CN109944382A - A kind of self-heat conserving TRC combined wall and preparation method thereof - Google Patents

A kind of self-heat conserving TRC combined wall and preparation method thereof Download PDF

Info

Publication number
CN109944382A
CN109944382A CN201910257344.3A CN201910257344A CN109944382A CN 109944382 A CN109944382 A CN 109944382A CN 201910257344 A CN201910257344 A CN 201910257344A CN 109944382 A CN109944382 A CN 109944382A
Authority
CN
China
Prior art keywords
trc
self
heat conserving
concrete
combined wall
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201910257344.3A
Other languages
Chinese (zh)
Inventor
杨叶松
蔡东毅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China MCC17 Group Co Ltd
Original Assignee
China MCC17 Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China MCC17 Group Co Ltd filed Critical China MCC17 Group Co Ltd
Priority to CN201910257344.3A priority Critical patent/CN109944382A/en
Publication of CN109944382A publication Critical patent/CN109944382A/en
Pending legal-status Critical Current

Links

Landscapes

  • Finishing Walls (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention discloses a kind of self-heat conserving TRC combined walls and preparation method thereof, are related to building material technical field.Self-heat conserving TRC combined wall, including insulating layer, the two sides of the insulating layer are provided with structure sheaf, and the surface of the structure sheaf is provided with TRC thin plate made by fiber knitted net enhancing concrete.Self-heat conserving TRC combined wall and preparation method thereof, the composite wall body structure is light-weight, intensity is high, durability is good, thermal insulation property is superior, the energy-saving effect of Outer Protective Structure of Dwelling House can be effectively improved, guarantee thickness and weight that wall is reduced under the premise of wall panel intensity, improve combined wall overall stiffness, combined wall core material regenerates light aggregate concrete, reduce wall heating conduction, greatly improve the heat-insulated efficiency of wall thermal insulating, the precast concrete external wall panel prepared compared to traditional ordinary cement, with lightweight, it is high-strength, fire prevention, self-heat conserving, decoration, waterproof and the performances such as environmentally protective.

