CN105948668B - A kind of lightweight concrete for 3D printing and preparation method and application - Google Patents
A kind of lightweight concrete for 3D printing and preparation method and application Download PDFInfo
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- CN105948668B CN105948668B CN201610458374.7A CN201610458374A CN105948668B CN 105948668 B CN105948668 B CN 105948668B CN 201610458374 A CN201610458374 A CN 201610458374A CN 105948668 B CN105948668 B CN 105948668B
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Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/06—Aluminous cements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/40—Porous or lightweight materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/30—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values
- C04B2201/32—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values for the thermal conductivity, e.g. K-factors
Abstract
The present invention provides a kind of lightweight concrete for 3D printing and preparation method and application, and the lightweight concrete includes the raw material of following parts by weight：6 12 parts of the quick hardening sulphoaluminate cement of 100 parts of 52.5R Portland cements, strength grade not less than 42.5,7 10 parts of flyash, 100 250 parts of composite inert light filler, 1.2 ~ 6.5 parts of polypropylene fibre, 0.06 ~ 0.2 part of viscosity modifier, 0.5 1.5 parts of soft readjustment agent, 25 40 parts of water.The material own wt of the present invention significantly reduces 25% 40% relative to conventional concrete material, greatly reduce print procedure pressure distortion of the material to lower floor at the middle and upper levels, the disposable number of plies continuously printed can further be lifted, shorten construction duration, in addition, this material itself also has certain heat preservation and insulation so that lightweight concrete of the present invention is applied to more energy-conserving and environment-protective during building field.
Description
Technical field
The present invention relates to building material field, more particularly to a kind of lightweight concrete for 3D printing and its preparation side
Method and application.
Background technology
3D printing is a kind of advanced Digitized manufacturing mode, also known as " increasing material manufacturing ", different from traditional manufacture method,
This technology only needs that threedimensional model is passed through into series of algorithms and software processing in a computer, it is possible to directly successively to tire out
The mode of product material produces entity, without proembryo and mould, simplifies the fabrication schedule of product, has saved manpower, improve
Production efficiency.
3D printing building mainly carries out 3D modeling by computer, using the software program set, is controlled by machinery
System, the concrete mix prepared is extruded into layering printing by nozzle, is successively formed by stacking, without mould during building is molded
Tool support, this requires concrete mix in the presence of deadweight and dynamic loading is born, indeformable, rapid condensation and can have
Good adhesive property, traditional concrete material can not substantially meet the performance requirement of 3D printing structure material, urgently
It is to be modified.
The content of the invention
In view of the above the shortcomings that prior art, it is an object of the invention to provide a kind of lightweight for 3D printing to mix
Solidifying soil and preparation method and application, for solve in the prior art concrete material bad adhesion, it is yielding, be not suitable for 3D
The problems such as printing.
In order to achieve the above objects and other related objects, first aspect present invention provides a kind of lightweight for 3D printing and mixed
Solidifying soil, include the raw material of following parts by weight：100 parts of 52.5R Portland cements, strength grade are not less than 42.5 fast hard sulphur
Aluminate cement 6-12 parts, flyash 7-10 parts, composite inert light filler 100-250 parts, polypropylene fibre 1.2-6.5
Part, viscosity modifier 0.06-0.2 parts, soft readjustment agent 0.5-1.5 parts, water 25-40 parts.
Further, the raw material of the composite inert light filler and its weight ratio are middle sand：Pottery sand：Glass bead：
Granular polystyrene=(20-40)：(40-80)：(8-16)：(2-5).Pottery sand therein includes but is not limited to the pottery sand of mud firing,
The own wt 25%-40% of concrete material can be significantly reduced using pottery sand, glass bead and granular polystyrene, so as to
Reducing print procedure, material to lower floor's pressure distortion, and can make concrete material have the effect of heat-insulation and heat-preservation at the middle and upper levels.
Further, the particle diameter of the pottery sand is less than 5mm.
Further, the length of the polypropylene fibre is 20-35mm.
Further, the viscosity modifier is maltodextrin, non-ionic polyacrylamide, welan gum, hydroxypropyl first
One or more combination in base cellulose ether.The addition of viscosity modifier mainly adjusts the thixotropy of material, i.e., one touches i.e.
The property of change.So that material denseness when by shearing force diminishes, there is stronger plasticity；When shearing force stops
Wait material denseness and become big, lose plasticity.Wherein, the molecular weight of non-ionic polyacrylamide is preferably 8,000,000 to 15,000,000.
