KR100757375B1 - making method of the environmental-friendly concrete block - Google Patents

making method of the environmental-friendly concrete block Download PDF

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KR100757375B1
KR100757375B1 KR1020060063721A KR20060063721A KR100757375B1 KR 100757375 B1 KR100757375 B1 KR 100757375B1 KR 1020060063721 A KR1020060063721 A KR 1020060063721A KR 20060063721 A KR20060063721 A KR 20060063721A KR 100757375 B1 KR100757375 B1 KR 100757375B1
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concrete block
microorganisms
diffuser
cement
composition
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KR1020060063721A
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Korean (ko)
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KR20070023513A (en
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서경진
박유석
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(주)대호콘크리트
주식회사 엠투원환경기연
서경진
박유석
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
    • B28B11/04—Apparatus or processes for treating or working the shaped or preshaped articles for coating or applying engobing layers
    • B28B11/06—Apparatus or processes for treating or working the shaped or preshaped articles for coating or applying engobing layers with powdered or granular material, e.g. sanding of shaped articles
    • 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
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F2003/001—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0001—Living organisms, e.g. microorganisms, or enzymes
    • 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
    • C04B2111/74—Underwater applications

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Revetment (AREA)

Abstract

본 발명은 친환경 콘크리트블록 제조방법에 관한 것으로서, 더욱 구체적으로는 통상적인 방법에 의해 포자화가 가능한 미생물을 포자화 한 다음 이를 분말화 하는 단계와; 상기 유포자 미생물 분말을 콘크리트블록 제조용 시멘트에 첨가하여 친환경 조성물을 만드는 단계에 의해 얻어진 조성물로 콘크리트블록을 제조할 수 있도록 함으로써 미생물의 급격한 유실이 방지되고, 또 정화기능도 보다 지속적으로 유지되는 콘크리트블록을 얻을 수 있도록 하고, 뿐만 아니라 수생식물의 생육에는 지장을 주지 않으면서 정화능력은 우수함은 물론 시멘트의 독성으로 부터 수생 동식물의 생태계를 보호할 수 있는 콘크리트블록을 얻을 수 있도록 한 것이다.The present invention relates to a method for manufacturing an environmentally friendly concrete block, and more specifically, spore-forming microorganisms capable of being sporadized by a conventional method and then powdering them; By adding the diffuser microbial powder to the cement for manufacturing concrete block to make the concrete block with the composition obtained by the step of making an environmentally friendly composition to prevent the rapid loss of microorganisms, and to further maintain the purification function In addition, it is possible to obtain a concrete block that can protect the ecosystem of aquatic plants and plants from the toxicity of cement as well as excellent purification ability without affecting the growth of aquatic plants.

콘크리트블록, 유포자, 미생물, 조성물, 정화 Concrete block, diffuser, microorganism, composition, purification

Description

친환경 콘크리트블록 제조방법{making method of the environmental-friendly concrete block}Making method of the environmental-friendly concrete block

도 1은 본 발명에 의해 제조되는 콘크리트블록 예시도1 is an exemplary view of a concrete block manufactured by the present invention

도 2는 도 1의 정면 예시도FIG. 2 is a front view of FIG. 1

도 3은 본 발명의 또 다른 예시도 이다.3 is another exemplary view of the present invention.

* 도면의 중요부분에 대한 부호의 설명 *Explanation of symbols on important parts of drawing

1 : 콘크리트블록 11 : 식생공간부1: concrete block 11: vegetation space

12 : 정화층12: Purification layer

본 발명은 본원 출원인이 선 출원한 특허출원 2005-0010886호(이하 '선 출원특허'라 함), 미생물을 이용하여 하수 및 폐수를 정화할 수 있도록 한 친환경 콘크리트블록을 개선하기 위해 발명한 것으로서, 이를 좀 더 구체적으로 설명하자면 미 생물의 개체를 적정 수준으로 유지할 수 있고 또 미생물의 유실도 쉽게 발생 되지 않는 콘크리트블록을 얻을 수 있도록 함으로써 정화기능이 우수함과 동시에 지속적으로 정화 능력을 발휘할 수 있는 콘크리트블록을 제공할 수 있도록 한 것이다.The present invention is a patent application 2005-0010886 (hereinafter referred to as "prior application patent") filed by the applicant of the present application, which was invented to improve the eco-friendly concrete block to clean the sewage and waste water using microorganisms, More specifically, the concrete block can maintain the microorganisms at an appropriate level and obtain concrete blocks that do not easily lose microorganisms. It would be to provide.