Description

A kind of self-heat conserving TRC combined wall and preparation method thereof
Technical field
The present invention relates to building material technical field, specially a kind of self-heat conserving TRC combined wall and preparation method thereof.
Background technique
It is a kind of novel height that fiber knitted net, which enhances concrete (Textile Reinforced Concrete, abbreviation TRC), Performance cement-base composite material, has obtained increasingly extensive concern in recent years, TRC have corrosion-resistant, light-weight, bearing capacity is high, The advantages that good toughness, component protective layer thickness need to only meet the anchoring requirement of fiber knitted net, be particularly suitable for thin-walled is made light The panel member of matter has broad application prospects in architectural exterior-protecting construction field.
Important component of the building enclosure (such as exterior wall, roofing, door and window, basement) as building structure, wherein wall Body accounts for the 70% of building enclosure, and the height of the thermal and insulating performance of the superiority and inferiority and building enclosure of building thermal environments is closely related, hair Exhibition high quality exterior wall composite thermal insulation wall is the important shortcut realized housing industrialization and promote energy saving building.
Normal concrete is generallyd use in existing combined wall as structure sheaf, central filler heat preserving and insulating material, as a result Cause wall weight big, the deficiencies of surface is easy crack, poor durability, thermal insulation material thermal coefficient is relatively high, influences energy conservation The reasons such as effect restrict the development of energy-saving wall.
Summary of the invention
(1) the technical issues of solving
In view of the deficiencies of the prior art, the present invention provides a kind of self-heat conserving TRC combined walls and preparation method thereof, solve Normal concrete is generallyd use as structure sheaf in existing combined wall, as a result central filler heat preserving and insulating material leads to wall The deficiencies of body weight is big, and surface is easy crack, poor durability, thermal insulation material thermal coefficient is relatively high, influences energy-saving effect etc. Reason restricts the problem of energy-saving wall development.
(2) technical solution
In order to achieve the above object, the present invention is achieved by the following technical programs: a kind of self-heat conserving TRC combined wall, Including insulating layer, the two sides of the insulating layer are provided with structure sheaf, and the surface of the structure sheaf is provided with fiber knitted net increasing TRC thin plate made by reinforced concrete.
Preferably, the structure sheaf inner surface reserves groove, and groove is coated with magnesium phosphate water at zigzag, and in groove Mud.
Preferably, the insulating layer is made of regeneration light aggregate concrete, and regeneration light aggregate concrete is by regenerating light collection Material, glass bead, haydite etc. are made, and coagulation compression strength is greater than 14MPa, and dry density is less than 1000kg/m3, and thermal coefficient is small In 0.05w/ (m.k), water absorption rate 7-10%, coefficient of softing is greater than 0.83, and the insulation layer thickness is 50-100mm.
Preferably, the TRC thin plate is by basalt fibre net, sand, portland cement, the powder that partial size is 0.6mm-1.2mm Coal ash water-reducing agent and water are formulated for primary raw material, and the TRC lamella thickness is 15-50mm.
A kind of preparation method of self-heat conserving TRC combined wall, method includes the following steps:
S1, preparation TRC thin plate: fiber knitted net enhancing concrete is placed in corresponding mould, conserves 7 at room temperature Demoulding obtains TRC thin plate after it, and TRC thin plate preparation process is as follows:
1,480:260:1200~1400:3.0 in mass ratio~4.0:150~170 weigh respectively cement, water, fine aggregate, Water-reducing agent and flyash, 30~60s of uniform stirring, after fiber knitted net enhancing concrete needed for original concrete;
2, basalt fibre mesh grid is handled: basalt fibre net is carried out using epoxy resin to soak stagnant processing, will be located The fiber knitted net managed solidifies for 24 hours in the environment of being placed on well-ventilated;
3, gained original concrete points 3 layers are poured and in element mold, has often been poured institute after the original concrete of upper layer Basalt fibre mesh grid is layed in its surface and pours underlying substrate concrete again, become TRC thin plate after maintenance molding;
It is S2, two pieces of TRC thin plates are relatively fixed, three of them side is sealed using aluminum alloy mould plate, and in structure sheaf After magnesium phosphate cement is smeared on surface, regeneration light aggregate concrete is poured from unencapsulated side, regenerates light-weight aggregate coagulation Native preparation process is as follows:
1,300:(150~180 in mass ratio): (60~70): (200~300): (100~180): (0.1~0.2) point Also known as take cement, water, slag, haydite, glass bead and coagulant;
2,60~90s of stirring is mixed in cement, water, slag, haydite, glass bead and coagulant can be obtained foam Concrete;
S3, dismounting aluminum alloy mould plate obtain self-heat conserving TRC combined wall after conserving 28 days in standard curing room.
Preferably, in step sl, silicic acid salt slurry of the strength of cement marked as 52.5, fine aggregate are that partial size is less than 1.2mm Quartz sand, water-reducing agent is the polycarboxylate water-reducer that water-reducing rate is 40%~50%, and flyash is second-level ash.
Preferably, in step sl, basalt fibre mesh grid is having a size of for 10mm × 10mm
Preferably, in step s 2, it is 42.5 ordinary portland cements that cement, which is strength grade, and water-reducing agent subtracts for polycarboxylic acids Aqua, hydrogen peroxide content are 30wt%~50wt%, and coagulant is commercially pure Li2CO3
(3) beneficial effect