Further, the soft readjustment agent is allyl ether series polymer or acrylic polymer, such polymer
It is soluble in water for powdery, it is specifically as follows polyethylene glycol mono allyl ether, polymethyl methacrylate etc..Soft readjustment agent has
There is scattered and interlayer lubrication so that material is overall finer and smoother, continuous, is advantageous to the continuity of print procedure, to ensure
Be not in the situation of fracture so that the product appearance printed is more attractive in appearance.
Second aspect of the present invention provides the above-mentioned lightweight concrete preparation method for 3D printing, comprises the following steps：
S1, by formula ratio each raw material of composite inert light filler is mixed, stir, composite inert lightweight is made
Inserts, it is standby.
S2, by formula ratio 52.5R is led into portland cement, quick hardening sulphoaluminate cement, flyash, polypropylene fibre, viscous
Conditioning agent, soft readjustment agent mixing are spent, is stirred, mixture is made, it is standby.
S3, the composite inert light filler as made from formula ratio by step S1 are added in mixture made from step S2,
Stir, powder is made, it is standby.
S4, the powder as made from formula ratio by step S3 mix with water, stir and evenly mix, are made for building structure 3D printing
Lightweight concrete.
Further, in the step S4, when being stirred to the mixture of powder and water, mixing speed is 100 ± 5r/
min。
Further, in the step S4, when being stirred to the mixture of powder and water, mixing time 1-2min.
Third aspect present invention provides the above-mentioned application for the lightweight concrete of 3D printing in 3D printing.It is above-mentioned to be used for
The lightweight concrete of 3D printing can be used for the printing of polymorphic structure, solve this hardly possible of profiled template in conventional casting concrete
Topic.Secondly, the present invention is short for the presetting period of the lightweight concrete of 3D printing, can complete to print quickly, can be significantly
Shorten the duration.Finally, this lightweight concrete carries heat insulating effect, belongs to environmentally friendly material.
As described above, lightweight concrete for 3D printing of the present invention and preparation method and application, has with following
Beneficial effect：Concrete gravity of the present invention is lighter, and sand, pottery sand, glass bead are as light filler in, in same volume
Under the conditions of, material own wt of the invention significantly reduces 25%-40% relative to conventional concrete material, greatly reduces and beats
Pressure distortion of the upper layer of material to lower floor during print so that the structure of printing is apparent more uniformly attractive in appearance, and can enter one
The disposable number of plies continuously printed of step lifting, shortens construction duration, can be that the intellectuality for quickly realizing industrialized production building is done
Support, in addition, this material itself also has certain heat preservation and insulation so that lightweight concrete of the present invention is applied to building and led
More energy-conserving and environment-protective during domain.
Embodiment
Illustrate embodiments of the present invention below by way of specific instantiation, those skilled in the art can be by this specification
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also pass through specific realities different in addition
The mode of applying is embodied or practiced, the various details in this specification can also be based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under the spirit of the present invention.
In following embodiment, quick hardening sulphoaluminate cement meets professional standard GB 20472-2006《Aluminium sulfate water
Mud》；Flyash meets standard GB/T 1596-2005《For the flyash in cement and concrete》；Middle sand meets standard GB/
T14684-2011《Construction sand》；Pottery sand meets standard GB T 17431.1-2010《Light-weight aggregate and its test method the 1st
Point：Light-weight aggregate》, following embodiment use mud fire pottery sand；Glass bead meets standard JCT 1042-2007《Expansion
Glass bead》；Granular polystyrene meets standard JG158-2004《Glue powder polyphenyl granule exterior wall outer heat preservation system》.
Embodiment 1
A kind of lightweight concrete for 3D printing, include the raw material of following parts by weight：52.5R Portland cements
100 parts, 11 parts of 42.5 quick hardening sulphoaluminate cement, 7 parts of flyash, 150 parts of composite inert light filler, length be 20mm
1.2 parts of polypropylene fibre, 0.12 part of viscosity modifier, 0.5 part of soft readjustment agent, 40 parts of water.
Raw material and its weight ratio of composite inert light filler are middle sand：Particle diameter is less than 5mm pottery sand：Glass bead：
Granular polystyrene=20：70：10：2.Viscosity modifier is maltodextrin, and soft readjustment agent is polyethylene glycol mono allyl ether.