본원 출원인이 선 출원특허에서 제안한 콘크리트블록은 수용성 다당류가 첨가된 미생물을 콘크리트블록의 표면 전체에 도포하여 미생물막을 형성하고, 위 미생물막 외방의 탈리 현상 등을 억제하기 위하여 고형용액을 도포하여 고정막을 형성한 구조로 되어 있다.The concrete block proposed by the applicant in the prior application patent is applied to the entire surface of the concrete block to the microorganism to which the water-soluble polysaccharides are added to form a microbial membrane, and a solid solution is applied by applying a solid solution in order to suppress the detachment phenomenon of the outer microbial membrane. It has a formed structure.

그러나 이와 같은 콘크리트블록은 미생물막이 외부로 노출되어 있으므로 미생물이 정상적으로 번식하기 전에 이미 대부분의 미생물이 급격하게 유실되는 문제점이 있었고, 이를 방지하기 위하여 미생물막 외방에 고형용액을 도포하여 고정막을 형성하였지만 위 고정막은 미생물의 번식을 방해하지 않는 다공 형태로 되기 때문에 미생물의 유실을 적극적으로 막을 수 없음은 물론 이를 배제하더라도 고정막이 미생물막 외면에 형성되므로 미생물막 자체의 유실(콘크리트블록 표면에서 탈리되는 현상)에 대해서는 대응할 수 없었다. However, such a concrete block has a problem that most of the microorganisms are rapidly lost before the microorganisms propagate normally because the microbial membrane is exposed to the outside. In order to prevent this, the fixed block was formed by applying a solid solution to the outside of the microbial membrane. Since the fixed membrane is a porous form that does not interfere with the growth of microorganisms, it is impossible to actively prevent the loss of microorganisms. We could not cope with.

또한 미생물막에 고정막을 형성하여 콘크리트블록 상에 고정시켜 놓았다 하더라도 수중이 아닌 외부상에 장시간 노출될 경우 미생물막 내의 수분이 증발하여 수축현상이 일어나고 이 수축현상은 콘크리트불록이 현장에 설치되기 전에 미생물 막의 탈리현상을 초래하여 미생물막의 유실을 더욱 배가시켰다.In addition, even if a fixed membrane is formed on the concrete block and fixed on the concrete block, if it is exposed to the outside for a long time instead of underwater, the moisture in the microbial membrane evaporates and shrinkage occurs. This resulted in the desorption of the membrane, which further doubled the loss of the microbial membrane.

본 발명은 위와 같이 선 출원특허에서 나타나는 문제점 등을 한꺼번에 해결하기 위함에 그 기술적인 과제를 두고 발명한 것으로서, 특히 미생물의 유실률은 극히 낮으면서 수질과 주위 환경을 정화할 수 있는 콘크리트블록을 제안함에 그 목적이 있는 것이다.The present invention has been invented with the technical problem in order to solve the problems shown in the above patent application at the same time, in particular to propose a concrete block that can purify the water quality and the surrounding environment while the loss rate of microorganisms is extremely low. The purpose is.

이를 더욱 상세히 설명을 하면 다음과 같다.This will be described in more detail as follows.

본 발명을 설명하기 전에 먼저 콘크리트블록의 특성을 살펴보면, 첫째로는 콘크리트블록이 제조되면 시멘트의 특성상 콘크리트블록이 굳어지면서 열이 발생하며 강알칼리를 띄게 되고, 대체적으로 제조된 지 1일이 경과 되지 않은 콘크리트블록의 알칼리수치는 pH 12.5 ~ 13.5 사이로 측정되고, 둘째로는 콘크리트블록이 제조되고 짧은 시간 안에 시공이 되는 것이 아닐 수도 있으므로 장시간 대기중에 노출이 되었을 때 콘크리트 내부에 수분은 증발하게 되고 미생물의 최소 생존 가능 수분의 부족현상이 발생하게 된다. 따라서 콘크리트블록에 채용되는 미생물은 열과 강알칼리 상태 및 최소 생존 가능수분의 부족에도 생존할 수 있는 미생물이 필요하게 된다.Before describing the present invention, first, look at the characteristics of the concrete block, first, when the concrete block is manufactured due to the characteristics of the cement harden the concrete block, heat is generated and has a strong alkali, generally not more than one day after being manufactured Alkali levels of concrete blocks are measured between pH 12.5 and 13.5. Second, concrete blocks may not be manufactured and constructed in a short period of time. Therefore, moisture is evaporated inside the concrete when exposed to the air for a long time. Possible water shortage will occur. Therefore, the microorganisms employed in the concrete block need microorganisms that can survive the heat and strong alkali state and the lack of minimum viable moisture.

