12/29/12 Nanotechnology in the cement industry - a patent analysis

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Posted: Dec 17th, 2012

Nanotechnology in the cement industry - a patent

analysis
(Nanowerk Spotlight) Cement is one of the most widely used materials in
construction industry. In 2011, the expected total worldwide production of cement
was 3,400 million tonnes. China is the largest producer accounting for 2 billion
tonnes in production with India in second position (210 million tonnes) followed by
the USA (68 million tonnes)1. Despite being widely used, cement-based materials
have poor mechanical properties and are highly permeable to water and other
aggressive chemicals, which reduces their durability. Moreover, the cement industry
is one of the significant sources of CO2 emissions, which accounts for 5-6% of
global man-made CO2 emission annually. However, the increasing demand for high
performance structural materials and components has led to the rapid development
of new classes of materials.

Nanotechnology can play a significant role in the construction industry and stands
at eighth position in terms of most significant areas of applications in
nanotechnology2. Nanoengineering of cement-based materials can result in
outstanding or smart properties. Introduction of nanotechnology in cement industry
has the potential to address some of the challenges such as CO2 emissions, poor
crack resistance, long curing time, low tensile strength, high water absorption, low
ductility and many other mechanical performances. A remarkable improvement in

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12/29/12 Nanotechnology in the cement industry - a patent analysis

the mechanical properties and durability of cementitious materials can be observed

with incorporation of nanomaterials such as nano-SiO2, ZnO2, Al2O3, TiO2, carbon
nanotubes, nano-clays, carbon nanofibers and other nanomaterials.

Patent Analysis

The current patent analysis has been conducted to get an overview of patent
landscape for nanotechnology applications in cement industry, with focus on
identifying nanomaterials for property enhancement, emerging trends, the major
assignees, and applications in this area. All keywords relevant to cementitious
materials along with possible synonyms, abbreviations were collected by studying
full text of selected patents, which exactly relate to the concept of hydraulic
cements.

Growth in Patents

The analysis of patenting activity pertaining to nanotechnology applications in

cement industry resulted in 368 patents. Figure 1 depicts the patenting trend in the
field of nanotechnology applications in cement industry. A sharp increase in year
wise publication of granted/published patents can be observed from 2007 onwards
due to the commercial success in using nano-scale materials as cementitious
ingredients. The tally of 154 granted patents from a total list of 368 patents clearly
shows a high output of commercialization and research in this field.

Fig. 1: Yearwise patent publication trend for nanotechnology applications in cement

industry.
Nano-enabled Cement Patent Classification

The patent analysis is restricted to nanotechnology applications in hydraulic cement

(cement that will set and harden after being combined with water). Nanomaterials
are widely used in portland cement industry (prepared by heating clay and
limestone in a kiln and pulverizing the mixture) when compared to non-portland
cements, which can be clearly observed from the number of patent filings in both

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12/29/12 Nanotechnology in the cement industry - a patent analysis

classes. Majority of patents are filed in the area of composite cement (74 patents)
and ordinary portland cement (OPC) (71 patents) respectively, followed by gypsum-
based cement with 27 patent filings.

Fig. 2: Classification of patents based on the type of nano-enabled cement.

Geographical Distribution
China is the world leader of patent filings, their 154 patent applications contributing
41% of overall filings, representing the major and active R&D player in the area of
nano-based cementitious materials. South Korea is the second leading country with
55 patents (15% of patent filings) on nano-enabled cement, closely followed by
United States with 51 patents. Russia, Germany, Japan, France and India are the
other leading patent filing countries with 37, 18, 11, 9 and 5 patents respectively,
while the remaining patents represent a minor contribution from rest of the world.

Assignee Analysis

Dagestan State University (Russia) is the leading assignee with 15-patents to its
credit, which are mainly focussed on the development of heat resistant and high

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12/29/12 Nanotechnology in the cement industry - a patent analysis

compression strength concrete materials. Halliburton Energy Services Inc (USA)

comes second with 14-patents that are directed towards well bore cementing for
the gas, oil or water wells using nano-cementitious materials. Other major
assignees are either universities or companies from China. Among all the assignees,
companies contribute 60% (221 patents) of the total patents filed on
nanotechnology applications in cement industry worldwide, indicating a high rate of
commercialization and R&D on a large scale, while universities/academic institutes
own 24% (89 patents) of patents while rest of the patents are filed by individual
inventors.

Technology Analysis

Introduction of nanoscale materials into cementitious materials has emerged as a

promising solution for enhancing the properties and performance of cement
materials. A list of various nanomaterials that are added to cement as fillers along
with their effect on properties are given in Table 1.

Table 1: Various nanomaterials that are incorporated in cement and their effect on
properties.