The present invention provides a kind of self-heat conserving TRC combined walls and preparation method thereof.Have following the utility model has the advantages that the self-insurance Warm TRC combined wall and preparation method thereof, the composite wall body structure is light-weight, intensity is high, durability is good, and thermal insulation property is superior, The energy-saving effect of Outer Protective Structure of Dwelling House can be effectively improved, guarantees the thickness for reducing wall under the premise of wall panel intensity And weight, combined wall overall stiffness is improved, combined wall core material regenerates light aggregate concrete, reduces wall thermal conductivity Can, the heat-insulated efficiency of wall thermal insulating is greatly improved, compared to precast concrete external wall panel prepared by traditional ordinary cement, is had light Matter, high-strength, fire prevention, self-heat conserving, decoration, waterproof and the performances such as environmentally protective.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of self-heat conserving TRC combined wall of the present invention.
In figure: 1, structure sheaf;2, insulating layer;3, TRC thin plate.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other Embodiment shall fall within the protection scope of the present invention.
Referring to Fig. 1, the present invention provides a kind of technical solution: a kind of self-heat conserving TRC combined wall, including insulating layer 2 are protected Warm layer 2 is made of regeneration light aggregate concrete, and regeneration light aggregate concrete is made by regeneration light-weight aggregate, glass bead, haydite etc. At coagulation compression strength is greater than 14MPa, and dry density is less than 1000kg/m3, and thermal coefficient is less than 0.05w/ (m.k), water absorption rate For 7-10%, coefficient of softing is greater than 0.83, and insulation layer thickness 50-100mm, the two sides of insulating layer 2 are provided with structure sheaf 1, 1 inner surface of structure sheaf reserves groove, and groove is coated with magnesium phosphate cement at zigzag in groove, the surface setting of structure sheaf 1 There is TRC thin plate 3 made by fiber knitted net enhancing concrete, TRC thin plate 3 is by basalt fibre net, partial size 0.6mm- Sand, portland cement, flyash water-reducing agent and the water of 1.2mm is formulated for primary raw material, and TRC thin plate 3 is with a thickness of 15- 50mm。
A kind of preparation method of self-heat conserving TRC combined wall, method includes the following steps:
S1, preparation TRC thin plate 3: fiber knitted net enhancing concrete is placed in corresponding mould, is conserved at room temperature Demoulding obtains TRC thin plate 3 after 7 days, and 3 preparation process of TRC thin plate is as follows:
1,480:260:1200~1400:3.0 in mass ratio~4.0:150~170 weigh respectively cement, water, fine aggregate, Water-reducing agent and flyash, 30~60s of uniform stirring, after fiber knitted net enhancing concrete needed for original concrete (cement is strong Spend silicic acid salt slurry marked as 52.5, fine aggregate is the quartz sand that partial size is less than 1.2mm, water-reducing agent be water-reducing rate be 40%~ 50% polycarboxylate water-reducer, flyash are second-level ash);
2, basalt fibre mesh grid is handled: basalt fibre net is carried out using epoxy resin to soak stagnant processing, will be located The fiber knitted net managed solidified within 24 hours in the environment of being placed on well-ventilated (basalt fibre mesh grid having a size of for 10mm×10mm);
3, gained original concrete points 3 layers are poured and in element mold, has often been poured institute after the original concrete of upper layer Basalt fibre mesh grid is layed in its surface and pours underlying substrate concrete again, become TRC thin plate 3 after maintenance molding;
It is S2, two pieces of TRC thin plates 3 are relatively fixed, three of them side is sealed using aluminum alloy mould plate, and in structure sheaf After magnesium phosphate cement is smeared on surface, regeneration light aggregate concrete is poured from unencapsulated side, regenerates light-weight aggregate coagulation Native preparation process is as follows:
1,300:(150~180 in mass ratio): (60~70): (200~300): (100~180): (0.1~0.2) point Also known as take cement, water, slag, haydite, glass bead and coagulant;
2,60~90s of stirring is mixed in cement, water, slag, haydite, glass bead and coagulant can be obtained foam (cement is that strength grade is 42.5 ordinary portland cements to concrete, and water-reducing agent is polycarboxylate water-reducer, and hydrogen peroxide content is 30wt%~50wt%, coagulant are commercially pure Li2CO3);
S3, dismounting aluminum alloy mould plate obtain self-heat conserving TRC combined wall after conserving 28 days in standard curing room.
In conclusion self-heat conserving TRC combined wall and preparation method thereof, the composite wall body structure is light-weight, intensity is high, Durability is good, and thermal insulation property is superior, can effectively improve the energy-saving effect of Outer Protective Structure of Dwelling House, guarantees wall panel intensity Under the premise of reduce the thickness and weight of wall, improve combined wall overall stiffness, combined wall core material regenerates light-weight aggregate Concrete reduces wall heating conduction, greatly improves the heat-insulated efficiency of wall thermal insulating, pre- compared to prepared by traditional ordinary cement Concrete external wall panel processed has lightweight, high-strength, fire prevention, self-heat conserving, decoration, waterproof and the performances such as environmentally protective.
It should be noted that, in this document, relational terms such as first and second and the like are used merely to a reality Body or operation are distinguished with another entity or operation, are deposited without necessarily requiring or implying between these entities or operation In any actual relationship or order or sequence.Moreover, the terms "include", "comprise" or its any other variant are intended to Non-exclusive inclusion, so that the process, method, article or equipment including a series of elements is not only wanted including those Element, but also including other elements that are not explicitly listed, or further include for this process, method, article or equipment Intrinsic element.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding And modification, the scope of the present invention is defined by the appended.