이에 본 발명은 이러한 특성을 가진 콘크리트블록이더라도 이를 친환경화 할 수 있음은 물론 그 친환경효과도 지속적으로 유지될 수 있는 콘크리트블록 제조방법을 제시하고자 하는 것으로서, 본 발명은 식물의 식생공간부(11)을 한 개 또는 그 이상으로 가지는 콘크리트블록(1)를 제조할 때 콘크리트블록(1) 자체에 유포자 미생물을 첨가하여 콘크리트블록이 친환경화 되도록 하고, 또는 콘크리트 상측 표면에 유포자 미생물이 첨가된 정화층(12)을 형성하여 친환경적 콘크리트블록이 되도록 한 것이다. Therefore, the present invention is to provide a concrete block manufacturing method that can be environmentally friendly as well as environmentally friendly even if the concrete block having such characteristics, the present invention provides a vegetation space portion 11 of the plant When manufacturing the concrete block (1) having one or more to add the diffuser microorganisms to the concrete block (1) itself to make the concrete block environmentally friendly, or purifying layer 12 to which the diffuser microorganisms are added to the upper surface of the concrete Formed to be an environmentally friendly concrete block.

이를 실시 예를 통하여 구체적으로 설명하면, If this is described in detail through the embodiment,

<실시 예><Example>

바실러스류(바실러스 서브틸러스MB43 등) 또는 효모류 등과 같이 포자화가 가능한 미생물을 2 × 1011 cfu/ml로 포자화 한 다음 이를 분말화 하고, 이 유포자 미생물 분말을 콘크리트블록 제조용 시멘트에 첨가하여 친환경 조성물을 만들되, 조성물의 조성비율은 시멘트를 500중량%으로 하였을 때 1중량%로 하며, 상기 조성물을 이용하여 20㎜×20㎜×5㎜(가로×세로×높이)의 친환경 콘크리트블록 전체를 제조할 수 있도록 하여서 된 것인데, 상기에서 미생물을 포자화 하는 것은 통상과 같이 하면 된다. Sporeable microorganisms such as Bacillus (Bacillus subtilis MB43) or yeast are sporulated at 2 × 10 11 cfu / ml, and then powdered, and the diffuser microorganism powder is added to cement for manufacturing concrete blocks to create an eco-friendly composition. However, the composition ratio of the composition is 1% by weight when the cement to 500% by weight, using the composition to produce the entire eco-friendly concrete block of 20 mm × 20 mm × 5 mm (width × height × height). The microorganisms can be sporadized as described above.

이렇게 제조되는 콘크리트블록에 유포자 미생물의 생존 여부를 측정하기 위 하여 친환경 콘크리트블록 본체를 시간의 경과에 따라 일부를 파쇄하여 그 안의 생존하는 미생물 마릿수를 측정하였고 그 결과는 아래의 표와 같았다.In order to measure the viability of the diffuser microorganisms in the concrete block thus manufactured, some of the eco-friendly concrete block body was crushed over time to measure the number of microorganisms that survive in it, and the results are shown in the table below.

(단위 :cfu/㎖)(Unit: cfu / ml)

1차(제조 1일 경과)1st (production day passes) 2차(제조 5일 경과)Second (5 days after manufacture) 3차(제조 15일 경과)3rd (after 15 days of manufacture) 실험샘플 1Experiment Sample 1 3 × 108 3 × 10 8 2 × 107 2 × 10 7 2.6 × 107 2.6 × 10 7 실험샘플 2Experiment Sample 2 7 × 107 7 × 10 7 1.2 × 106 1.2 × 10 6 2 × 107 2 × 10 7

한편 본 발명에서 시멘트에 첨가되는 유포자 미생물 분말과 이를 이용하여 제조한 친환경 콘크리트블록 그리고 대조구(일반 콘크리트블록)의 수질 정화기능을 비교하기 위하여 위 분말, 친환경 콘크리트블록, 대조구를 각각 인공폐수(글루코스 첨가)에 70시간 동안 침수시켜 COD의 경감에 대해 각기 관찰하였고, 그 관찰 결과는 아래의 그래프와 같았다.On the other hand, in order to compare the water purification function of the diffuser microbial powder added to the cement in the present invention and the eco-friendly concrete block and control (general concrete block) prepared using the same, each of the above powder, eco-friendly concrete block, control was added to artificial wastewater (glucose) ) Was immersed for 70 hours and observed for the reduction of COD, respectively. The results are shown in the graph below.