The preparation method of the above-mentioned lightweight concrete for 3D printing comprises the following steps：
S1, by formula ratio will middle sand, particle diameter less than being mixed in 5mm pottery sand, glass bead, granular polystyrene input mixer
Close, stir, composite inert light filler is made, it is standby.
S2,52.5R is led into portland cement, quick hardening sulphoaluminate cement, flyash, length by formula ratio is the poly- of 20mm
Tacryl, viscosity modifier, soft readjustment agent input stirrer for mixing, stir, mixture are made, standby.
S3, the composite inert light filler as made from formula ratio by step S1 are added in mixture made from step S2,
Stir, powder is made, it is standby.
S4, the powder as made from formula ratio by step S3 mix with water, are quickly stirred with 100 ± 5r/min mixing speed
1min, mix, the lightweight concrete for building structure 3D printing is made, you can as the ink of 3D printer, carry out 3D and beat
Print.
Embodiment 2
A kind of lightweight concrete for 3D printing, include the raw material of following parts by weight：52.5R Portland cements
100 parts, 9 parts of 42.5 quick hardening sulphoaluminate cement, 8 parts of flyash, 120 parts of composite inert light filler, length be 30mm
1.2 parts of polypropylene fibre, 0.1 part of viscosity modifier, 1 part of soft readjustment agent, 30 parts of water.
Raw material and its weight ratio of composite inert light filler are middle sand：Particle diameter is less than 5mm pottery sand：Glass bead：
Granular polystyrene=20：70：10：4.Viscosity modifier is welan gum, and soft readjustment agent is polymethyl methacrylate.
The preparation method of the above-mentioned lightweight concrete for 3D printing comprises the following steps：
S1, by formula ratio will middle sand, particle diameter less than being mixed in 5mm pottery sand, glass bead, granular polystyrene input mixer
Close, stir, composite inert light filler is made, it is standby.
S2, by formula ratio 52.5R is led into portland cement, 42.5 quick hardening sulphoaluminate cements, flyash, length 20mm
Polypropylene fibre, viscosity modifier, soft readjustment agent input stirrer for mixing, stir, be made mixture, it is standby.
S3, the composite inert light filler as made from formula ratio by step S1 are added in mixture made from step S2,
Stir, powder is made, it is standby.
S4, the powder as made from formula ratio by step S3 mix with water, are quickly stirred with 100 ± 5r/min mixing speed
1.5min, mix, the lightweight concrete for building structure 3D printing is made, you can as the ink of 3D printer, carry out 3D
Printing.
Embodiment 3
A kind of lightweight concrete for 3D printing, include the raw material of following parts by weight：52.5R Portland cements
100 parts, 10 parts of 42.5 quick hardening sulphoaluminate cement, 9 parts of flyash, 180 parts of composite inert light filler, length be 30mm
1.2 parts of polypropylene fibre, 0.1 part of viscosity modifier, 0.8 part of soft readjustment agent, 35 parts of water.
Raw material and its weight ratio of composite inert light filler are middle sand：Particle diameter is less than 5mm pottery sand：Glass bead：
Granular polystyrene=35：62：15：2.5.Viscosity modifier is hydroxypropyl methyl cellulose ether, and soft readjustment agent is polyethyleneglycol
The mixture of allyl ether and polymethyl methacrylate.
The preparation method of the above-mentioned lightweight concrete for 3D printing comprises the following steps：
S1, by formula ratio will middle sand, particle diameter less than being mixed in 5mm pottery sand, glass bead, granular polystyrene input mixer
Close, stir, composite inert light filler is made, it is standby.
S2,52.5R is led into portland cement, quick hardening sulphoaluminate cement, flyash, length by formula ratio is the poly- of 30mm
Tacryl, viscosity modifier, soft readjustment agent input stirrer for mixing, stir, mixture are made, standby.
S3, the composite inert light filler as made from formula ratio by step S1 are added in mixture made from step S2,
Stir, powder is made, it is standby.
S4, the powder as made from formula ratio by step S3 mix with water, are quickly stirred with 100 ± 5r/min mixing speed
2min, mix, the lightweight concrete for building structure 3D printing is made, you can as the ink of 3D printer, carry out 3D and beat
Print.