Claims (8)

1. a kind of self-heat conserving TRC combined wall, it is characterised in that: including insulating layer (2), the two sides of the insulating layer (2) are all provided with It is equipped with structure sheaf (1), the surface of the structure sheaf (1) is provided with TRC thin plate made by fiber knitted net enhancing concrete (3)。
2. a kind of self-heat conserving TRC combined wall according to claim 1, it is characterised in that: structure sheaf (1) inner surface Reserved groove, groove are coated with magnesium phosphate cement at zigzag in groove.
3. a kind of self-heat conserving TRC combined wall according to claim 1, it is characterised in that: the insulating layer (2) is using again Raw light aggregate concrete is made, and regeneration light aggregate concrete is made of regeneration light-weight aggregate, glass bead, haydite etc., and coagulation is anti- Compressive Strength is greater than 14MPa, and dry density is less than 1000kg/m3, and thermal coefficient is less than 0.05w/ (m.k), and water absorption rate 7-10% is soft Change coefficient and be greater than 0.83, the insulation layer thickness is 50-100mm.
4. a kind of self-heat conserving TRC combined wall according to claim 1, it is characterised in that: the TRC thin plate (3) is by profound Sand, portland cement, flyash water-reducing agent and the water that military rock web, partial size are 0.6mm-1.2mm be primary raw material prepare and At the TRC thin plate (3) is with a thickness of 15-50mm.
5. a kind of preparation method of self-heat conserving TRC combined wall, it is characterised in that: method includes the following steps:
S1, preparation TRC thin plate (3): fiber knitted net enhancing concrete is placed in corresponding mould, conserves 7 at room temperature Demoulding obtains TRC thin plate (3) after it, and TRC thin plate (3) preparation process is as follows:
1,480:260:1200~1400:3.0 in mass ratio~4.0:150~170 weigh cement, water, fine aggregate, diminishing respectively Agent and flyash, 30~60s of uniform stirring, after fiber knitted net enhancing concrete needed for original concrete;
2, basalt fibre mesh grid is handled: basalt fibre net is carried out using epoxy resin to soak stagnant processing, will be handled well Fiber knitted net be placed on well-ventilated in the environment of solidify within 24 hours;
3, by gained original concrete points 3 layers pour in element mold, often poured it is gained is profound after the original concrete of upper layer Military rock fiber knitted net is layed in its surface and pours underlying substrate concrete again, becomes TRC thin plate (3) after maintenance molding;
It is S2, two pieces of TRC thin plates (3) are relatively fixed, three of them side is sealed using aluminum alloy mould plate, and the table in structure sheaf After magnesium phosphate cement is smeared in face, regeneration light aggregate concrete is poured from unencapsulated side, regenerates light aggregate concrete Preparation process is as follows:
1,300:(150~180 in mass ratio): (60~70): (200~300): (100~180): (0.1~0.2) claims respectively Take cement, water, slag, haydite, glass bead and coagulant;
2,60~90s of stirring is mixed in cement, water, slag, haydite, glass bead and coagulant can be obtained foam coagulation Soil;
S3, dismounting aluminum alloy mould plate obtain self-heat conserving TRC combined wall after conserving 28 days in standard curing room.
6. a kind of preparation method of self-heat conserving TRC combined wall according to claim 5, it is characterised in that: in step S1 In, silicic acid salt slurry of the strength of cement marked as 52.5, fine aggregate is the quartz sand that partial size is less than 1.2mm, and water-reducing agent is water-reducing rate For 40%~50% polycarboxylate water-reducer, flyash is second-level ash.
7. a kind of preparation method of self-heat conserving TRC combined wall according to claim 5, it is characterised in that: in step S1 In, basalt fibre mesh grid is having a size of for 10mm × 10mm.
8. a kind of preparation method of self-heat conserving TRC combined wall according to claim 5, it is characterised in that: in step S2 In, cement is that strength grade is 42.5 ordinary portland cements, and water-reducing agent is polycarboxylate water-reducer, hydrogen peroxide content 30wt% ~50wt%, coagulant are commercially pure Li2CO3
CN201910257344.3A 2019-04-01 2019-04-01 A kind of self-heat conserving TRC combined wall and preparation method thereof Pending CN109944382A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910257344.3A CN109944382A (en) 2019-04-01 2019-04-01 A kind of self-heat conserving TRC combined wall and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910257344.3A CN109944382A (en) 2019-04-01 2019-04-01 A kind of self-heat conserving TRC combined wall and preparation method thereof

