embodiment 1：
The fluxing agent is B2O3、K2CO3And Na2CO3According to weight ratio 1：3：5 mix, and the fining agent is CaF2。
Embodiment 5
Difference lies in the artificial color changing gem includes the raw material of following parts by weight to embodiment 5 with embodiment 1：
The fluxing agent is B2O3、K2CO3And Na2CO3According to weight ratio 1：1：5 mix, and the fining agent is CaF2。
Embodiment 6
Embodiment 6 and embodiment 1 difference lies in：
A kind of preparation method of artificial color changing gem, includes the following steps：
(1) each raw material is mixed in proportion, is stirred evenly, obtain mixture A；
(2) mixture A is heated to 1450 DEG C, is kept for 20 hours so that mixture A is completely melt, obtains molten mass B；
(3) molten mass B is cooled to 1200 DEG C, pours into mold after being kept for 4 hours, obtains stone C；
(4) stone C is annealed, obtains artificial color changing gem.
Embodiment 7
Embodiment 7 and embodiment 1 difference lies in：
A kind of preparation method of artificial color changing gem, includes the following steps：
(1) each raw material is mixed in proportion, is stirred evenly, obtain mixture A；
(2) mixture A is heated to 1500 DEG C, is kept for 20 hours so that mixture A is completely melt, obtains molten mass B；
(3) molten mass B is cooled to 1200 DEG C, pours into mold after being kept for 4 hours, obtains stone C；
(4) stone C is annealed, obtains artificial color changing gem.
Embodiment 8
Embodiment 8 and embodiment 1 difference lies in：
A kind of preparation method of artificial color changing gem, includes the following steps：
(1) each raw material is mixed in proportion, is stirred evenly, obtain mixture A；
(2) mixture A is heated to 1500 DEG C, is kept for 20 hours so that mixture A is completely melt, obtains molten mass B；
(3) molten mass B is cooled to 1250 DEG C, pours into mold after being kept for 4 hours, obtains stone C；
(4) stone C is annealed, obtains artificial color changing gem.
Embodiment 9
Embodiment 9 and embodiment 1 difference lies in：
Mixture A is put into pot furnace in the step (2) and is heated.
Embodiment 10
Embodiment 10 and embodiment 1 difference lies in：Annealing includes such as the next stage in the step (4)：
(a) stone C is warming up to 520 DEG C by the heating period；
(b) temperature of holding stage, holding stage is 490 DEG C, keeps the temperature 24 hours；
(c) slow cooling stage, slow cooling stage are cooled to the strain point of glass with the cooling rate of 10 DEG C/min；
(d) rapid cooling stage, rapid cooling stage are cooled to room temperature with the cooling rate of 20 DEG C/min from the strain point of glass.
Further, the heating period in the step (a) is warming up to 520 DEG C with the heating rate of 25 DEG C/min.
Embodiment 11
Embodiment 11 and embodiment 1 difference lies in：Annealing includes such as the next stage in the step (4)：
(a) stone C is warming up to 530 DEG C by the heating period；
(b) temperature of holding stage, holding stage is 490 DEG C, keeps the temperature 24 hours；
(c) slow cooling stage, slow cooling stage are cooled to the strain point of glass with the cooling rate of 10 DEG C/min；
(d) rapid cooling stage, rapid cooling stage are cooled to room temperature with the cooling rate of 20 DEG C/min from the strain point of glass.
Further, the heating period in the step (a) is warming up to 520 DEG C with the heating rate of 20 DEG C/min.
Embodiment 12
Embodiment 12 and embodiment 1 difference lies in：Annealing includes such as the next stage in the step (4)：
(a) stone C is warming up to 530 DEG C by the heating period；
(b) temperature of holding stage, holding stage is 510 DEG C, keeps the temperature 20 hours；
(c) slow cooling stage, slow cooling stage are cooled to the strain point of glass with the cooling rate of 15 DEG C/min；
(d) rapid cooling stage, rapid cooling stage are cooled to room temperature with the cooling rate of 40 DEG C/min from the strain point of glass.
Further, the heating period in the step (a) is warming up to 530 DEG C with the heating rate of 30 DEG C/min.