Embodiment 4
A kind of lightweight concrete for 3D printing, include the raw material of following parts by weight：52.5R Portland cements
100 parts, 6 parts of 42.5 quick hardening sulphoaluminate cement, 10 parts of flyash, 160 parts of composite inert light filler, length be 20mm
6 parts of polypropylene fibre, 0.6 part of viscosity modifier, 1.4 parts of soft readjustment agent, 25 parts of water.
Raw material and its weight ratio of composite inert light filler are middle sand：Particle diameter is less than 5mm pottery sand：Glass bead：
Granular polystyrene=40：46：12：3.Viscosity modifier is maltodextrin, non-ionic polyacrylamide, hydroxypropyl methyl cellulose
The mixture of ether, soft readjustment agent are polyethylene glycol mono allyl ether.The molecular weight of non-ionic polyacrylamide be 8,000,000 to
15000000.
The preparation method of the above-mentioned lightweight concrete for 3D printing comprises the following steps：
S1, by formula ratio will middle sand, particle diameter less than being mixed in 5mm pottery sand, glass bead, granular polystyrene input mixer
Close, stir, composite inert light filler is made, it is standby.
S2,52.5R is led into portland cement, quick hardening sulphoaluminate cement, flyash, length by formula ratio is the poly- of 30mm
Tacryl, viscosity modifier, soft readjustment agent input stirrer for mixing, stir, mixture are made, standby.
S3, the composite inert light filler as made from formula ratio by step S1 are added in mixture made from step S2,
Stir, powder is made, it is standby.
S4, the powder as made from formula ratio by step S3 mix with water, are quickly stirred with 100 ± 5r/min mixing speed
2min, mix, the lightweight concrete for building structure 3D printing is made, you can as the ink of 3D printer, carry out 3D and beat
Print.
Performance detection is tested
Performance detection, its result such as following table are carried out to the lightweight concrete for being used for 3D printing made from embodiment 1-4：
Table 1 is used for the lightweight concrete performance detection table of 3D printing
| Project | Unit weight (kg/m3) | Thermal conductivity factor (W/ (mK)) | Presetting period (min) |
| Embodiment 1 | 1473 | 0.22 | 22 |
| Embodiment 2 | 1575 | 0.28 | 35 |
| Embodiment 3 | 1490 | 0.23 | 28 |
| Embodiment 4 | 1650 | 0.37 | 47 |
As can be seen from Table 1, unit weight≤1650kg/m of the lightweight concrete produced by the present invention for 3D printing3,
Thermal conductivity factor≤0.37W/ (mK), presetting period≤47min, the reduction of unit weight so that product has the characteristics of lightweight, simultaneously
Effectively solve in product print procedure, the problem of upper layer of material causes deformation of products to the pressure of lower floor, the reduction of thermal conductivity factor,
So that product has good insulation capacity, the shortening in presetting period, also effectively solve the problems, such as that product is easily deformed, show
Write the quality for improving product.
In summary, concrete gravity of the present invention is lighter, in sand, pottery sand, glass bead as light filler,
Under conditions of same volume, material own wt of the invention significantly reduces 25%-40% relative to conventional concrete material, greatly
Reducing print procedure greatly, material to the pressure distortion of lower floor, can further lift the disposable layer continuously printed at the middle and upper levels
Number, shorten construction duration, can be that the intellectuality for quickly realizing industrialized production building supports, in addition, this material itself also has
There is certain heat preservation and insulation so that building more energy-conserving and environment-protective.
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any ripe
Know the personage of this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete without departing from disclosed spirit and institute under technological thought such as
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (9)
1. a kind of lightweight concrete for 3D printing, it is characterised in that be made up of the raw material of following parts by weight：52.5R is common
The quick hardening sulphoaluminate cement 6-12 parts of 100 parts of portland cement, strength grade not less than 42.5, flyash 7-10 parts, answer
Close inertia light filler 100-250 parts, polypropylene fibre 1.2-6.5 parts, viscosity modifier 0.06-0.2 parts, soft readjustment
Agent 0.5-1.5 parts, water 25-40 parts；
The raw material and its weight ratio of the composite inert light filler are middle sand：Pottery sand：Glass bead：Granular polystyrene=（20-
40）：（40-80）：（8-16）：（2-5）.
2. the lightweight concrete according to claim 1 for 3D printing, it is characterised in that：The particle diameter of the pottery sand is less than
5mm。
3. the lightweight concrete according to claim 1 for 3D printing, it is characterised in that：The length of the polypropylene fibre
Spend for 20-35mm.