Publications (1)

Publication Number Publication Date
CN109944382A true CN109944382A (en) 2019-06-28

Family

ID=67012436

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910257344.3A Pending CN109944382A (en) 2019-04-01 2019-04-01 A kind of self-heat conserving TRC combined wall and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109944382A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111606714A (en) * 2020-06-03 2020-09-01 陈杰明 Environment-friendly anticorrosive building ceramic material and preparation method thereof
CN111809790A (en) * 2020-06-19 2020-10-23 滁州职业技术学院 TRC recycled aggregate concrete block and processing method thereof
CN111844362A (en) * 2020-06-23 2020-10-30 中建西部建设建材科学研究院有限公司 Composite heat-insulating wallboard and preparation method thereof
CN112549672A (en) * 2020-12-02 2021-03-26 湖南大学 Protection and heat preservation integrated composite wallboard and manufacturing method thereof
CN114055597A (en) * 2021-11-22 2022-02-18 中国矿业大学 Fiber woven mesh reinforced ECC sandwich heat-insulation composite wallboard and manufacturing method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1563557A (en) * 2004-04-05 2005-01-12 华南理工大学 Fiber sheet plate and usage
CN1831270A (en) * 2005-10-28 2006-09-13 广州市壁神新型建材有限公司 Light compound side fascia and its manufacturing method
CN102733536A (en) * 2012-07-06 2012-10-17 杭州固华复合材料科技有限公司 Novel composite insulating thin-wall external wall board and manufacturing method thereof
US20150118393A1 (en) * 2012-09-25 2015-04-30 Romeo Ilarian Ciuperca High performance, lightweight precast composite insulated concrete panels and high energy-efficient structures and methods of making same
CN107043237A (en) * 2017-04-25 2017-08-15 天津和兴源建筑工程有限公司 A kind of self-insulating concrete and preparation method thereof
US20180171641A1 (en) * 2016-12-15 2018-06-21 Dryvit Systems, Inc. Building material cladding components and methods