The artificial color changing gem of the present invention is under tungsten filament light irradiation, refractive index 1.63, under different light, presents different
Color, there is the distinct green color changeable effect of purple.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other manner,
Any obvious replacement is not departed under the premise of present inventive concept within protection scope of the present invention.
Claims (10)
1. artificial color changing gem, it is characterised in that：Include the raw material of following parts by weight：
2. artificial color changing gem described in claim 1, it is characterised in that：Include the raw material of following parts by weight：
3. the artificial color changing gem described in claim 2, it is characterised in that：Include the raw material of following parts by weight：
4. artificial color changing gem described in claim 1, it is characterised in that：The fluxing agent is B2O3、K2CO3And Na2CO3In
It is at least one.
5. artificial color changing gem described in claim 1, it is characterised in that：The fining agent is Sb2O3And CaF2In one kind or
Two kinds.
6. the preparation method of any artificial color changing gem in claim 1-5, it is characterised in that：Include the following steps：
(1) each raw material is mixed in proportion, is stirred evenly, obtain mixture A；
(2) mixture A is heated to 1350-1500 DEG C, keeps the temperature 19.5-20.5 hours so that mixture A is completely melt, is obtained
Molten mass B；
(3) molten mass B is cooled to 1200-1250 DEG C, heat preservation pours into mold after 3.5-4.5 hours, obtains stone C；
(4) stone C is annealed, obtains artificial color changing gem.
7. the preparation method of the artificial color changing gem described in claim 6, it is characterised in that：In the step (2), by mixture
A is put into electric melting furnace or pot furnace and is heated.
8. the preparation method of the artificial color changing gem described in claim 6, it is characterised in that：In the step (2), by mixture
A is heated to 1450 DEG C, is kept for 20 hours so that mixture A is completely melt, obtains molten mass B, in the step (3), will melt
Body B be cooled to 1250 DEG C keep 4 hours after pour into mold, obtain stone C.
9. the preparation method of the artificial color changing gem described in claim 6, it is characterised in that：It anneals in the step (4) and includes
Such as the next stage：
(a) stone C is warming up to 500-530 DEG C by the heating period；
(b) temperature of holding stage, holding stage is 480-510 DEG C, keeps the temperature 20-24 hours；
(c) slow cooling stage, slow cooling stage are cooled to the strain point of glass with the cooling rate of 5-15 DEG C/min；
(d) rapid cooling stage, rapid cooling stage are cooled to room temperature with the cooling rate of 20-40 DEG C/min from the strain point of glass.
10. the preparation method of the artificial color changing gem described in claim 9, it is characterised in that：Heating rank in the step (a)
Section is warming up to 500-530 DEG C with the heating rate of 20-30 DEG C/min.
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| CN109516677A (en) * | 2018-10-31 | 2019-03-26 | 成都鑫扬锦睿合成材料有限公司 | A kind of synthetic cut stone cylinder moulding process |
| CN109576790A (en) * | 2018-10-31 | 2019-04-05 | 成都鑫扬锦睿合成材料有限公司 | A kind of synthetic cut stone circular cone moulding process |
| CN113816605A (en) * | 2021-09-01 | 2021-12-21 | 北京科技大学 | Imitated color sapphire glass and preparation method and application thereof |
| CN113816603A (en) * | 2021-09-01 | 2021-12-21 | 北京科技大学 | Jewel-imitated color-changing glass with excellent performance and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109516677A (en) * | 2018-10-31 | 2019-03-26 | 成都鑫扬锦睿合成材料有限公司 | A kind of synthetic cut stone cylinder moulding process |
| CN109576790A (en) * | 2018-10-31 | 2019-04-05 | 成都鑫扬锦睿合成材料有限公司 | A kind of synthetic cut stone circular cone moulding process |
| CN113816605A (en) * | 2021-09-01 | 2021-12-21 | 北京科技大学 | Imitated color sapphire glass and preparation method and application thereof |
| CN113816603A (en) * | 2021-09-01 | 2021-12-21 | 北京科技大学 | Jewel-imitated color-changing glass with excellent performance and preparation method and application thereof |
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Inventor after: Guan Shanyue Inventor after: Xiong Shengrong Inventor after: Hou Changhong Inventor before: Guan Shanyue Inventor before: Xiong Shengrong Inventor before: Hou Changhong |