4. the lightweight concrete according to claim 1 for 3D printing, it is characterised in that：The viscosity modifier is wheat
One or more combination in bud dextrin, non-ionic polyacrylamide, welan gum, hydroxypropyl methyl cellulose ether.
5. the lightweight concrete according to claim 1 for 3D printing, it is characterised in that：The soft readjustment agent is alkene
Propyl group ether polymer or acrylic polymer.
6. the preparation method of the lightweight concrete for 3D printing according to claim any one of 1-5, it is characterised in that
Comprise the following steps：
S1, by formula ratio each raw material of composite inert light filler is mixed, stir, composite inert light filling is made
Material, it is standby；
S2, by formula ratio by 52.5R Portland cements, quick hardening sulphoaluminate cement, flyash, polypropylene fibre, viscosity
Conditioning agent, soft readjustment agent mixing, stir, and mixture is made, standby；
S3, the composite inert light filler as made from formula ratio by step S1 are added in mixture made from step S2, stirring
Uniformly, powder is made, it is standby；
S4, the powder as made from formula ratio by step S3 mix with water, stir and evenly mix, are made for the light of building structure 3D printing
Matter concrete.
7. the preparation method of the lightweight concrete according to claim 6 for 3D printing, it is characterised in that：The step
In S4, when being stirred to the mixture of powder and water, mixing speed is 100 ± 5r/min.
8. the preparation method of the lightweight concrete according to claim 6 for 3D printing, it is characterised in that：The step
In S4, when being stirred to the mixture of powder and water, mixing time 1-2min.
9. the application for the lightweight concrete of 3D printing in 3D printing according to claim any one of 1-5.
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| CN106495610A (en) * | 2016-10-26 | 2017-03-15 | 成都大学 | A kind of concrete for 3D printing |
| CN107311561B (en) * | 2017-06-22 | 2019-08-06 | 同济大学 | A kind of 3D printing cement-based material and preparation method thereof for underwater construction |
| CN107555895B (en) * | 2017-08-21 | 2020-04-17 | 南京理工大学 | Functional gradient and density gradient concrete material for 3D printing and preparation method thereof |
| CN108623268B (en) * | 2018-05-22 | 2021-02-19 | 中北大学 | Self-insulation bearing concrete based on 3D printing performance and preparation method thereof |
| CN108658549B (en) * | 2018-05-30 | 2021-04-02 | 贵州师范大学 | Green high-performance 3D printing concrete and preparation method thereof |
| CN108947577A (en) * | 2018-08-28 | 2018-12-07 | 张家口盛博建筑科技有限公司 | A kind of foamed cement and preparation method thereof, application |
| CN109721298B (en) * | 2019-02-27 | 2021-07-27 | 济南大学 | Red mud 3D printing alkali-activated cementing material and use method thereof |
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| CN110105029B (en) * | 2019-05-13 | 2020-09-11 | 中国十七冶集团有限公司 | Waterproof thermal insulation mortar for 3D printing building and preparation method and application thereof |
| CN111018448B (en) * | 2019-12-31 | 2021-02-19 | 浙江大学 | Anti-freezing concrete for 3D printing in low-temperature environment and construction method thereof |
| CN112299874A (en) * | 2020-10-29 | 2021-02-02 | 南京绿色增材智造研究院有限公司 | Light foamed concrete material for building 3D printing, preparation process and application |
| CN112551968B (en) * | 2020-11-06 | 2022-01-04 | 浙江大学 | Desert sand-ferrochromium slag 3D printing concrete material and construction method thereof |
| CN113372075B (en) * | 2021-07-02 | 2022-12-16 | 桂林理工大学 | Concrete based on 3D printing, preparation method thereof and 3D printing column template |
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Address after: The 7th floor, 8th floor and 9th floor, 1596 Jinkai Avenue, North District, Chongqing Economic Development Zone 401120 Patentee after: CHONGQING CONSTRUCTION ENGINEERING BUILDING MATERIALS & LOGISTICS Co.,Ltd. Patentee after: CHONGQING CONSTRUCTION ENGINEERING GROUP Co.,Ltd. Address before: 401122, No. 1666, Golden Road, North New District, Chongqing, attached No. 2 Patentee before: CHONGQING CONSTRUCTION ENGINEERING NEW BUILDING MATERIALS Co.,Ltd. Patentee before: CHONGQING CONSTRUCTION ENGINEERING GROUP Co.,Ltd. |
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