Figure 112006048699220-pat00001
Figure 112006048699220-pat00001

위 그래프에서 분말은 유포자 미생물 분말, concrete는 친환경 콘크리트블록, control은 대조구를 나타낸 것이다. In the above graph, the powder is the diffuser microbial powder, the concrete is the eco-friendly concrete block, and the control is the control.

이상과 같이 관찰한 결과 본 발명을 달성케 하는 유포자 미생물의 분말의 경우 1600ppm의 인공폐수의 수질을 빠르게 정화한다는 것을 알 수 있으며, 위 분말을 이용한 친환경 콘크리트블록 역시 900ppm의 인공폐수의 수질을 빠르게 정화한다는 것을 위 그래프를 통하여 알 수 있다.As a result of the above observation, it can be seen that in the case of the microorganism powder of the diffuser which achieves the present invention, it can quickly purify the water quality of the artificial wastewater of 1600 ppm, and the eco-friendly concrete block using the powder also quickly purifies the water quality of the 900 ppm artificial wastewater. You can see from the graph above.

<실시 예 2><Example 2>

통상과 같이 일반 시멘트로 콘크리트블록을 제조한 후 위 콘크리트블록을 양생하기 전에 <실시 예1>에서 얻어진 조성물을 위 콘크리트블록 상측 표면에 도포한 다음 양생하여 콘크리트블록 상면에 정화층(12)이 형성되도록 한 것인데, 여기서 조성물을 이루는 시멘트와 콘크리트블록(1) 제조용 시멘트의 물성을 동일하게 하면 상측에 정화층(12)이 일체형으로 되는 이중 구조의 친환경 콘크리트블록(1)을 얻을 수 있게 된다. After manufacturing the concrete block as usual cement and before curing the concrete block, the composition obtained in <Example 1> is applied to the upper surface of the upper concrete block and then cured to form a purification layer 12 on the upper surface of the concrete block. In this case, if the physical properties of the cement constituting the composition and the cement for the production of the concrete block (1) the same, it is possible to obtain an environmentally friendly concrete block (1) of a dual structure in which the purification layer 12 is integrated on the upper side.

이와 같이 친환경 콘크리트블록(1) 상측에만 정화층(12)을 형성하더라도 폐수의 수질 정화기능은 <실시 예 1>의 친환경 콘크리트블록의 정화기능을 그대로 유지할 수 있게 되며, 그 이유는 <실시 예 1> 및 <실시 예 2>에 사용되는 조성물의 유포자 미생물은 활동에 알맞는 환경조건이 조성되어야만 비로소 활동을 하기 때문 일 뿐만 아니라 또 유포자 미생물은 널리 알려진 바와 같이 악조건 환경에서 미생물이 그의 생존을 영위하기 위하여 포자를 형성하여 스스로를 보호할 수 있는 미생물이고, 또 이 미생물이 포자를 형성하면 고온 또는 강알칼리 상태나 생존에 필요한 최소한 수분부족과 같은 외부의 악조건에서도 내부의 미생물에는 큰 영향을 받지 않기 때문에 미생물의 생존에는 문제가 없기 때문이다.Thus, even if the purification layer 12 is formed only on the upper side of the eco-friendly concrete block 1, the water purification function of the wastewater can maintain the purification function of the eco-friendly concrete block of <Example 1>, and the reason is <Example 1 > And <Diffuser microorganisms of the composition used in Example 2> is not only because the activity must be formed when the environmental conditions suitable for the activity, but also the diffuser microorganisms, as is widely known, the microorganisms to survive their adverse conditions It is a microorganism that can protect itself by forming spores, and when these microorganisms form spores, microorganisms are not affected by the internal microorganisms even under external adverse conditions such as high temperature or strong alkali state or lack of moisture required for survival. Because there is no problem in the survival of the.