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12/29/12 Nanotechnology in the cement industry - a patent analysis

The patents are segregated with respect to the characteristic property imparted by
incorporated nanomaterials and is represented in the form of a bubble chart as
shown in Fig. 3 below. The percentage of patents given in the chart is based on the
size of the bubble i.e. bigger size indicates greater number of patent filings
corresponding to that specific attribute.
The analysis shows that nanomaterials are mainly incorporated to enhance various
mechanical properties of cementitious materials. Introduction of carbon nanotubes
(CNTs) in cement results in the improvement of various mechanical properties and
also imparts sensing characteristics to the cement. However, the poor dispersion of
CNTs is a major obstacle in achieving good mechanical performance in a composite.
Effective methods for dispersion of CNTs such as ultrasonication and use of a
surfactant are discussed in the prior art for the preparation of high strength
concrete.

Nano-silica is increasingly being used as a replacement for micro-silica in cement

industry. Because of its high reactivity and ultra fine nature, it is commonly used in
concrete mixes in large quantities, thereby reducing the cement content by 40%
resulting in less CO2 emissions and environmental contamination. Incorporation of
nano-silica in cement slurry gives enhanced mechanical properties, lower porosity
and permeability, which are crucial factors for increased durability.

Fig. 3: Bubble chart showing the percentage-wise distribution of patents based on

characteristic property imparted by the added nanomaterials.

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12/29/12 Nanotechnology in the cement industry - a patent analysis

Nano-titania is well known for its chemical stability and low toxicity. Moreover, it
acts as an oxidizing agent at near UV-radiation. Concrete containing nano-titania
showed effective self-cleaning property and it is used as a major component in
polymer cement mortar for photo-catalytically degrading nitrogen oxide (NOx) and
other pollutants.

Nano-alumina is widely used in cement mortar for increasing the elastic modulus of
the cementitious material. The alundum-mullite pouring product has high
compressive strength, good washing resistance, corrosion resistance and high
thermal shock resistance, and can withstand rapid temperature changes.

Addition of calcium carbonate to cement-based aqueous composite provides

improved hardness and abrasion resistance to concrete. The compressive strength
of composition containing nano-calcium carbonate increased by at least 25% and
showed 40% improvement in fluid loss, as compared to a cement composition
without the nano-calcium carbonate.
Calcium carbonate is also used as a nano modifier for reducing C3S hydration
induction period resulting in improved resistance to high temperature degradation
of concrete. Polymer-clay nanocomposites show an improvement in mechanical
properties and barrier properties of nano-enabled cement.

Nano-silica, carbon nanotubes, nano-calcium carbonate, nano-titania, nano-alumina

and polymer/clay nanocomposites are the most commonly used nanomaterials.
These nanomaterials are mainly used to enhance various mechanical properties of
the cementitious materials such as crack resistance, corrosion resistance, tensile
strength and compressive strength.

Conclusions
The first patent on nano-enabled cement was published in 1996 and since then the
patenting activity has continuously increased with an exponential rise after 2007.
China has emerged as the major contributor in this area with 41% of global patents
filings. It is also interesting to note that 60% of the patents are filed by corporates
showing a clear trend of high rate of commercialization.

The emergence of nanotechnology in cement industry has already shown a

remarkable impact on mechanical properties of cementitious materials with
patented commercial products such as Cor-Tuf®, HuberCrete®, Alpol, Nycon-G Nano
etc. are already available in market. These products have shown a significant
improvement in tensile strength, corrosion resistance, crack resistance, heat
resistance, high strength and many other mechanical properties of the cementitious
materials. Moreover, nanotechnology can help to overcome major environmental
challenges faced by the conventional cement materials, making them more

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12/29/12 Nanotechnology in the cement industry - a patent analysis

environmental friendly with reduced CO2 emissions and long durability.

Though the application of nanotechnology in cement industry is an emerging area,

the trends in patent data indicate that commercial adaptation of this technology has
already been started and in the near future nano-enabled cement is poised to
occupy the cement industry in a big way.

References

1. minerals.usgs.gov/minerals/pubs/mcs/2012/mcs2012.pdf

2. A.K. Mukhopadhyay, “Next-generation nano-based concrete construction

products: A review”, In K. Gopalakrishnan, B. Birgisson, P. Tylor, N. A-Okhine (Eds.)
“Nanotechnology in civil infrastructure”, p 207-223, Springer ( 2011), ISBN 978-3-
642-16656-3

By MD Shakeel Iqbal (shakeel@ckmnt.com) and Yashwant Mahajan

(mahajanyrm@ckmnt.com), CKMNT. A comprehensive Market Research Report on
“Nanotechnology in Cement Industry" is proposed to be released by CKMNT in the
near future. Interested readers may please contact Dr. Y. R. Mahajan, Technical
Adviser and Editor, Nanotech Insights or Mr. H. Purushotham, Team Leader
purushotham@ckmnt.com.

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