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1563557A (en) * 2004-04-05 2005-01-12 华南理工大学 Fiber sheet plate and usage
CN1831270A (en) * 2005-10-28 2006-09-13 广州市壁神新型建材有限公司 Light compound side fascia and its manufacturing method
CN102733536A (en) * 2012-07-06 2012-10-17 杭州固华复合材料科技有限公司 Novel composite insulating thin-wall external wall board and manufacturing method thereof
US20150118393A1 (en) * 2012-09-25 2015-04-30 Romeo Ilarian Ciuperca High performance, lightweight precast composite insulated concrete panels and high energy-efficient structures and methods of making same
US20180171641A1 (en) * 2016-12-15 2018-06-21 Dryvit Systems, Inc. Building material cladding components and methods
CN107043237A (en) * 2017-04-25 2017-08-15 天津和兴源建筑工程有限公司 A kind of self-insulating concrete and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111606714A (en) * 2020-06-03 2020-09-01 陈杰明 Environment-friendly anticorrosive building ceramic material and preparation method thereof
CN111809790A (en) * 2020-06-19 2020-10-23 滁州职业技术学院 TRC recycled aggregate concrete block and processing method thereof
CN111844362A (en) * 2020-06-23 2020-10-30 中建西部建设建材科学研究院有限公司 Composite heat-insulating wallboard and preparation method thereof
CN112549672A (en) * 2020-12-02 2021-03-26 湖南大学 Protection and heat preservation integrated composite wallboard and manufacturing method thereof
CN114055597A (en) * 2021-11-22 2022-02-18 中国矿业大学 Fiber woven mesh reinforced ECC sandwich heat-insulation composite wallboard and manufacturing method thereof

Similar Documents

Publication Publication Date Title
CN109944382A (en) A kind of self-heat conserving TRC combined wall and preparation method thereof
CN103410232A (en) Outer-wall external thermal-insulating system utilizing inorganic compound thermal-insulating board
CN1425628A (en) Light composite heat insulation block material
CN104860714A (en) Single-component lightweight sound-insulating heat-preserving mortar material and construction method thereof
CN102020449B (en) Composite silicate heat preservation mortar
CN203487643U (en) Exterior wall outer heat preservation system with inorganic composite heat preservation plate
CN105089201A (en) Fibre concrete composite vacuum insulation wall panel and production method thereof
CN114055597A (en) Fiber woven mesh reinforced ECC sandwich heat-insulation composite wallboard and manufacturing method thereof
CN201495627U (en) Gypsum-concrete mixed energy saving housing construction structure
CN108329002A (en) A kind of light foam geo-polymer composite insulation boards and preparation method thereof
CN210086632U (en) Homogeneous passive room building module with high-strength heat-preservation embedded pendant
CN101775861B (en) Cast in situs construction method for light heat-insulation integral wall of energy-saving construction house and light heat-insulation wall material
CN101708979A (en) High-performance aerated concrete plastering mortar
CN1274927C (en) Novel anti-crack internal insulation wall and construction technique
CN114592643A (en) Steel bar truss and surface layer reinforced aluminum alloy plate facing foamed ceramic composite wallboard and manufacturing method thereof
CN114197773A (en) Vitrified micro bubble heat preservation and insulation building wall and construction process
CN204163228U (en) Air-entrained concrete building block heat preservation composite wall
CN203334530U (en) Novel cement foam composite insulation board
CN109881772A (en) A kind of no beam column plate-type house structural system
CN207812706U (en) A kind of structure-integrated template system of AS composite phase-changes insulation and decoration
CN114000653B (en) High-ductility green energy-saving anti-drop double-layer heat-insulation building structure and construction method thereof
CN109987915A (en) The preparation method of assembled magnesium cement foam concrete composite sand wiched wall board
CN1232711C (en) Light heat-insulating wall block
CN104831823B (en) Compound heat preservation die plate
CN216305040U (en) Bridge cut-off heat preservation light composite wall

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20190628

RJ01 Rejection of invention patent application after publication