이상과 같이 콘크리트블록 자체 또는 상층 표면의 일부에 악조건 상황에서도 생존할 수 있는 유포자 미생물을 포자화 하고 이를 분말화 하여 첨가함으로써 콘크리트블록 내에서 미생물의 생존율이 높아짐은 물론 미생물막이 아닌 콘크리트블록 내에 미생물이 존재하므로 미생물의 급격한 유실을 막을 수 있고, 나아가 콘크리트블록이 현장에 설치되기 전에 수축으로 인하여 미생물의 탈리현상이 방지되어 미생물의 유실문제도 해결할 수 있으며, 또한 유포자 미생물이 특성상 조건부 활동을 하기 때문에 미생물의 급격한 증식에 의한 수생생물의 생육에 지장을 주지 않게 된다.As described above, by sporifying and adding powdered diffuser microorganisms that can survive under adverse conditions on the concrete block itself or a part of the upper surface layer, the survival rate of microorganisms in the concrete block is increased and microorganisms in the concrete block are not microbial membranes. The presence of microorganisms prevents the rapid loss of microorganisms, and also prevents the microorganisms from falling off due to shrinkage before the concrete block is installed on site, and also solves the loss of microorganisms. The rapid proliferation of aquatic organisms will not interfere with the growth.

따라서 본 발명은 상기한 바와 같이 콘크리트블록에서 미생물의 급격한 유실을 방지할 수 있게 되어 정화기능이 보다 지속적으로 유지될 수 있는 이점이 있고, 뿐만 아니라 미생물들이 먹이 조건에 따라 활동하게 되므로 수생식물의 생육에는 지장을 주지 않으면서 정화능력은 우수한 기능성 콘크리트블록을 제공할 수 있는 효과가 있으며, 한편 본 발명에서와 같은 친환경 콘크리트블록은 콘크리트를 사용하여 하천을 개보수할 경우 시멘트의 독성으로 발생할 수 있는 자연정화능력 저하의 억제를 기대할 수 있어 수질 정화 및 수생 동식물의 생태계를 보호하고 하천정화 효율의 향상을 도모할 수 있게 된다.Therefore, the present invention can prevent the rapid loss of microorganisms in the concrete block as described above has the advantage that the purification function can be maintained more continuously, as well as the growth of aquatic plants because the microorganisms are active according to the feeding conditions Purification capacity without affecting the effect has the effect that can provide excellent functional concrete block, while the eco-friendly concrete block as in the present invention is a natural purification that can occur due to the toxicity of cement when the river is repaired using concrete It can be expected to suppress the deterioration of capacity, thereby protecting the water quality, protecting the ecosystem of aquatic plants and animals, and improving the efficiency of river purification.

Claims (5)

포자화 가능한 바실러스류 또는 효모류에서 선택되는 미생물을 포자화한 다음 이를 분말화 하는 단계; Sporeing and then pulverizing the microorganism selected from the sporizable Bacillus or yeast; 상기 분말을 시멘트에 첨가하여 친환경 조성물을 제조하는 단계; 및Adding the powder to cement to prepare an environmentally friendly composition; And 상기 친환경 조성물을, 양생되기 전의 콘크리트블록 상측 표면에 도포하여, 콘크리트블록 상면에 콘크리트블록과 일체형으로 되는 정화층을 형성시키는 단계;Applying the eco-friendly composition to the upper surface of the concrete block before curing, to form a purification layer integral with the concrete block on the upper surface of the concrete block; 를 포함하여 제조되는 친환경 콘크리트블록의 제조방법.Method of manufacturing an environmentally friendly concrete block is prepared, including. 삭제delete 삭제delete 삭제delete 삭제delete
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KR100807866B1 (en) 2007-06-29 2008-02-29 양지콘크리트(주) Method for preparing concreate vegetation shore protection block and the prepared concreate vegetation shore protection block by the same
KR100971619B1 (en) 2010-04-19 2010-07-22 노춘배 Eco-friendly, low-toxic color block

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KR100807866B1 (en) 2007-06-29 2008-02-29 양지콘크리트(주) Method for preparing concreate vegetation shore protection block and the prepared concreate vegetation shore protection block by the same
KR100971619B1 (en) 2010-04-19 2010-07-22 노춘배 Eco-friendly, low-toxic color block

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